WO2022244717A1 - Composition for forming polyimide-containing part, joined body manufacturing method, joined body, device manufacturing method and device - Google Patents

Composition for forming polyimide-containing part, joined body manufacturing method, joined body, device manufacturing method and device Download PDF

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Publication number
WO2022244717A1
WO2022244717A1 PCT/JP2022/020338 JP2022020338W WO2022244717A1 WO 2022244717 A1 WO2022244717 A1 WO 2022244717A1 JP 2022020338 W JP2022020338 W JP 2022020338W WO 2022244717 A1 WO2022244717 A1 WO 2022244717A1
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Prior art keywords
group
polyimide
containing portion
substrate
forming
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PCT/JP2022/020338
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French (fr)
Japanese (ja)
Inventor
峻輔 北島
敦 中村
俊之 齋江
健太 山▲ざき▼
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富士フイルム株式会社
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Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to JP2023522647A priority Critical patent/JPWO2022244717A1/ja
Priority to KR1020237039473A priority patent/KR20230171470A/en
Priority to CN202280035809.0A priority patent/CN117378044A/en
Publication of WO2022244717A1 publication Critical patent/WO2022244717A1/en

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    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Definitions

  • the present invention relates to a composition for forming a polyimide-containing part, a method for producing a joined body, a method for producing a joined body, a device, and a device.
  • Electronic devices such as mobile phones and tablet terminals are getting smaller and smaller, while their functions are diversifying. To meet these needs, electronic circuits incorporated in electronic devices are required to be further miniaturized, highly integrated, and mounted at high density.
  • Packaging technologies such as SIP (System in Package), MCM (Multi Chip Module), and POP (Package on Package) are attracting attention as technologies that achieve miniaturization while maintaining high performance and reliability with multiple functions. . Since these techniques can reduce the number of parts and simplify the semiconductor manufacturing process, they are also expected to reduce the cost of electronic devices.
  • FIG. 1 is a cross-sectional view showing the structure of a typical COC.
  • the COC in this example comprises a daughter chip (first substrate) 1 and a mother chip (second substrate) 2 .
  • An electronic circuit (not shown) and flip chip electrodes (not shown) are formed on the mother chip 2 , and the daughter chip 1 is supported and connected via solder electrodes (bumps) 93 .
  • the periphery of the solder electrode 93 is filled with an underfill 94 to ensure insulation.
  • the mother chip 2 is mounted on the base substrate 98 while maintaining insulation by being adhered to the base substrate 98 by the bonding film 91 .
  • the electrical connection is made through wire bonding pad 97b, wire bonding 96 and substrate electrode 97a.
  • Such a COC structure is sealed with a sealing resin 95 to form a semiconductor device 90 .
  • the semiconductor device 90 is provided with solder balls 99, through which it is incorporated into electronic equipment. Further, by further applying this flip-chip mounting technique, techniques and materials for three-dimensional mounting using TSV (Through Silicon Via) are being studied (Non-Patent Document 1).
  • the underfill 94 is filled in the gap. Therefore, a fluid resin is used as the material forming the underfill, and the resin is cured and molded after being filled between the solder bumps.
  • the daughter chip 1 and the mother chip 2 are bonded together by the adhesive strength of the resin, and from the viewpoint of improving the adhesiveness, it is desired to improve the maximum peeling resistance between these two substrates.
  • the present invention provides a composition for forming a polyimide-containing portion that can provide a bonded body having a large maximum peeling force between two substrates when bonding two substrates, and bonding using the composition for forming a polyimide-containing portion.
  • An object of the present invention is to provide a method for manufacturing a body, a bonded body obtained by the manufacturing method, a method for manufacturing a device including the method for manufacturing the bonded body, and a device including the bonded body.
  • the polyimide-containing portion is a member formed from the polyimide-containing portion-forming composition, A composition for forming a polyimide-containing portion, wherein the glass transition temperature of the polyimide-containing portion is lower than the bonding temperature in the bonding step.
  • composition for forming a polyimide-containing part according to ⁇ 1> containing a polyimide precursor and a solvent.
  • composition for forming a polyimide-containing part according to ⁇ 1> or ⁇ 2> further comprising a migration inhibitor.
  • ⁇ 4> The composition for forming a polyimide-containing portion according to any one of ⁇ 1> to ⁇ 3>, wherein the polyimide-containing portion has a glass transition temperature of 350° C. or lower.
  • ⁇ 5> The composition for forming a polyimide-containing part according to any one of ⁇ 1> to ⁇ 4>, wherein the glass transition temperature of the polyimide-containing part is lower than the bonding temperature in the bonding step by 30° C.
  • ⁇ 6> The composition for forming a polyimide-containing portion according to any one of ⁇ 1> to ⁇ 5>, wherein the bonding temperature in the bonding step is 380° C. or less.
  • ⁇ 7> The composition for forming a polyimide-containing portion according to any one of ⁇ 1> to ⁇ 6>, wherein the substrate A is in the form of a wafer.
  • ⁇ 8> The composition for forming a polyimide-containing part according to any one of ⁇ 1> to ⁇ 7>, wherein the form of the substrate B is a chip.
  • ⁇ 12> The composition for forming a polyimide-containing portion according to ⁇ 11>, wherein the planarization step is performed by physical polishing.
  • ⁇ 13> The composition for forming a polyimide-containing portion according to ⁇ 11>, wherein the planarization step is performed by chemical polishing.
  • the bonding step the electrodes included in the surface of the substrate A having the polyimide-containing portion and the electrodes on the surface of the substrate B including the wiring terminals are bonded so as to be in direct contact with each other, ⁇ 1> to The composition for forming a polyimide-containing portion according to any one of ⁇ 13>.
  • ⁇ 15> ⁇ 1> to ⁇ 14> further including a second polyimide-containing portion forming step of forming a second polyimide-containing portion on the surface of the substrate B provided with the wiring terminals before the bonding step.
  • the composition for forming a polyimide-containing portion according to any one of . ⁇ 16> The composition for forming a polyimide-containing portion according to any one of ⁇ 1> to ⁇ 15>, further comprising a photosensitive compound.
  • the polyimide-containing portion forming step includes applying a composition for forming a polyimide-containing portion onto the surface of the substrate A provided with the wiring terminal and heating the composition.
  • composition for forming a polyimide-containing portion according to 1.
  • ⁇ 20> A joined body obtained by the production method according to ⁇ 19>.
  • ⁇ 21> A method of manufacturing a device, including the method of manufacturing a joined body according to ⁇ 19>.
  • ⁇ 22> A device comprising the conjugate according to ⁇ 20>.
  • a composition for forming a polyimide-containing part that can obtain a bonded body having a large maximum peeling force between two substrates when bonding two substrates, and the composition for forming a polyimide-containing part are used.
  • a method for manufacturing a bonded body, a bonded body obtained by the manufacturing method a method for manufacturing a device including the method for manufacturing the bonded body, and a device including the bonded body.
  • FIG. 1 is a cross-sectional view schematically showing the structure of a COC semiconductor device
  • FIG. BRIEF DESCRIPTION OF THE DRAWINGS It is process explanatory drawing which showed the process when joining a board
  • FIG. 2 is a process explanatory diagram showing a schematic cross-sectional view of a process of bonding substrates in a method for manufacturing a bonded body using the composition for forming a polyimide-containing portion of the present invention according to one embodiment of the present invention (FIG. 2 continuation).
  • FIG. 2 is a process explanatory diagram showing a schematic cross-sectional view of a process of bonding substrates in a method for manufacturing a bonded body using the composition for forming a polyimide-containing portion of the present invention according to one embodiment of the present invention (FIG. 2
  • FIG. 2 is a process explanatory diagram showing a schematic cross-sectional view of a process of bonding substrates in a method for manufacturing a bonded body using the composition for forming a polyimide-containing portion of the present invention according to one embodiment of the present invention (FIG. 3 continued).
  • 1 is a cross-sectional view schematically showing an example of a three-dimensionally mounted semiconductor device using TSVs;
  • FIG. It is a schematic cross-sectional view showing details of a substrate used in Examples.
  • an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the term "exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
  • the light used for exposure generally includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays and electron beams.
  • EUV light extreme ultraviolet rays
  • a numerical range represented by "to” means a range including the numerical values before and after "to” as lower and upper limits.
  • (meth)acrylate represents both or either of “acrylate” and “methacrylate”
  • (meth)acrylic represents both “acrylic” and “methacrylic", or Either is represented
  • (meth)acryloyl represents both or either of “acryloyl” and “methacryloyl”.
  • process includes not only an independent process, but also when the intended action of the process is achieved even if it cannot be clearly distinguished from other processes.
  • the solid content is the mass percentage of other components excluding the solvent relative to the total mass of the composition. Further, the solid content concentration refers to the concentration at 25° C. unless otherwise specified. The temperature in the present invention is 25° C.
  • weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as polystyrene equivalent values according to gel permeation chromatography (GPC measurement), unless otherwise specified.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), guard column HZ-L, TSKgel Super HZM-M, TSKgel It can be obtained by using either Super HZ4000, TSKgel Super HZ3000, or TSKgel Super HZ2000 (manufactured by Tosoh Corporation).
  • THF tetrahydrofuran
  • a UV ray (ultraviolet) wavelength detector of 254 nm is used for detection.
  • composition for forming polyimide-containing part of the present invention includes: a step of preparing a substrate A having a surface provided with wiring terminals; a step of forming a polyimide-containing portion on the surface of the substrate A provided with the wiring terminals; A joined body comprising: a step of preparing a substrate B having a surface provided with wiring terminals; A composition for forming a polyimide-containing part used in the manufacturing method, wherein the polyimide-containing part is a member formed from the composition for forming a polyimide-containing part, and the glass transition temperature of the polyimide-containing part is the above bonding Lower than the bonding temperature in the process.
  • the composition for forming a polyimide-containing part of the present invention (hereinafter also simply referred to as "resin composition"), when bonding two substrates such as a wafer and a wafer or a wafer and a chip through the polyimide-containing part , it is possible to produce a bonded body with a high maximum peel force between the two substrates.
  • the glass transition temperature (Tg) of the polyimide-containing portion is lower than the bonding temperature, it is possible to ensure sufficient fluidity of the polyimide-containing portion during bonding. It is possible to increase the maximum peel resistance.
  • the bonding temperature is the temperature of the polyimide-containing portion during bonding, and can be, for example, the set temperature of the device used for bonding.
  • the bonding time can be shortened, and the tact time of the bonding process can also be reduced.
  • the alignment accuracy at the time of joining is low, and the joining gap between the metal parts such as electrodes on each substrate occurs, and the wiring part is exposed. may occur.
  • the polyimide-containing portion between the wiring portions is required to have withstand voltage performance.
  • the composition for forming the polyimide-containing portion contains a migration inhibitor, it is possible to suppress the migration of the metal from the metal portion to the polyimide-containing portion, thereby improving the withstand voltage performance. It is considered possible. Details of the resin composition of the present invention are described below.
  • a method for producing a bonded body using the composition for forming a polyimide-containing portion of the present invention includes a step of preparing a substrate A having a surface provided with wiring terminals.
  • the substrate A may be manufactured by a known method (for example, plating on a substrate such as a silicon substrate), or may be obtained by means such as purchase.
  • the substrate A has a surface with wiring terminals.
  • the wiring terminals on the substrate A are also referred to as wiring terminals A hereinafter.
  • the form of the substrate A may be either a wafer or a chip, but being a wafer is also one of the preferred aspects of the present invention.
  • a wafer means a substrate containing a semiconductor, and is a concept including a panel or the like formed of a plurality of elements such as semiconductors.
  • a chip means an individual piece containing a semiconductor formed by dicing or the like, and may be a single-sided chip or a double-sided chip.
  • the shape of the substrate A is not particularly limited, but examples thereof include a polygonal plate shape, a disc shape, and a polyhedron shape.
  • the thickness of the substrate A is preferably 0.1-5 mm, more preferably 0.2-1 mm.
  • the wiring terminal A on the substrate A is preferably a pillar electrode.
  • the wiring terminal A preferably contains a metal such as tin (Sn), gold (Au), silver (Ag), copper (Cu), aluminum (Al), tungsten (W), palladium (Pd), Platinum (Pt), Cobalt (Co), Nickel (Ni), Zinc (Zn), Ruthenium (Ru), Iridium (Ir), Rhodium (Rh), Lead (Pb), Bismuth (Bi) and Indium (In) More preferably, it contains at least one metal selected from the group consisting of, more preferably at least one metal selected from the group consisting of copper, tin and nickel.
  • a metal such as tin (Sn), gold (Au), silver (Ag), copper (Cu), aluminum (Al), tungsten (W), palladium (Pd), Platinum (Pt), Cobalt (Co), Nickel (Ni), Zinc (Zn), Ruthenium (Ru), Iridium (Ir), Rhodium (Rh), Lead (Pb), Bismuth (Bi) and Indium
  • the alloy may contain elements other than those exemplified above.
  • a copper alloy may contain silicon atoms to form a Corson alloy.
  • oxygen that is inevitably dissolved, organic residues of the raw material compound mixed during precipitation, and the like may be present.
  • the wiring terminal A may be a wiring terminal comprising a plurality of different members.
  • a substrate has a portion that is used as an electrode (hereinafter also referred to as an “electrode”) made of a metal such as copper, silver, gold, or an alloy containing one or more of these, and on the electrode such as copper , nickel, tin, lead, or an alloy containing one or more of these metals (hereinafter also referred to as a “conducting path”) that is used as solder is formed, and the electrode and the conducting path are formed.
  • One wiring terminal A may be formed by existing in series. Among these, the wiring terminal A preferably includes at least a member containing copper and a member containing tin.
  • An example of the substrate A having a surface provided with such wiring terminals A is the substrate b) used in the examples of the present application. In substrate b), conductive paths made of tin are formed on electrodes made of copper.
  • the electrodes are not particularly limited, but include tin, gold, silver, copper, aluminum, tungsten, palladium, platinum, cobalt, nickel, zinc, ruthenium, iridium, rhodium, and alloys thereof.
  • the electrode is preferably a metal containing copper, a metal containing aluminum, a metal containing tungsten, a metal containing nickel, or a metal containing gold, more preferably a metal containing copper, and still more preferably copper.
  • the metal used for the electrodes it is preferable to use a metal that does not melt even in the joining process.
  • the melting point of the metal used for the electrodes is preferably 500° C. or higher, more preferably 700° C.
  • the material used for the conductive path is not particularly limited, but includes tin, lead, silver, copper, zinc, bismuth, or indium, or alloys thereof. Among them, solder of tin or a tin alloy (a metal containing tin) is preferable in the present invention. Recently, the technology of lead-free solder, which does not use lead, is also progressing, and it is also preferable to select such a material.
  • the metal used for the conducting path a metal that melts in the joining process is preferable.
  • the melting point of the metal used for the conducting paths is preferably 400° C.
  • the lower limit of the melting point is not particularly limited as long as it is solid at room temperature. Moreover, it is preferable that a plurality of wiring terminals A are formed on the substrate A. As shown in FIG.
  • the material used for the substrate A is not particularly limited, and includes semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, deposited films, magnetic films, reflective films, Metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, plasma display panel (PDP) electrode plates, etc. are not particularly limited.
  • the substrate may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface.
  • HMDS hexamethyldisilazane
  • a semiconductor fabrication substrate is particularly preferred, and a silicon substrate (silicon wafer) is more preferred.
  • Substrate A may have an electronic circuit area containing electronic circuits. Moreover, the electronic circuit may have an element such as a semiconductor. Moreover, it is preferable that the electronic circuit is electrically connected to the wiring terminal A.
  • the diameter can be 100 mm or more. Moreover, as a large substrate, for example, it is preferably 200 mm or more, and more preferably 250 mm or more. Although there is no particular upper limit, it is preferably 2,000 mm or less.
  • the diameter is preferably 7 mm or more, more preferably 10 mm or more, and even more preferably 20 mm or more.
  • the upper limit is, for example, preferably 50 mm or less, more preferably 40 mm or less, and even more preferably 30 mm or less.
  • a method for producing a bonded body using the composition for forming a polyimide-containing portion of the present invention includes a polyimide-containing portion forming step of forming a polyimide-containing portion on the surface of the substrate A provided with the wiring terminal (wiring terminal A). .
  • the polyimide-containing portion is preferably formed so as to be in contact with the wiring terminal A, and more preferably formed so as to fill the concave portion between the wiring terminals A.
  • the polyimide-containing portion may be formed on at least a part of the wiring terminals A, but for example, an embodiment in which the polyimide-containing portion is formed on all of the wiring terminals A is also one of the preferred embodiments of the present invention.
  • the polyimide-containing portion forming step preferably includes applying a composition for forming a polyimide-containing portion onto the surface of the substrate A provided with the wiring terminals and heating. Application and heating details are described below.
  • the polyimide-containing portion is a member formed from the polyimide-containing portion-forming composition, and is preferably a member obtained by at least heating the polyimide-containing portion-forming composition.
  • the polyimide-containing portion is a member containing polyimide, and may further contain components other than polyimide.
  • components other than polyimide include components other than polyimide and its precursor contained in the resin composition described later, and components modified by heating (decomposition, polymerization, structural change, etc.).
  • the glass transition temperature of the polyimide-containing portion may be lower than the bonding temperature in the bonding step, but is preferably 350° C. or lower, more preferably 320° C. or lower, and even more preferably 300° C. or lower.
  • the lower limit of the glass transition temperature is not particularly limited, it is preferably 200° C. or higher from the viewpoint of heat resistance.
  • the glass transition temperature of the polyimide-containing portion is preferably 30 ° C. or more lower than the bonding temperature in the bonding step, more preferably 50 ° C. or more, and further preferably 70 ° C. or more. preferable.
  • the glass transition temperature of the polyimide-containing portion is preferably 30° C. or more higher than the bonding temperature in the bonding step.
  • the thickness of the polyimide-containing portion is not particularly limited, but from the viewpoint of exhibiting the effect of its physical properties, the thickness immediately before the bonding step (when the planarization step described later is performed, the state immediately before the planarization step is performed) thickness) is preferably 100 nm or more, more preferably 300 nm or more, still more preferably 500 nm or more, still more preferably 1 ⁇ m or more, and even more preferably 2 ⁇ m or more. Although there is no particular upper limit, it is preferably 1 mm or less, more preferably 500 ⁇ m or less, and even more preferably 200 ⁇ m or less.
  • the thickness of the film can be measured using a known film thickness measuring device.
  • the thermal diffusivity of the polyimide-containing portion in the joined body described later is preferably 2.0 ⁇ 10 ⁇ 7 m 2 s ⁇ 1 or more, and more preferably 3.0 ⁇ 10 ⁇ 7 m 2 s ⁇ 1 or more. More preferably, it is 5.0 ⁇ 10 ⁇ 7 m 2 s ⁇ 1 or more.
  • the thermal diffusivity of the polyimide-containing part is, for example, when the polyimide-containing part contains a filler, the material type of the filler, the particle size of the filler (a combination of the particle sizes when two or more types of filler are included), and the thermal diffusion of the filler. It can be adjusted by designing factors such as the rate, content of filler, structure of polyimide, thermal diffusivity of polyimide, content of polyimide, and the like.
  • the polyimide-containing portion is preferably an insulating member.
  • the insulation (electrical resistance) of the polyimide-containing portion is not particularly limited, but the volume resistivity is preferably 1 ⁇ 10 15 ⁇ cm or more, more preferably 1 ⁇ 10 16 ⁇ cm or more. Although there is no particular upper limit, it is practical to be 1 ⁇ 10 19 ⁇ cm or less.
  • the dielectric breakdown voltage is preferably 1 kV/mm or more, more preferably 10 kV/mm or more. Although the upper limit is not particularly limited, it is practically 1000 kV/mm or less. In this specification, measurements of volume resistivity and dielectric breakdown voltage shall comply with JIS C2151:2006 and JIS C2318:2007.
  • the polyimide-containing portion forming step is a step including applying the polyimide-containing portion forming composition (resin composition) of the present invention onto the surface of the substrate A having the wiring terminal A (application step). is preferred.
  • Means for applying the resin composition onto the substrate A include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, A slit coat method, an inkjet method, and the like are exemplified. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet method is more preferable, and spin coating from the viewpoint of uniformity of film thickness and productivity. and slit coating methods are preferred. A film having a desired thickness can be obtained by adjusting the solid content concentration and application conditions of the resin composition according to the method. In addition, the coating method can be appropriately selected depending on the shape of the substrate. Spin coating, spray coating, inkjet method, etc.
  • slit coating and spray coating are preferable for rectangular substrates.
  • method, inkjet method, and the like are preferred.
  • the spin coating method for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.
  • a method of transferring a coating film, which is formed on a temporary support in advance by the application method described above, onto a base material can be applied.
  • the transfer method the manufacturing methods described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0096-0108 of JP-A-2006-047592 can also be preferably used in the present invention.
  • a step of removing excess film at the edge of the substrate may be performed.
  • processes include edge bead rinsing (EBR), back rinsing, and the like.
  • EBR edge bead rinsing
  • a pre-wetting step may also be employed in which the substrate is coated with various solvents before applying the resin composition to the substrate to improve the wettability of the substrate, and then the resin composition is applied.
  • a step (drying step) of drying the member (hereinafter also simply referred to as "film") made of the resin composition is performed.
  • the drying temperature in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, even more preferably 90 to 110°C.
  • the drying time is exemplified from 30 seconds to 20 minutes, preferably from 1 minute to 10 minutes, more preferably from 2 minutes to 7 minutes.
  • the thickness immediately after application (the thickness after drying when a drying step is performed) is not particularly limited, and may be adjusted as appropriate so that the thickness of the resulting polyimide-containing portion will be the thickness described later.
  • the polyimide-containing portion forming step may include a step of patterning the member made of the resin composition.
  • a resin composition containing a photosensitive compound such as a photopolymerization initiator, which will be described later, is used, this patterning can be performed by exposure and development.
  • the surface After forming the polyimide-containing portion, the surface may be planarized. Details of the planarization will be described later. Note that when patterning is performed, the thickness of the portion removed by development or the like is not used for calculating the film thickness difference (T1-T2) described later.
  • the film may be subjected to an exposure step that selectively exposes the film. That is, it is also referred to as a polyimide-containing portion (hereinafter, “cured product”) related to the composition for forming a polyimide-containing portion of the present invention. ) may include an exposure step of selectively exposing the film formed by the applying step. Selectively exposing means exposing a portion of the film. Also, by selectively exposing, the film is formed with exposed regions (exposed portions) and non-exposed regions (non-exposed portions). The amount of exposure is not particularly defined as long as the resin composition of the present invention can be cured . is more preferred.
  • the exposure wavelength can be appropriately determined in the range of 190-1,000 nm, preferably 240-550 nm.
  • the exposure wavelength is (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) ), F2 excimer laser ( wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, etc.
  • semiconductor laser wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355
  • the resin composition of the present invention exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is particularly preferred. Thereby, particularly high exposure sensitivity can be obtained.
  • the method of exposure is not particularly limited as long as at least a part of the film made of the resin composition of the present invention is exposed. Exposure using a photomask, exposure by a laser direct imaging method, etc. mentioned.
  • the film may be subjected to a step of heating after exposure (post-exposure heating step). That is, the method for producing a cured product of the composition for forming a polyimide-containing portion of the present invention may include a post-exposure heating step of heating the film exposed in the exposure step.
  • the post-exposure heating step can be performed after the exposure step and before the development step.
  • the heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C.
  • the heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
  • the heating rate in the post-exposure heating step is preferably 1 to 12° C./min, more preferably 2 to 10° C./min, still more preferably 3 to 10° C./min, from the temperature at the start of heating to the maximum heating temperature. Also, the rate of temperature increase may be appropriately changed during heating.
  • the heating means in the post-exposure heating step is not particularly limited, and known hot plates, ovens, infrared heaters and the like can be used. Moreover, it is also preferable to carry out the heating in an atmosphere of low oxygen concentration by, for example, flowing an inert gas such as nitrogen, helium or argon.
  • the film after exposure may be subjected to a development step in which the film is developed using a developer to form a pattern.
  • the method for producing a cured product of the composition for forming a polyimide-containing portion of the present invention may include a development step of developing a film exposed in the exposure step with a developer to form a pattern. By performing development, one of the exposed and non-exposed portions of the film is removed to form a pattern.
  • development in which the unexposed portion of the film is removed by the development process is called negative development
  • development in which the exposed portion of the film is removed by the development process is called positive development.
  • Examples of the developer used in the development process include an aqueous alkaline solution and a developer containing an organic solvent.
  • basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts.
  • TMAH tetramethylammonium hydroxide
  • potassium hydroxide sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine , dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide , butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)am
  • the content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass, based on the total mass of the developer. is more preferred.
  • the organic solvent may be an ester such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, Methyl lactate, ethyl lactate, ⁇ -butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, alkyl alkyloxyacetate (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g.
  • 3-alkyloxypropionate alkyl esters e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., 3-methoxy methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.
  • 2-alkyloxypropionate alkyl esters e.g.
  • methyl 2-alkyloxypropionate, 2- ethyl alkyloxypropionate, propyl 2-alkyloxypropionate, etc. e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionic acid ethyl
  • methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate e.g.
  • ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene Glycol monoethyl ether acetate
  • the organic solvent can be used singly or in combination of two or more.
  • a developer containing at least one selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, and cyclopentanone and ⁇ -butyrolactone. and dimethylsulfoxide is more preferred, and a developer containing cyclopentanone is most preferred.
  • the content of the organic solvent relative to the total weight of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, and 80% by mass or more. is more preferable, and 90% by mass or more is particularly preferable. Moreover, the content may be 100% by mass.
  • the developer may further contain other components.
  • Other components include, for example, known surfactants and known antifoaming agents.
  • the method of supplying the developer is not particularly limited as long as the desired pattern can be formed, and a method of immersing the substrate on which the film is formed in the developer, and supplying the developer to the film formed on the substrate using a nozzle.
  • the type of nozzle is not particularly limited, and straight nozzles, shower nozzles, spray nozzles and the like can be mentioned. From the viewpoint of permeability of the developer, removability of the non-image area, and efficiency in production, a method of supplying the developer with a straight nozzle or a method of continuously supplying the developer with a spray nozzle is preferable.
  • the method of supplying with a spray nozzle is more preferable.
  • the substrate is spun to remove the developer from the substrate.
  • a step of removing from above may be employed, and this step may be repeated multiple times.
  • the method of supplying the developer in the development process includes a process in which the developer is continuously supplied to the base material, a process in which the developer is kept substantially stationary on the base material, and a process in which the developer exceeds the developer on the base material.
  • a process of vibrating with sound waves or the like and a process of combining them can be employed.
  • the development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
  • the temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.
  • the pattern may be washed (rinsed) with a rinse.
  • a method of supplying the rinse liquid before the developer in contact with the pattern is completely dried may be adopted.
  • Rinse liquid When the developer is an alkaline aqueous solution, water, for example, can be used as the rinse.
  • the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer) is used as the rinse liquid. be able to.
  • the organic solvent includes esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyl butyrate. , methyl lactate, ethyl lactate, ⁇ -butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, alkyl alkyloxyacetates (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g.
  • 3-alkyloxypropionate alkyl esters e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., 3- methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.
  • 2-alkyloxypropionate alkyl esters e.g.
  • methyl 2-alkyloxypropionate 2 -ethyl alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionate ethyl acid)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g.
  • ethers such as diethylene glycol dimethyl ether, tetrahydrofuran , ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), Propylene glycol monoethyl ether a
  • the organic solvent can be used singly or in combination of two or more.
  • the organic solvent can be used singly or in combination of two or more.
  • cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA and PGME are particularly preferred, cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, PGMEA and PGME are more preferred, and cyclohexanone and PGMEA are more preferred. More preferred.
  • the rinse liquid contains an organic solvent
  • the rinse liquid is preferably 50% by mass or more of the organic solvent, more preferably 70% by mass or more of the organic solvent, and 90% by mass or more of the organic solvent. is more preferred. Further, 100% by mass of the rinse liquid may be an organic solvent.
  • the rinse solution may further contain other components.
  • Other components include, for example, known surfactants and known antifoaming agents.
  • the method of supplying the rinse solution is not particularly limited as long as the desired pattern can be formed, and includes a method of immersing the base material in the rinse solution, a method of supplying the rinse solution to the base material by piling up the base material, and a method of supplying the rinse solution to the base material by showering. and a method of continuously supplying the rinsing liquid onto the substrate by means of a straight nozzle or the like.
  • the permeability of the rinse liquid From the viewpoint of the permeability of the rinse liquid, the removability of the non-image areas, and the efficiency in manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a straight nozzle, a spray nozzle, etc., and a continuous supply method using a spray nozzle is preferable. From the viewpoint of the permeability of the rinsing liquid to the image area, the method of supplying the rinsing liquid with a spray nozzle is more preferable.
  • the type of nozzle is not particularly limited, and straight nozzles, shower nozzles, spray nozzles and the like can be mentioned.
  • the rinsing step is preferably a step of supplying the rinse liquid to the film after exposure through a straight nozzle or a step of continuously supplying the same, and more preferably a step of supplying the rinse liquid through a spray nozzle.
  • the method of supplying the rinse liquid in the rinse step includes a process in which the rinse liquid is continuously supplied to the base material, a process in which the rinse liquid is kept substantially stationary on the base material, and a process in which the rinse liquid is kept on the base material in a substantially stationary state. A process of vibrating with sound waves or the like and a process of combining them can be adopted.
  • the rinse time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
  • the temperature of the rinsing liquid during rinsing is not particularly specified, but is preferably 10 to 45°C, more preferably 18 to 30°C.
  • the pattern obtained by the developing step (the pattern after rinsing when the rinsing step is performed) is preferably subjected to a heating step of heating the pattern obtained by the above developing (the member made of the resin composition). That is, the method for producing a cured product of the composition for forming a polyimide-containing portion of the present invention may include a heating step of heating the pattern obtained by the developing step. Further, the method for producing a cured product according to the composition for forming a polyimide-containing portion of the present invention includes a pattern obtained by another method without performing the developing step, or a heating step of heating the film obtained by the applying step It is also preferable to include a heating step of heating the film obtained by the applying step without performing the developing step.
  • a resin such as a polyimide precursor is cyclized into a resin such as polyimide.
  • cross-linking of unreacted cross-linkable groups in the specific resin or a cross-linking agent other than the specific resin also progresses.
  • the heating temperature (maximum heating temperature) in the heating step is preferably 375° C. or lower, more preferably 350° C. or lower, even more preferably 300° C. or lower, and may be 250° C. or lower.
  • the lower limit of the heating temperature is preferably 160° C. or higher, more preferably 170° C. or higher, and even more preferably 180° C. or higher.
  • heating conditions such as heating temperature and heating time in the heating step
  • the heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor in the pattern by the action of the base generated from the base generator by heating.
  • Heating in the heating step is preferably carried out at a temperature rising rate of 1 to 12° C./min from the temperature at the start of heating to the maximum heating temperature.
  • the rate of temperature increase is more preferably 2 to 10°C/min, still more preferably 3 to 10°C/min.
  • By setting the temperature rise rate to 1°C/min or more it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity.
  • the residual stress of the object can be relaxed.
  • the temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C.
  • the temperature at the start of heating refers to the temperature at which the process of heating up to the maximum heating temperature is started.
  • the temperature of the film (layer) after drying is, for example, the boiling point of the solvent contained in the resin composition of the present invention.
  • the heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, even more preferably 15 to 240 minutes.
  • the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, and further preferably 100° C. or higher, from the viewpoint of adhesion between layers. 120° C. or higher is particularly preferred.
  • the upper limit of the heating temperature is preferably 350° C. or lower, more preferably 250° C. or lower, and even more preferably 240° C. or lower.
  • Heating may be done in stages. As an example, the temperature is raised from 25° C. to 120° C. at 3° C./min, held at 120° C. for 60 minutes, heated from 120° C. to 180° C. at 2° C./min, and held at 180° C. for 120 minutes. , may be performed. It is also preferable to carry out the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such a pretreatment process can improve the properties of the film.
  • the pretreatment step is preferably performed for a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
  • the pretreatment may be performed in two or more steps.
  • the first pretreatment step may be performed in the range of 100 to 150°C, and then the second pretreatment step may be performed in the range of 150 to 200°C. good. Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5°C/min.
  • the heating step is preferably carried out in an atmosphere of low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium or argon, or under reduced pressure, in order to prevent decomposition of the specific resin.
  • the oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.
  • the heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, an infrared oven and the like.
  • the pattern obtained by the development step (the pattern after rinsing when the rinsing step is performed) is subjected to a post-development exposure step of exposing the pattern after the development step instead of or in addition to the heating step.
  • the method for producing a cured product of the composition for forming a polyimide-containing portion of the present invention may include a post-development exposure step of exposing the pattern obtained in the development step.
  • the method for producing a cured product of the composition for forming a polyimide-containing portion of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.
  • the post-development exposure step for example, a reaction in which cyclization of a polyimide precursor or the like proceeds by exposure of a photobase generator, or a reaction in which elimination of an acid-decomposable group proceeds by exposure of a photoacid generator is promoted. can do.
  • the post-development exposure step at least part of the pattern obtained in the development step may be exposed, but it is preferable to expose the entire pattern.
  • the exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ/cm 2 , more preferably 100 to 15,000 mJ/cm 2 in terms of exposure energy at the wavelength to which the photosensitive compound is sensitive. preferable.
  • the post-development exposure step can be performed using, for example, the light source used in the exposure step described above, and broadband light is preferably used.
  • a method for manufacturing a bonded body using the composition for forming a polyimide-containing portion of the present invention includes a step of preparing a substrate B having a surface provided with wiring terminals.
  • the form of the substrate B may be either a wafer or a chip. These may be selected according to the desired design of the joined body.
  • the substrate B has wiring terminals.
  • the wiring terminals on the substrate B are also referred to as wiring terminals B hereinafter.
  • the thickness of the substrate B is preferably 0.1-5 mm, more preferably 0.2-1 mm. At least a portion of the wiring terminal B is electrically connected to the wiring terminal A on the substrate A in the bonded body obtained by the bonding step described later.
  • the material used for the substrate B is not particularly limited, and the same materials as those for the substrate A described above are preferably used.
  • the preferable aspect of the wiring terminal B is also the same as the preferable aspect of the wiring terminal A.
  • Substrate B may have an electronic circuit area containing electronic circuits.
  • the electronic circuit may have an element such as a semiconductor.
  • it is preferable that the electronic circuit is electrically connected to the wiring terminal.
  • the diameter maximum diameter if the substrate B is not circular
  • it is preferably 200 mm or more, and more preferably 250 mm or more.
  • the diameter is preferably 7 mm or more, more preferably 8 mm or more, and even more preferably 10 mm or more.
  • the upper limit is, for example, preferably 50 mm or less, more preferably 30 mm or less, and even more preferably 20 mm or less.
  • a second polyimide-containing portion is formed on the surface of the substrate B provided with the wiring terminal. It is preferable to further include a polyimide-containing portion forming step.
  • the second polyimide-containing portion forming step can be performed, for example, by the same method as the polyimide-containing portion forming step for the substrate A described above.
  • the composition for forming a polyimide-containing portion of the present invention may be used, or another known composition for forming a polyimide-containing portion may be used. It is preferable to use the polyimide-containing part-forming composition of the invention.
  • the composition of the polyimide-containing portion-forming composition of the present invention used in the second polyimide-containing portion-forming step the composition of the polyimide-containing portion-forming composition of the present invention used in the second polyimide-containing portion-forming step,
  • the composition for forming the polyimide-containing portion used in the step of forming the polyimide-containing portion on the substrate A may be the same as or different from the composition.
  • Preferred aspects of the second polyimide-containing portion are the same as preferred aspects of the polyimide-containing portion formed on the substrate A described above. It is believed that in the bonding step described later, the second polyimide-containing portion and the polyimide-containing portion formed on the substrate A are bonded so that at least a portion thereof is in contact with each other, thereby improving the adhesiveness of the bonded body.
  • the glass transition temperature of the second polyimide-containing portion is preferably lower than the bonding temperature in the bonding step.
  • the glass transition temperature of the second polyimide-containing portion is preferably 30 ° C. or more lower than the bonding temperature in the bonding step, more preferably 50 ° C. or more, and 70 ° C. or more. is more preferred.
  • the glass transition temperature of the second polyimide-containing portion is preferably 30° C. or more higher than the bonding temperature in the bonding step.
  • a planarization step of planarizing the surface of the polyimide-containing portion of the substrate A is performed between the polyimide-containing portion forming step and the bonding step. It is preferred to include In the bonding step described later, the flattened polyimide-containing portion of the base material A and the surface of the base material B (or the surface of the second polyimide-containing portion, which may be flattened) are in contact with each other. preferably.
  • the wiring terminal A on the substrate A is exposed from the polyimide-containing portion by the planarization.
  • the flattening may be performed by physical polishing such as cutting, mechanical polishing, grinding, plasma treatment, laser ablation, or by chemical polishing such as CMP (Chemical Mechanical Polishing). Also, these methods may be combined, such as performing CMP after cutting. Specifically, for example, the surface of the polyimide-containing portion is cut with a diamond cutting tool to expose a new surface of the polyimide-containing portion and the wiring terminal A. By flattening the wiring terminal A and the polyimide-containing portion on the substrate A so that the wiring terminal A is exposed, the wiring terminal A and the polyimide-containing portion can be collectively flattened to expose the wiring terminal A. Become.
  • Planarization can be performed, for example, with a surface planer.
  • the surface planer include those in which a diamond tool is attached to a spindle, such as DFS8910, DFS8960, DAS8920, and DAS8930 (all trade names) manufactured by Disco.
  • the polyimide-containing portion is preferably planarized together with the wiring terminal A.
  • the TTV (Total Thickness Variation) of the polyimide-containing portion and the wiring terminal A is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and 3 ⁇ m or less. More preferred.
  • TTV means that the area 1 mm or more inside from the edge of the polyimide-containing portion is divided into 2 mm square sections (if the area of the polyimide containing portion is small, etc., it cannot be divided into 2 mm square sections,
  • the entire area inside 1 mm or more from the edge of the part is defined as one section), and for each section, the maximum thickness between one surface and the other surface (T1), and the one surface and the other surface Measure the minimum thickness (T2) between, calculate the film thickness difference (T1-T2) for each section, rank each section in descending order of the film thickness difference (T1-T2), the highest section
  • the number of partition groups corresponding to 10% of the total number of partitions (rounded down if there is a decimal point) and the lowest partition (smallest film thickness difference) in descending order of film thickness difference from (largest film thickness difference) 10% of the total number of compartments (rounded down if there is a decimal point) in descending order of film thickness difference from the remaining compartment groups.
  • TTV of a polyimide-containing portion when specifically referring to the TTV of a polyimide-containing portion as defined herein, it may be referred to as a "compartment-rated TTV.”
  • the TTV of the polyimide-containing portion By setting the TTV of the polyimide-containing portion to the upper limit value or less, the film thickness becomes generally uniform, and the adhesiveness to the substrate B is improved.
  • the polyimide-containing portion of the present invention preferably has a surface roughness Ra of 10 nm or more and 1.5 ⁇ m or less on the side opposite to the side in contact with the surface of the substrate A.
  • the upper limit is preferably 1 ⁇ m or less, more preferably 500 nm or less, still more preferably 300 nm or less, even more preferably 200 nm or less, even more preferably 150 nm or less, and 120 nm. The following are even more preferred.
  • a second planarization for planarizing the surface of the second polyimide-containing portion is performed between the step of forming the second polyimide-containing portion and the bonding step. It is preferable to include steps.
  • the second planarization process can be performed by the same method as the planarization process for the substrate A described above.
  • a method for producing a bonded body using the composition for forming a polyimide-containing portion of the present invention includes a bonding step of bonding the surface of the substrate A having the polyimide-containing portion and the surface of the substrate B having the wiring terminal. .
  • the bonding step is a step of bonding the surface of the substrate A having the polyimide-containing portion and the surface of the substrate B having the second polyimide-containing portion.
  • the wiring terminal A on the substrate A and the wiring terminal B on the substrate B are electrically bonded.
  • the electrodes included in the surface of the substrate A having the polyimide-containing portion and the electrodes on the surface of the substrate B having the wiring terminals are in direct contact with each other. is one of That is, it is also preferable that neither the wiring terminal A nor the wiring terminal B have a conducting path.
  • the glass transition temperature of the polyimide-containing portion is lower than the bonding temperature, so that the adhesiveness and electrical connectivity between the substrates A and B can be ensured even when no conducting paths are used. .
  • Bonding is preferably performed by means including heating, more preferably by means including heating and pressure.
  • the temperature during bonding (bonding temperature) is preferably 100° C. or higher, more preferably 150° C. or higher, and even more preferably 180° C. or higher.
  • the upper limit is preferably 450°C or lower, more preferably 400°C or lower, even more preferably 380°C or lower, particularly preferably 350°C or lower, and preferably 300°C or lower. It is more preferably 280° C. or lower, even more preferably 260° C. or lower, and even more preferably 250° C. or lower.
  • This temperature is preferably a temperature near the melting point of the conductive path, considering that the conductive path is melted and the electrodes can be joined together, as described above.
  • the heating time in the bonding step is not particularly limited, but is preferably 5 seconds or longer, more preferably 1 minute or longer, and even more preferably 2 minutes or longer.
  • a practical upper limit is 30 minutes or less.
  • the heating environment is not particularly limited, but it is preferable to perform the heating under a reduced pressure atmosphere while mechanically pressurizing the polyimide-containing portion.
  • the atmospheric pressure is preferably 1 ⁇ 10 ⁇ 5 mbar or higher, more preferably 1 ⁇ 10 ⁇ 4 mbar or higher, and even more preferably 5 ⁇ 10 ⁇ 4 mbar or higher.
  • the upper limit is preferably 0.1 mbar or less, more preferably 1 ⁇ 10 ⁇ 2 mbar or less, and even more preferably 5 ⁇ 10 ⁇ 3 mbar or less.
  • Bonding is preferably performed by sandwiching two substrates (substrate A and substrate B), and at this time, it is preferable to apply pressure to the substrates.
  • the pressure applied to the substrate is preferably 1 kN or more, more preferably 5 kN or more, and even more preferably 10 kN or more.
  • a practical upper limit is 100 kN or less.
  • the device used in the bonding step is not particularly limited, but a device used for reflowing electronic components can be preferably used.
  • the temperature of the substrate A provided with the polyimide-containing portion is preheated to 70° C. or higher.
  • the substrate B includes the second polyimide-containing part, it is also preferable that the temperature of the substrate B is preheated to 70° C. or higher.
  • the temperature is preferably 70° C. or higher, more preferably 90° C. or higher.
  • the upper limit of the temperature is not particularly limited, it is preferably 130° C. or less. According to the above aspect, the tact time of the bonding process can be reduced. In addition, the fluidity of the polyimide-containing portion during bonding is improved, and the maximum peel resistance may be improved.
  • the method for producing a joined body using the composition for forming a polyimide-containing portion of the present invention does not preclude interposing other steps between the steps defined above.
  • the bonding process the example in which the substrate A and the substrate B are faced face-to-face and bonded has been mainly described, but a form in which a plurality of substrates B are arranged in parallel with respect to the substrate A and bonded together has been described. good too.
  • FIG. 2 is a process explanatory view schematically showing (a part of) the process of bonding the substrates in the method of manufacturing a joined body according to one embodiment of the present invention, using cross-sectional views.
  • a substrate A (underlying substrate) 1 having an electronic circuit region 8 provided on a silicon wafer 1x and electrodes 31 (wiring terminals A) attached thereon is prepared (FIG. 2(a)).
  • An electronic circuit 81 made of a conductor or a semiconductor is already formed inside the electronic circuit area 8 of the substrate A1.
  • a method for forming an electronic circuit is not particularly limited, and it can be formed by a standard method.
  • the structure and members of the electronic circuit are not particularly limited, and examples thereof include a transistor and a wiring structure that electrically connects the transistor to an electrode.
  • a member (resin composition layer) 4 made of the resin composition is formed by applying a resin composition to the surface P0 of the substrate A1 on which the electrodes are arranged (the surface having the electronic circuit region) (FIG. 2(b)).
  • the resin composition layer may be heated and dried (drying step). After drying, the resin composition layer 4 may be patterned by photolithography, ion sputtering, or the like.
  • the resin composition layer 4 is heated to promote cyclization to form a cured polyimide-containing portion 41 (FIG. 2(c)).
  • a polyimide-containing portion-provided substrate 1y in which the polyimide-containing portion 41 is disposed on the substrate A1 is formed.
  • the polyimide-containing portion 41 may shrink compared to the resin composition layer 4 due to curing.
  • the shrinkage rate is not particularly limited, and a smaller shrinkage rate may be used, or no shrinkage may occur upon curing.
  • the substrate A shown in the drawing has only the electrodes 31 as the wiring terminals A, a conductive path may be formed on the electrodes 31 .
  • the conductive path may be formed in the substrate A from the beginning, or the polyimide-containing portion may be patterned before curing, and the conductive path may be formed in the patterned portion by plating or the like.
  • the heights h1 and h2 of the electrodes 31 vary.
  • the surface 4a of the polyimide-containing portion is also wavy and not flat.
  • planarization is performed to eliminate such variations in the height of the electrode 31, expose the tip surface thereof, and planarize the surface of the polyimide-containing portion. It is considered that the adhesion of the substrate is improved by planarizing in this way. Also, it is considered that the bondability between the wiring terminals can be improved without forming the conducting path.
  • FIG. 3 shows the polyimide-containing portion-disposed substrate (laminate) 1z after flattening.
  • the tip 31a of the electrode 31 is exposed on the surface 4b of the polyimide-containing portion, and the entire surface 4b of the polyimide-containing portion is flattened.
  • a substrate B is separately prepared for the laminate (flattened polyimide-containing portion-disposed substrate) 1z (FIG. 4A).
  • the substrate B2 includes a silicon wafer 2x having through-hole electrodes 2y, a circuit wiring region 8 having circuit wiring 81 disposed therein, and electrodes 32 (wiring terminals B) formed in the circuit wiring region 8.
  • the second polyimide-containing portion 42 is also formed on the surface of the substrate B having the wiring terminal B, and the surface 2a thereof is planarized in the same manner as the surface of the polyimide-containing portion 41 of the substrate A.
  • the formation and flattening of the second polyimide-containing portion 42 can be performed by the same method as the formation and flattening of the polyimide-containing portion 41 .
  • the surface of the polyimide-containing portion 41 and the electrode 31 of the substrate A and the surface of the second polyimide-containing portion 42 and the electrode 32 of the substrate B are both flattened. Even if there is no conductive path, the electrical connectivity is improved. At this time, alignment (alignment) is performed so that the electrodes 31 of the laminate and the electrodes 32 provided on the substrate B2 are in contact with each other.
  • alignment is performed so that the electrodes 31 of the laminate and the electrodes 32 provided on the substrate B2 are in contact with each other.
  • the electrode 31 is separated from the polyimide-containing portion 41 (second polyimide-containing portion 41).
  • a conductive path may be formed on the electrode 32 at the wiring terminal B as well.
  • the conducting path may be formed in the substrate B from the beginning, or the second polyimide-containing portion may be patterned before curing, and the patterning portion may be plated to form the conducting path.
  • the aligned substrate B2 and the laminate 1z are brought into contact with each other via the polyimide-containing portion 41 and the second polyimide-containing portion 42 at the bonding surface P1 and bonded (FIG. 4B). ).
  • a bonded body 100 in which two substrates are bonded is formed.
  • the electrodes 31 and 32 are electrically joined (joining step).
  • the polyimide-containing portion 41 is softened by the above heating, and the surface 4b of the polyimide-containing portion of the laminate 1z and the surface 2a of the substrate B (flattened surface of the second polyimide-containing portion 42) are bonded together. to form the bonded body 100 .
  • the glass transition temperature of the polyimide-containing portion is lower than the bonding temperature in the bonding step, the polyimide-containing portion is sufficiently softened and is considered to have excellent adhesiveness.
  • the substrate A and the substrate B can be electrically connected to each other, and both can be firmly fixed.
  • the contact surfaces are in a precise and accurate contact state with the substrate B2. can be obtained. By realizing a more precise and accurate contact state, it is possible to effectively suppress voids that tend to occur on the contact surface.
  • a device according to the present invention includes a joined body obtained by a method for producing a joined body using the composition for forming a polyimide-containing portion of the present invention.
  • a method of manufacturing a semiconductor device of the present invention includes the method of manufacturing a bonded body of the present invention.
  • Devices according to the present invention include semiconductor devices, electronic devices, etc., and are preferably semiconductor devices or electronic devices. For devices, see, for example, "Illustrated All About State-of-the-Art Semiconductor Package Technology" edited by the Semiconductor New Technology Study Group, pp.
  • composition for forming a polyimide-containing portion of the present invention can be applied to a wide variety of applications such as mounting of LED (light emitting diode) elements, mounting of optical elements for flat panel displays, and mounting of power semiconductor packages.
  • FIG. 5 is a cross-sectional view schematically showing a three-dimensional mounting device.
  • a laminate 101 in which a plurality of semiconductor elements (semiconductor chips) 101a to 101d are laminated is arranged on a wiring substrate 120.
  • Each of the plurality of semiconductor elements 101a-101d is made of a semiconductor wafer such as a silicon substrate.
  • a laminated body 101 has a structure in which a semiconductor element 101a having no through electrodes and semiconductor elements 101b to 101d having through electrodes 102b to 102d are flip-chip connected. Connection pads on the semiconductor element side having through electrodes are connected by metal bumps 103a, 103b, 103c such as solder bumps.
  • a resin layer 110 is formed between the semiconductor elements 101a to 101d.
  • the method for manufacturing a joined body in the present invention can be used. That is, for example, at least one (preferably all) of the resin layers 110 can be a polyimide-containing portion made of the composition for forming a polyimide-containing portion of the present invention.
  • a surface electrode 120 a is provided on one surface of the wiring board 120 .
  • An insulating layer 115 having a rewiring layer 105 formed thereon is arranged between the wiring substrate 120 and the laminate (substrate/substrate laminate) 101 .
  • One end of the rewiring layer 105 is connected to an electrode pad formed on the surface of the semiconductor element 101d facing the rewiring layer 105 via a metal bump 103d such as a solder bump.
  • the other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump.
  • a resin layer 110 a is formed between the insulating layer 115 and the laminate 101 .
  • the composition for forming a polyimide-containing portion of the present invention can also be used to bond the insulating layer 115 and the laminate 101 together. That is, for example, the resin layer 110a can be used as the polyimide-containing portion described above. A resin layer 110 b is formed between the insulating layer 115 and the wiring board 120 .
  • the composition for forming a polyimide-containing portion of the present invention can also be used to bond the insulating layer 115 and the wiring substrate 120 together. That is, for example, the resin layer 110b can be the polyimide-containing portion described above.
  • the composition for forming a polyimide-containing part of the present invention preferably contains at least one resin selected from the group consisting of polyimides and polyimide precursors (hereinafter also referred to as "specific resin"), and a solvent. It preferably contains a precursor and a solvent. Moreover, it is preferable that the composition for forming a polyimide-containing part of the present invention further contains a photosensitive compound.
  • the photosensitive compound includes a photopolymerization initiator, a photoacid generator, and the like, and a photopolymerization initiator is preferred.
  • the resin composition of the present invention preferably contains at least one resin (specific resin) selected from the group consisting of polyimides and polyimide precursors, and more preferably contains a polyimide precursor.
  • the specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group.
  • the resin composition of the present invention preferably contains a radical polymerization initiator described later, and contains a radical polymerization initiator described later and a radical cross-linking agent described later. is more preferred.
  • a sensitizer described later can be included.
  • a negative photosensitive film is formed from the resin composition of the present invention.
  • the specific resin may have a polarity conversion group such as an acid-decomposable group.
  • the resin composition of the present invention preferably contains a photoacid generator, which will be described later. From such a resin composition of the present invention, for example, a chemically amplified positive photosensitive film or negative photosensitive film is formed.
  • polyimide precursor Although the type of the polyimide precursor used in the present invention is not particularly limited, it preferably contains a repeating unit represented by the following formula (2).
  • a 1 and A 2 each independently represent an oxygen atom or -NH-
  • R 111 represents a divalent organic group
  • R 115 represents a tetravalent organic group
  • R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group.
  • a 1 and A 2 in formula (2) each independently represent an oxygen atom or —NH—, preferably an oxygen atom.
  • R 111 in formula (2) represents a divalent organic group.
  • divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, linear or branched aliphatic groups having 2 to 20 carbon atoms, A cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable.
  • the hydrocarbon group in the chain may be substituted with a group containing a hetero atom, and in the cyclic aliphatic group and the aromatic group, the ring member hydrocarbon group is a hetero atom.
  • may be substituted with a group containing Groups represented by -Ar- and -Ar-L-Ar- are exemplified as preferred embodiments of the present invention, and groups represented by -Ar-L-Ar- are particularly preferred.
  • Ar is each independently an aromatic group
  • L is a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO -, -S-, -SO 2 - or -NHCO-, or a group consisting of a combination of two or more of the above. Preferred ranges for these are as described above.
  • R 111 is preferably derived from a diamine.
  • Diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferably a diamine containing, more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. In the straight-chain or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a heteroatom. may be substituted with a group containing Examples of groups containing aromatic groups include:
  • * represents a binding site with other structures.
  • diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 1,6-diaminohexane; ,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4- aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4′-diamino-3,3′-dimethylcyclohexylmethane or isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4′- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3, 3,3
  • diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598.
  • diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 are preferably used.
  • R 111 is preferably represented by -Ar-L-Ar- from the viewpoint of the flexibility of the resulting organic film.
  • Ar is each independently an aromatic group
  • L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- , —SO 2 — or —NHCO—, or a group consisting of a combination of two or more of the above.
  • Ar is preferably a phenylene group
  • L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- or -SO 2 - .
  • the aliphatic hydrocarbon group here is preferably an alkylene group.
  • R 111 is preferably a divalent organic group represented by the following formula (51) or (61).
  • a divalent organic group represented by Formula (61) is more preferable.
  • Equation (51) In formula (51), R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group or a trifluoro It is a methyl group, and each * independently represents a binding site to the nitrogen atom in formula (2).
  • the monovalent organic groups represented by R 50 to R 57 include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), A fluorinated alkyl group and the like can be mentioned.
  • R 58 and R 59 are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * is each independently a bonding site to the nitrogen atom in formula (2) show.
  • Diamines that give the structure of formula (51) or (61) include 2,2′-dimethylbenzidine, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 2,2′-bis (Fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like. These may be used alone or in combination of two or more.
  • R 115 in formula (2) represents a tetravalent organic group.
  • a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or (6) is more preferable.
  • each * independently represents a binding site to another structure.
  • R 112 is a single bond or a divalent linking group, a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms optionally substituted with a fluorine atom, —O—, -CO-, -S-, -SO 2 -, and -NHCO-, and preferably a group selected from combinations thereof, and the number of carbon atoms optionally substituted with a single bond or a fluorine atom It is more preferably a group selected from 1 to 3 alkylene groups, -O-, -CO-, -S- and -SO 2 -, and -CH 2 -, -C(CF 3 ) 2 -, - More preferably, it is a divalent group selected from the group consisting of C(CH 3 ) 2 -, -O-, -CO-, -S- and -SO 2 -.
  • R 115 includes a tetracarboxylic acid residue remaining after removal of an anhydride group from a tetracarboxylic dianhydride.
  • the polyimide precursor may contain only one type of tetracarboxylic dianhydride residue as a structure corresponding to R115 , or may contain two or more types thereof.
  • the tetracarboxylic dianhydride is preferably represented by the following formula (O).
  • R 115 represents a tetravalent organic group.
  • the preferred range of R 115 is synonymous with R 115 in formula (2), and the preferred range is also the same.
  • tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′- Diphenyl sulfide tetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′ ,4,4′-diphenylmethanetetracarboxylic dianhydride, 2,2′,3,3′-diphenylmethanetetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride,
  • tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017/038598 are also preferred examples.
  • R 111 and R 115 has an OH group. More specifically, R 111 includes residues of bisaminophenol derivatives.
  • R 113 and R 114 in formula (2) each independently represent a hydrogen atom or a monovalent organic group.
  • the monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group.
  • At least one of R 113 and R 114 preferably contains a polymerizable group, more preferably both contain a polymerizable group. It is also preferred that at least one of R 113 and R 114 contains two or more polymerizable groups.
  • the polymerizable group is a group capable of undergoing a cross-linking reaction by the action of heat, radicals, or the like, and is preferably a radically polymerizable group.
  • the polymerizable group examples include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. be done.
  • a group having an ethylenically unsaturated bond is preferred.
  • Groups having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), and a (meth)acrylamide group.
  • a (meth)acryloyloxy group a group represented by the following formula (III), and the like, and a group represented by the following formula (III) is preferable.
  • R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, preferably a hydrogen atom or a methyl group.
  • * represents a binding site with another structure.
  • R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH(OH)CH 2 —, a cycloalkylene group or a polyalkyleneoxy group.
  • R 201 examples include ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, alkylene groups such as dodecamethylene, 1,2-butanediyl, 1, 3-butanediyl group, —CH 2 CH(OH)CH 2 —, polyalkyleneoxy group, ethylene group, alkylene group such as propylene group, —CH 2 CH(OH)CH 2 —, cyclohexyl group, polyalkylene An oxy group is more preferred, and an alkylene group such as an ethylene group, a propylene group, or a polyalkyleneoxy group is even more preferred.
  • alkylene groups such as dodecamethylene, 1,2-butanediyl, 1, 3-butanediyl group, —CH 2 CH(OH)CH 2 —, polyalkyleneoxy group, ethylene group, alkylene group such as propylene group, —CH 2 CH(OH)CH 2
  • a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded.
  • the alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
  • the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement or a block arrangement. Alternatively, it may be arranged in a pattern such as an alternating pattern.
  • the number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6.
  • the said alkylene group may have a substituent.
  • Preferred substituents include alkyl groups, aryl groups, and halogen atoms.
  • the number of alkyleneoxy groups contained in the polyalkyleneoxy group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
  • a group to which an oxy group is bonded is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is still more preferable.
  • the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, or may be arranged to form blocks. , may be arranged in a pattern such as alternately. Preferred embodiments of the number of repetitions of ethyleneoxy groups and the like in these groups are as described above.
  • the polyimide precursor when R 113 is a hydrogen atom, or when R 114 is a hydrogen atom, the polyimide precursor may form a tertiary amine compound having an ethylenically unsaturated bond and a counter salt. good.
  • tertiary amine compounds having such ethylenically unsaturated bonds include N,N-dimethylaminopropyl methacrylate.
  • R 113 and R 114 may be a polarity conversion group such as an acid-decomposable group.
  • the acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxyl group. , a tertiary alkyl ester group and the like are preferable, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferable.
  • acid-decomposable groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, and tert-butoxycarbonylmethyl. groups, trimethylsilyl ether groups, and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.
  • the polyimide precursor preferably has a fluorine atom in its structure.
  • the content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
  • the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
  • an aliphatic group having a siloxane structure there is an embodiment using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like as the diamine.
  • the repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one polyimide precursor used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by the formula (2-A) in the polyimide precursor, it becomes possible to further widen the width of the exposure latitude.
  • a 1 and A 2 represent an oxygen atom
  • R 111 and R 112 each independently represent a divalent organic group
  • R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group
  • at least one of R 113 and R 114 is a group containing a polymerizable group, and both are preferably groups containing a polymerizable group.
  • a 1 , A 2 , R 111 , R 113 and R 114 are each independently synonymous with A 1 , A 2 , R 111 , R 113 and R 114 in formula (2), and preferred ranges are also the same.
  • R 112 has the same definition as R 112 in formula (5), and the preferred range is also the same.
  • the polyimide precursor may contain one type of repeating unit represented by formula (2), but may contain two or more types. It may also contain structural isomers of the repeating unit represented by formula (2). It goes without saying that the polyimide precursor may also contain other types of repeating units in addition to the repeating units of formula (2) above.
  • the content of the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units.
  • the total content is more preferably 70 mol % or more, still more preferably 90 mol % or more, and particularly preferably more than 90 mol %.
  • the upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor excluding terminals may be repeating units represented by formula (2).
  • the weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, still more preferably 15,000 to 40,000. Also, the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, still more preferably 4,000 to 20,000.
  • the polyimide precursor preferably has a molecular weight distribution of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. Although the upper limit of the polyimide precursor's molecular weight dispersity is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
  • the molecular weight dispersity is a value calculated by weight average molecular weight/number average molecular weight.
  • the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one polyimide precursor are preferably within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated from the plurality of types of polyimide precursors as one resin are within the ranges described above.
  • the polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer containing an organic solvent as a main component.
  • the alkali-soluble polyimide refers to a polyimide that dissolves in 100 g of a 2.38% by mass tetramethylammonium aqueous solution at 23° C. by 0.1 g or more, and from the viewpoint of pattern formation, 0.5 g or more. It is preferably a polyimide that dissolves, and more preferably a polyimide that dissolves 1.0 g or more. Although the upper limit of the dissolved amount is not particularly limited, it is preferably 100 g or less.
  • the polyimide is preferably a polyimide having a plurality of imide structures in its main chain from the viewpoint of the film strength and insulating properties of the resulting organic film.
  • the term "main chain” refers to the relatively longest linking chain in the molecule of the polymer compound that constitutes the resin, and the term “side chain” refers to the other linking chain.
  • the polyimide preferably has a fluorine atom.
  • a fluorine atom is preferably included in, for example, R 132 in a repeating unit represented by formula (4) described later or R 131 in a repeating unit represented by formula (4) described later, and the formula ( It is more preferably contained as a fluorinated alkyl group in R 132 in the repeating unit represented by 4) or R 131 in the repeating unit represented by formula (4) described later.
  • the amount of fluorine atoms relative to the total mass of polyimide is preferably 5% by mass or more and preferably 20% by mass or less.
  • the polyimide preferably has a silicon atom.
  • a silicon atom for example, is preferably contained in R 131 in a repeating unit represented by formula (4) described later, and R 131 in a repeating unit represented by formula (4) described later is an organically modified (poly ) is more preferably contained as a siloxane structure.
  • the silicon atom or the organically modified (poly)siloxane structure may be contained in the side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
  • the amount of silicon atoms relative to the total mass of polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.
  • the polyimide preferably has an ethylenically unsaturated bond.
  • the polyimide may have an ethylenically unsaturated bond at the end of its main chain or in a side chain, preferably in a side chain.
  • the ethylenically unsaturated bond preferably has radical polymerizability.
  • the ethylenically unsaturated bond is preferably contained in R 132 in a repeating unit represented by the formula (4) described later, or R 131 in a repeating unit represented by the formula (4) described later.
  • the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by formula (4) described later, and ethylene is contained in R 131 in the repeating unit represented by formula (4) described later It is more preferably included as a group having a polyunsaturated bond.
  • the group having an ethylenically unsaturated bond includes a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acrylamide group, a (meth) Examples include an acryloyloxy group and a group represented by the following formula (IV).
  • R 20 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, preferably a hydrogen atom or a methyl group.
  • R 21 is an alkylene group having 2 to 12 carbon atoms, —O—CH 2 CH(OH)CH 2 —, —C( ⁇ O)O—, —O(C ⁇ O)NH— , a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, 1 to 6 are more preferable, and 1 to 3 are particularly preferable), or a group in which two or more of these are combined.
  • the alkylene group having 2 to 12 carbon atoms may be a linear, branched, cyclic, or a combination of these alkylene groups.
  • an alkylene group having 2 to 8 carbon atoms is preferable, and an alkylene group having 2 to 4 carbon atoms is more preferable.
  • R 21 is preferably a group represented by any one of the following formulas (R1) to (R3), more preferably a group represented by formula (R1).
  • L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are combined
  • X represents an oxygen atom or a sulfur atom
  • * represents a bonding site with another structure
  • ⁇ represents a bonding site with the oxygen atom to which R 21 in formula (IV) bonds.
  • a preferred embodiment of an alkylene group having 2 to 12 carbon atoms or a (poly)alkyleneoxy group having 2 to 30 carbon atoms in L is the above-mentioned R 21 having 2 to 12 carbon atoms. It is the same as the preferred embodiment of the 12 alkylene group or the (poly)alkyleneoxy group having 2 to 30 carbon atoms.
  • X is preferably an oxygen atom.
  • * has the same meaning as * in formula (IV), and preferred embodiments are also the same.
  • the structure represented by formula (R1) is, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group, and a compound having an isocyanato group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate, etc.). Obtained by reaction.
  • the structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (eg, 2-hydroxyethyl methacrylate, etc.).
  • the structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate, etc.) can get.
  • a polyimide having a hydroxy group such as a phenolic hydroxy group
  • a compound having a glycidyl group and an ethylenically unsaturated bond e.g., glycidyl methacrylate, etc.
  • * represents a binding site with another structure, preferably a binding site with the main chain of polyimide.
  • the amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001-0.1 mol/g, more preferably 0.0005-0.05 mol/g.
  • Polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond.
  • Polymerizable groups other than groups having an ethylenically unsaturated bond include cyclic ether groups such as an epoxy group and an oxetanyl group, alkoxymethyl groups such as a methoxymethyl group, and methylol groups.
  • a polymerizable group other than a group having an ethylenically unsaturated bond is preferably included, for example, in R 131 in a repeating unit represented by formula (4) described below.
  • the amount of the polymerizable group other than the group having an ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, preferably 0.001 to 0.05 mol / g. more preferred.
  • the polyimide may have a polarity conversion group such as an acid-decomposable group.
  • the acid-decomposable group in the polyimide is the same as the acid-decomposable group described for R 113 and R 114 in formula (2) above, and preferred embodiments are also the same.
  • Polar conversion groups are included, for example, at R 131 and R 132 in the repeating unit represented by formula (4) described later, the terminal of polyimide, and the like.
  • the acid value of polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more, from the viewpoint of improving developability. is more preferable. Moreover, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less. Further, when the polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development” described later), the acid value of the polyimide is preferably 1 to 35 mgKOH/g, and 2 to 30 mgKOH.
  • the acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.
  • an acid group having a pKa of 0 to 10 is preferable, and an acid group having a pKa of 3 to 8 is more preferable, from the viewpoint of both storage stability and developability.
  • the pKa is a dissociation reaction in which hydrogen ions are released from an acid, and its equilibrium constant Ka is represented by its negative common logarithm pKa.
  • pKa is a value calculated by ACD/ChemSketch (registered trademark).
  • the acid group is a polyvalent acid such as phosphoric acid
  • the pKa is the first dissociation constant.
  • the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, more preferably a phenolic hydroxy group.
  • the polyimide preferably has a phenolic hydroxy group from the viewpoint of making the development speed with an alkaline developer appropriate.
  • the polyimide may have a phenolic hydroxy group at the end of the main chain or in the side chain.
  • a phenolic hydroxy group is preferably contained in, for example, R 132 in a repeating unit represented by formula (4) described later or R 131 in a repeating unit represented by formula (4) described later.
  • the amount of phenolic hydroxy groups relative to the total weight of the polyimide is preferably 0.1-30 mol/g, more preferably 1-20 mol/g.
  • the polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it preferably contains a repeating unit represented by the following formula (4).
  • R 131 represents a divalent organic group and R 132 represents a tetravalent organic group.
  • the polymerizable group may be located on at least one of R 131 and R 132 , and the terminal of the polyimide as shown in the following formula (4-1) or (4-2) may be located in Formula (4-1)
  • R 133 is a polymerizable group, and other groups are the same as in formula (4).
  • Formula (4-2) At least one of R 134 and R 135 is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups are as defined in formula (4).
  • R 131 represents a divalent organic group.
  • Examples of the divalent organic group are the same as those for R 111 in formula (2), and the preferred range is also the same.
  • R 131 also includes a diamine residue remaining after removal of the amino group of the diamine.
  • Diamines include aliphatic, cycloaliphatic or aromatic diamines.
  • a specific example is the example of R 111 in formula (2) of the polyimide precursor.
  • R 131 is preferably a diamine residue having at least two alkylene glycol units in its main chain from the viewpoint of more effectively suppressing warping during baking. More preferably, it is a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and more preferably the above diamine, which does not contain an aromatic ring. is.
  • Diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, and EDR. -148, EDR-176, D-200, D-400, D-2000, D-4000 (trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy) propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, and the like.
  • R 132 represents a tetravalent organic group.
  • examples of the tetravalent organic group are the same as those for R 115 in formula (2), and the preferred range is also the same.
  • four bonds of a tetravalent organic group exemplified as R 115 combine with four —C( ⁇ O)— moieties in the above formula (4) to form a condensed ring.
  • R 132 includes a tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride.
  • a specific example is the example of R 115 in formula (2) of the polyimide precursor. From the viewpoint of strength of the organic film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.
  • R 131 and R 132 has an OH group. More specifically, R 131 is 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2- Bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18) are preferred examples. and more preferred examples of R 132 are the above (DAA-1) to (DAA-5).
  • the polyimide preferably has a fluorine atom in its structure.
  • the content of fluorine atoms in the polyimide is preferably 10% by mass or more, and preferably 20% by mass or less.
  • the polyimide may be copolymerized with an aliphatic group having a siloxane structure.
  • the diamine component include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.
  • the main chain end of the polyimide is blocked with a terminal blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound. preferably.
  • monoamines examples include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7 -aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2 -hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6- Aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzoic acid
  • the imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, insulating properties, etc. of the resulting organic film. More preferably, it is 90% or more.
  • the upper limit of the imidization rate is not particularly limited, and may be 100% or less.
  • the imidization rate is measured, for example, by the method described below. The infrared absorption spectrum of the polyimide is measured, and the peak intensity P1 near 1377 cm ⁇ 1 , which is the absorption peak derived from the imide structure, is obtained. Next, after heat-treating the polyimide at 350° C.
  • the polyimide may contain repeating units represented by the above formula (4) that all contain one type of R 131 or R 132 , and the above formula ( 4) may contain a repeating unit. Moreover, the polyimide may contain other types of repeating units in addition to the repeating units represented by the above formula (4). Other types of repeating units include, for example, repeating units represented by formula (2) above.
  • polyimide for example, a method of reacting a tetracarboxylic dianhydride and a diamine (partially replaced with a monoamine terminal blocker) at a low temperature, a method of reacting a tetracarboxylic dianhydride (partially with an acid anhydride) at a low temperature a monoacid chloride compound or a monoactive ester compound) and a diamine, a diester is obtained by a tetracarboxylic dianhydride and an alcohol, and then a diamine (a part of which is a monoamine A method of reacting in the presence of a condensing agent) with a condensing agent, a diester is obtained by tetracarboxylic acid dianhydride and alcohol, then the remaining dicarboxylic acid is acid chloride, diamine (part of which is a monoamine Using a method such as a method of reacting with a terminal blocking agent) to obtain a polyimide precursor
  • the weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, still more preferably 15,000 to 40,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. A weight-average molecular weight of 15,000 or more is particularly preferable in order to obtain an organic film having excellent mechanical properties (e.g., elongation at break). Also, the number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, still more preferably 4,000 to 20,000. The polyimide has a molecular weight distribution of preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
  • the upper limit of the polyimide molecular weight dispersion is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
  • the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polyimide are preferably within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated using the above plural kinds of polyimides as one resin are within the ranges described above.
  • Polyimide precursors and the like for example, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature to obtain a polyamic acid, a condensing agent or an alkylating agent A method of esterification using a tetracarboxylic dianhydride and an alcohol to obtain a diester, followed by a reaction with a diamine in the presence of a condensing agent, a method of reacting a tetracarboxylic dianhydride and an alcohol to obtain a diester, After that, the remaining dicarboxylic acid can be acid-halogenated using a halogenating agent and reacted with a diamine.
  • the method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and reacting it with a diamine is more preferred.
  • the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N'-disuccinimidyl carbonate, trifluoroacetic anhydride and the like can be mentioned.
  • alkylating agent examples include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate and triethyl orthoformate.
  • halogenating agent examples include thionyl chloride, oxalyl chloride, phosphorus oxychloride and the like.
  • organic solvent In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction. One type of organic solvent may be used, or two or more types may be used.
  • the organic solvent can be appropriately determined depending on the raw material, but pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, ⁇ -butyrolactone, and the like. are exemplified.
  • a basic compound In the method for producing a polyimide precursor or the like, it is preferable to add a basic compound during the reaction.
  • One type of basic compound may be used, or two or more types may be used.
  • the basic compound can be appropriately determined depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-amino Pyridine and the like are exemplified.
  • terminal blocking agents include monoalcohols, phenols, thiols, thiophenols, monoamines, and the like. It is more preferable to use monoalcohols, phenols and monoamines from the viewpoint of their properties.
  • Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol and furfuryl alcohol, and isopropanol. , 2-butanol, cyclohexyl alcohol, cyclopentanol and 1-methoxy-2-propanol, and tertiary alcohols such as t-butyl alcohol and adamantane alcohol.
  • Preferable phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene.
  • Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6- aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1- Carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-amin
  • Preferred capping agents for amino groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromide, sulfonic acid chlorides, sulfonic anhydrides, sulfonic acid carboxylic acid anhydrides, etc., more preferably carboxylic acid anhydrides and carboxylic acid chlorides. preferable.
  • Preferred carboxylic anhydride compounds include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and the like. is mentioned.
  • Preferred compounds of carboxylic acid chlorides include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, and 1-adamantanecarbonyl chloride. , heptafluorobutyryl chloride, stearic acid chloride, benzoyl chloride, and the like.
  • a step of depositing a solid may be included in the production of the polyimide precursor or the like. Specifically, after filtering off the water absorption by-products of the dehydration condensation agent coexisting in the reaction solution as necessary, water, aliphatic lower alcohol, or a poor solvent such as a mixture thereof, the obtained A polyimide precursor or the like can be obtained by adding a polymer component and depositing the polymer component, depositing it as a solid, and drying it. In order to improve the degree of purification, operations such as redissolution, reprecipitation, drying, etc. of the polyimide precursor may be repeated. Furthermore, a step of removing ionic impurities using an ion exchange resin may be included.
  • the content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more with respect to the total solid content of the resin composition. is more preferable, and 50% by mass or more is even more preferable. Further, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, more preferably 98% by mass, based on the total solid content of the resin composition. % or less, more preferably 97 mass % or less, and even more preferably 95 mass % or less.
  • the resin composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition of the present invention preferably contains at least two resins.
  • the resin composition of the present invention may contain a total of two or more of the specific resin and other resins described later, or may contain two or more of the specific resins. It is preferable to include two or more kinds.
  • the resin composition of the present invention contains two or more specific resins, for example, two or more polyimides that are polyimide precursors and have different dianhydride-derived structures (R 115 in the above formula (2)) It preferably contains a precursor.
  • the resin composition of the present invention may contain the specific resin described above and other resins different from the specific resin (hereinafter also simply referred to as "other resins").
  • Other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. etc.
  • a resin composition having excellent applicability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
  • a high polymerizable group value having a weight average molecular weight of 20,000 or less for example, the molar amount of the polymerizable group in 1 g of the resin is 1 ⁇ 10 ⁇ 3 mol/g or more
  • the coating properties of the resin composition, the solvent resistance of the pattern (cured product), etc. can be improved.
  • Other resins can also be added to the resin composition as dispersants for fillers. In such an embodiment, as the other resin, a known filler dispersant can be used without particular limitation.
  • the content of the other resins is preferably 0.01% by mass or more, and 0.05% by mass or more, relative to the total solid content of the resin composition. More preferably, it is more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and further preferably 10% by mass or more. More preferred.
  • the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, based on the total solid content of the resin composition. It is more preferably 60% by mass or less, even more preferably 50% by mass or less.
  • the content of other resins may be low.
  • the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less, relative to the total solid content of the resin composition. is more preferable, 5% by mass or less is even more preferable, and 1% by mass or less is even more preferable.
  • the lower limit of the content is not particularly limited as long as it is 0% by mass or more.
  • the resin composition of the present invention may contain only one kind of other resin, or may contain two or more kinds thereof. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition of the present invention preferably contains a polymerizable compound.
  • Polymerizable compounds include radical cross-linking agents or other cross-linking agents.
  • the resin composition of the present invention preferably contains a radical cross-linking agent.
  • a radical cross-linking agent is a compound having a radically polymerizable group.
  • the radically polymerizable group a group containing an ethylenically unsaturated bond is preferred.
  • Examples of the group containing an ethylenically unsaturated bond include groups containing an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
  • the group containing an ethylenically unsaturated bond is preferably a (meth)acryloyl group, a (meth)acrylamide group, or a vinylphenyl group, and more preferably a (meth)acryloyl group from the viewpoint of reactivity.
  • the radical cross-linking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more.
  • the radical cross-linking agent may have 3 or more ethylenically unsaturated bonds.
  • the compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and 2 to 6.
  • the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferred to include
  • the molecular weight of the radical cross-linking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
  • the lower limit of the molecular weight of the radical cross-linking agent is preferably 100 or more.
  • radical cross-linking agent examples include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. They are esters of saturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds.
  • addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxy group, an amino group, or a sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, or monofunctional or polyfunctional is also preferably used.
  • addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and halogeno groups
  • substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a tosyloxy group and monofunctional or polyfunctional alcohols, amines, and thiols.
  • paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated herein.
  • the radical cross-linking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure.
  • examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, glycerin, trimethylolethane, etc.
  • polyfunctional (meth)acrylate obtained by reacting polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth)acrylate and an ethylenically unsaturated bond can also be used.
  • JP-A-2010-160418, JP-A-2010-129825, JP-A-4364216, etc. have a fluorene ring and an ethylenically unsaturated bond. It is also possible to use compounds having two or more groups and cardo resins.
  • JP-B-46-043946 JP-B-01-040337, JP-B-01-040336, and JP-A-02-025493.
  • vinyl phosphonic acid compounds and the like can also be mentioned.
  • Compounds containing perfluoroalkyl groups described in JP-A-61-022048 can also be used.
  • the journal of the Japan Adhesive Association vol. 20, No. 7, pp. 300-308 (1984) as photopolymerizable monomers and oligomers can also be used.
  • dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (Nippon Kayaku ( Ltd.), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipenta Erythritol hexa(meth)acrylate (commercially available products are KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), and their (meth)acryloyl groups are ethylene glycol,
  • radical cross-linking agents examples include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, SR-209, a bifunctional methacrylate having four ethyleneoxy chains, manufactured by Sartomer. 231, 239, Nippon Kayaku Co., Ltd.
  • DPCA-60 a hexafunctional acrylate having 6 pentyleneoxy chains, TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS-10 , UAB-140 (manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Japan Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blenmer PME400 (manufactured by NOF Corporation) etc.
  • radical cross-linking agents examples include urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, JP-B-02-016765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also suitable.
  • compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 are used. can also
  • the radical cross-linking agent may be a radical cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group.
  • a radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. is more preferable.
  • the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol is a compound.
  • Examples of commercially available products include polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd. such as M-510 and M-520.
  • the acid value of the radical cross-linking agent having an acid group is preferably 0.1-300 mgKOH/g, particularly preferably 1-100 mgKOH/g. If the acid value of the radical cross-linking agent is within the above range, the handleability in production is excellent, and furthermore the developability is excellent. Moreover, the polymerizability is good. The acid value is measured according to JIS K 0070:1992.
  • the resin composition preferably uses a bifunctional methacrylate or acrylate.
  • Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, and PEG600 diacrylate.
  • PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula weight of about 200.
  • a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent from the viewpoint of suppressing warpage associated with the elastic modulus control of the pattern (cured product).
  • Monofunctional radical cross-linking agents include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, ) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc.
  • N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam
  • allyl glycidyl ether are preferably used.
  • the monofunctional radical cross-linking agent a compound having a boiling point of 100° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
  • Other di- or higher functional radical cross-linking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.
  • a radical cross-linking agent When a radical cross-linking agent is contained, its content is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the resin composition of the present invention. More preferably, the lower limit is 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.
  • a single radical cross-linking agent may be used alone, or two or more may be used in combination. When two or more are used in combination, the total amount is preferably within the above range.
  • the resin composition of the present invention contains another cross-linking agent different from the radical cross-linking agent described above.
  • the other cross-linking agent refers to a cross-linking agent other than the above-described radical cross-linking agent, and the above-described photoacid generator or photobase generator reacts with other compounds in the composition or reacts with them.
  • the compound has a plurality of groups in the molecule that promote the reaction forming covalent bonds with the product, and covalent bonds are formed with other compounds in the composition or reaction products thereof. Compounds having a plurality of groups in the molecule, the reaction of which is promoted by the action of an acid or base, are preferred.
  • the acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
  • compounds having at least one group selected from the group consisting of acyloxymethyl groups, methylol groups and alkoxymethyl groups are preferred, and the compounds are preferably selected from the group consisting of acyloxymethyl groups, methylol groups and alkoxymethyl groups. More preferred is a compound having a structure in which at least one group is directly bonded to a nitrogen atom.
  • cross-linking agents include, for example, an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, and benzoguanamine, which is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is converted to an acyloxymethyl group, methylol group, or A compound having a structure substituted with an alkoxymethyl group can be mentioned.
  • the method for producing these compounds is not particularly limited as long as they have the same structure as the compounds produced by the above methods. Oligomers formed by self-condensation of methylol groups of these compounds may also be used.
  • a melamine-based crosslinking agent is a melamine-based crosslinking agent
  • a glycoluril, urea or alkyleneurea-based crosslinking agent is a urea-based crosslinking agent
  • an alkyleneurea-based crosslinking agent is an alkyleneurea-based crosslinking agent.
  • a cross-linking agent using benzoguanamine is called a benzoguanamine-based cross-linking agent.
  • the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based cross-linking agents and melamine-based cross-linking agents. More preferably, it contains at least one compound selected from the group consisting of agents.
  • an alkoxymethyl group or an acyloxymethyl group is directly substituted on the nitrogen atom of an aromatic group or the following urea structure, or on a triazine.
  • the alkoxymethyl group or acyloxymethyl group of the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.
  • the total number of alkoxymethyl groups and acyloxymethyl groups in the above compound is preferably 1-10, more preferably 2-8, and particularly preferably 3-6.
  • the molecular weight of the compound is preferably 1500 or less, preferably 180-1200.
  • R 100 represents an alkyl group or an acyl group.
  • R 101 and R 102 each independently represent a monovalent organic group and may combine with each other to form a ring.
  • Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted by an aromatic group include compounds represented by the following general formula.
  • X represents a single bond or a divalent organic group
  • each R 104 independently represents an alkyl group or an acyl group
  • R 103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group , or a group that decomposes under the action of an acid to produce an alkali-soluble group (e.g., a group that leaves under the action of an acid, a group represented by —C(R 4 ) 2 COOR 5 (R 4 is independently It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 represents a group that leaves under the action of an acid.)).
  • R 105 each independently represents an alkyl group or alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3 , a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less.
  • R 5 in the group represented by —C(R 4 ) 2 COOR 5 a group that is decomposed by the action of an acid to produce an alkali-soluble group, a group that is eliminated by the action of an acid, and —C(R 36 )(R 37 )(R 38 ), —C(R 36 )(R 37 )(OR 39 ), —C(R 01 )(R 02 )(OR 39 ), and the like.
  • R 36 to R 39 each independently represent an alkyl group, cycloalkyl group, aryl group, aralkyl group or alkenyl group.
  • R 36 and R 37 may combine with each other to form a ring.
  • alkyl group an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
  • the alkyl group may be linear or branched.
  • a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable.
  • the cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring.
  • the aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a phenyl group.
  • an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable.
  • the aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as the preferred embodiments of the alkyl and aryl groups described above.
  • the alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, more preferably an alkenyl group having 3 to 16 carbon atoms. Moreover, these groups may further have a known substituent within the range in which the effects of the present invention can be obtained.
  • R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
  • the group that is decomposed by the action of an acid to form an alkali-soluble group or the group that is eliminated by the action of an acid is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, or the like. More preferred are tertiary alkyl ester groups and acetal groups.
  • compounds having an alkoxymethyl group include the following structures.
  • Examples of the compound having an acyloxymethyl group include compounds obtained by changing the alkoxymethyl group of the following compounds to an acyloxymethyl group.
  • Compounds having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds.
  • the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group a commercially available one or a compound synthesized by a known method may be used. From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.
  • melamine-based cross-linking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.
  • urea-based cross-linking agents include monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, and dimethoxymethylated glycol.
  • Uril trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril , dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, or tetrabutoxymethylated glycoluril glycoluril-based crosslinkers such as uril; urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea; monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated
  • benzoguanamine-based cross-linking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine.
  • tetramethoxymethylated benzoguanamine monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetra propoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, and the like.
  • the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group includes at least one group selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring).
  • Compounds to which a seed group is directly attached are also preferably used. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate.
  • suitable commercial products include 46DMOC, 46DMOEP (manufactured by Asahi Organic Chemicals Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, and DML-OEP.
  • DML-34X DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP -Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML -BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (Honshu Chemical Industry Co., Ltd.), Nikalac (registered
  • the resin composition of the present invention preferably contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds as another cross-linking agent.
  • Epoxy compound (compound having an epoxy group) -
  • the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
  • the epoxy group undergoes a cross-linking reaction at 200° C. or less and does not undergo a dehydration reaction resulting from the cross-linking, so film shrinkage does not easily occur. Therefore, containing an epoxy compound is effective for low-temperature curing and suppression of warpage of the resin composition of the present invention.
  • the epoxy compound preferably contains a polyethylene oxide group.
  • the polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2-15.
  • epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether.
  • alkylene glycol type epoxy resins such as trimethylolpropane triglycidyl ether or polyhydric alcohol hydrocarbon type epoxy resins
  • polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether
  • epoxy groups such as polymethyl (glycidyloxypropyl) siloxane Examples include, but are not limited to, containing silicones and the like.
  • Epiclon (registered trademark) 850-S Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-830LVP, Epiclon (registered trademark) EXA-8183, Epiclon (registered trademark) EXA-8169, Epiclon (registered trademark) N-660, Epiclon (registered trademark) N-665-EXP-S, Epiclon (registered trademark) N-740 (trade name, manufactured by DIC Corporation), Ricaresin (registered trademark) BEO-20E, Jamaicaresin (registered trademark) BEO-60E, Ricaresin (registered trademark) ) HBE-100, Ricaresin (registered trademark) DME-100, Ricaresin (registered trademark)
  • n is an integer of 1-5 and m is an integer of 1-20.
  • n 1 to 2 and m is 3 to 7 from the viewpoint of achieving both heat resistance and elongation improvement.
  • oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl)methoxy]methyl ⁇ benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester and the like can be mentioned.
  • Aron oxetane series manufactured by Toagosei Co., Ltd. eg, OXT-121, OXT-221
  • OXT-121, OXT-221 can be suitably used, and these can be used alone or in combination of two or more. good.
  • a benzoxazine compound (compound having a benzoxazolyl group)-
  • a benzoxazine compound is preferable because it is a cross-linking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and thermal shrinkage is reduced to suppress the occurrence of warping.
  • benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (these are trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, phenol novolac-type dihydrobenzoxazines, oxazine compounds. These may be used alone or in combination of two or more.
  • the content of the other cross-linking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. It is more preferably 5 to 15% by mass, particularly preferably 1.0 to 10% by mass.
  • Other cross-linking agents may be contained alone, or may be contained in two or more. When two or more other cross-linking agents are contained, the total is preferably within the above range.
  • the resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat. In particular, it preferably contains a photopolymerization initiator.
  • the photopolymerization initiator is preferably a photoradical polymerization initiator.
  • the radical photopolymerization initiator is not particularly limited and can be appropriately selected from known radical photopolymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. It may also be an activator that produces an active radical by producing some action with a photoexcited sensitizer.
  • the radical photopolymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 within the wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). is preferred.
  • the molar extinction coefficient of a compound can be measured using known methods. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.
  • any known compound can be used as the photoradical polymerization initiator.
  • halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
  • acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc.
  • ketone compounds include compounds described in paragraph 0087 of JP-A-2015-087611, the content of which is incorporated herein.
  • Kayacure-DETX-S manufactured by Nippon Kayaku Co., Ltd. is also suitably used.
  • a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be suitably used as the radical photopolymerization initiator. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used. incorporated.
  • ⁇ -hydroxyketone initiators include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE -2959 and IRGACURE 127 (trade names: both manufactured by BASF) can be used.
  • ⁇ -aminoketone initiators examples include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all BASF company) can be used.
  • the compound described in JP-A-2009-191179 whose maximum absorption wavelength is matched to a wavelength light source such as 365 nm or 405 nm can also be used, the content of which is incorporated herein.
  • Acylphosphine oxide initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
  • Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), IRGACURE-819 and IRGACURE-TPO (trade names: all manufactured by BASF) can also be used.
  • metallocene compounds examples include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF) and Keycure VIS 813 (manufactured by King Brother Chem).
  • the photoradical polymerization initiator is more preferably an oxime compound.
  • an oxime compound By using an oxime compound, the exposure latitude can be improved more effectively.
  • Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.
  • oxime compound examples include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp.1653-1660); C. S. Compounds described in Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2017-019766, compounds described in Patent No.
  • Preferred oxime compounds include, for example, compounds having the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy( imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino)) -1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one, etc.
  • an oxime compound an oxime-based radical photopolymerization initiator
  • DFI-091 manufactured by Daito Chemix Co., Ltd.
  • SpeedCure PDO manufactured by SARTOMER ARKEMA
  • an oxime compound having the following structure can be used.
  • An oxime compound having a fluorene ring can also be used as the photoradical polymerization initiator.
  • Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466 and compounds described in Japanese Patent No. 06636081, the contents of which are incorporated herein.
  • an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
  • Specific examples of such oxime compounds include compounds described in WO2013/083505, the contents of which are incorporated herein.
  • oxime compound having a fluorine atom examples include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. and compound (C-3) described in paragraph 0101 of JP-A-164471, the contents of which are incorporated herein.
  • An oxime compound having a nitro group can be used as the photopolymerization initiator.
  • the oxime compound having a nitro group is also preferably a dimer.
  • Specific examples of the oxime compound having a nitro group include the compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249 and paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466; Included are compounds described in paragraphs 0007-0025 of Japanese Patent No. 4223071, the contents of which are incorporated herein.
  • the oxime compound having a nitro group also includes ADEKA Arkles NCI-831 (manufactured by ADEKA Co., Ltd.).
  • An oxime compound having a benzofuran skeleton can also be used as the photoradical polymerization initiator.
  • Specific examples include OE-01 to OE-75 described in WO 2015/036910.
  • an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used.
  • photoinitiators include compounds such as those described in WO2019/088055, the contents of which are incorporated herein.
  • an oxime compound having an aromatic ring group Ar 2 OX1 in which an electron-withdrawing group is introduced into the aromatic ring (hereinafter also referred to as oxime compound OX) can be used.
  • the electron-withdrawing group of the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group.
  • a benzoyl group may have a substituent.
  • substituents include halogen atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, It is preferably an acyl group or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group.
  • a sulfanyl group or an amino group is more preferred.
  • the oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), more preferably the compound represented by the formula (OX2). preferable.
  • R X1 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl a group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group
  • R X2 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group,
  • R X12 is an electron-withdrawing group
  • R X10 , R X11 , R X13 and R X14 are preferably hydrogen atoms.
  • oxime compound OX examples include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein.
  • oxime compounds having specific substituents shown in JP-A-2007-269779 and oxime compounds having a thioaryl group shown in JP-A-2009-191061. incorporated herein.
  • photoradical polymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds; are preferred.
  • More preferred radical photopolymerization initiators are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds.
  • At least one compound selected from the group consisting of trihalomethyltriazine compounds, ⁇ -aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferred, and metallocene compounds or oxime compounds are even more preferred. .
  • the photoradical polymerization initiator includes benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone such as N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), 2-benzyl -aromatic ketones such as 2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, alkylanthraquinones, etc.
  • benzophenone N,N'-tetraalkyl-4,4'-diaminobenzophenone
  • 2-benzyl -aromatic ketones such as 2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, alkylanthr
  • benzoin ether compounds such as benzoin alkyl ether
  • benzoin compounds such as benzoin and alkylbenzoin
  • benzyl derivatives such as benzyl dimethyl ketal
  • a compound represented by the following formula (I) can also be used.
  • R 100 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, Alternatively, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, a carbon number interrupted by one or more oxygen atoms a phenyl group or a biphenyl group substituted with at least one of an alkyl group having 2 to 18 carbon atoms and an alkyl group having 1 to 4 carbon atoms, and R I01 is a group represented by formula (II); R 102 to R 104 are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an
  • R 105 to R 107 are the same as R 102 to R 104 in formula (I) above.
  • radical photopolymerization initiator a difunctional or trifunctional or higher radical photopolymerization initiator may be used.
  • a radical photopolymerization initiator two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained.
  • the crystallinity is lowered, the solubility in a solvent or the like is improved, and precipitation becomes difficult over time, and the stability over time of the resin composition can be improved.
  • Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No.
  • a photopolymerization initiator When a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. , more preferably 0.5 to 15% by mass, and still more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range. In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking by the photopolymerization initiator may be further advanced by heating with an oven, a hot plate, or the like.
  • the resin composition according to the present invention preferably also contains a thermal polymerization initiator.
  • the thermal polymerization initiator can be selected depending on the type of polymerizable compound, but a thermal radical polymerization initiator is preferred.
  • a thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes a polymerization reaction of a polymerizable compound.
  • the photopolymerization initiator described above may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.
  • thermal polymerization initiators include known azo compounds and known peroxide compounds.
  • azo-based compounds include azobis-based compounds.
  • the azo compound may be a compound having a cyano group or a compound having no cyano group.
  • Peroxide compounds include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters, and the like.
  • thermal polymerization initiator such as V-40, V-601, and VF-096 manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., perhexyl O manufactured by NOF Corporation, per Hexyl D, Perhexyl I, Perhexa 25O, Perhexa 25Z, Percmyl D, Percmyl D-40, Percmyl D-40MB, Percmyl H, Percmyl P, Percmyl ND and the like.
  • specific examples of thermal radical polymerization initiators include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein.
  • the content of the thermal polymerization initiator in the resin composition is preferably 0.05% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 10% by mass or less, relative to the total solid content of the composition. , more preferably 0.1% by mass or more and 5% by mass or less, and particularly preferably 0.5% by mass or more and 3% by mass or less.
  • the resin composition (particularly, the second resin composition) may contain one type of thermal polymerization initiator alone, or two or more types thereof. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition may contain a sensitizer.
  • a sensitizer absorbs specific actinic radiation and enters an electronically excited state.
  • the sensitizer in an electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and causes electron transfer, energy transfer, heat generation, or the like.
  • the thermal radical polymerization initiator and the photoradical polymerization initiator undergo chemical changes and are decomposed to generate radicals, acids or bases.
  • Usable sensitizers include benzophenones, Michler's ketones, coumarins, pyrazole azos, anilinoazos, triphenylmethanes, anthraquinones, anthracenes, anthrapyridones, benzylidenes, oxonols, and pyrazolotriazole azos. , pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo compounds.
  • Sensitizers include, for example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal) Cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyl denindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)iso naphthothiazole,
  • the content of the sensitizer is preferably 0.01 to 20% by mass, preferably 0.1 to 15% by mass, based on the total solid content of the resin composition. more preferably 0.5 to 10% by mass.
  • the sensitizers may be used singly or in combination of two or more.
  • the resin composition of the present invention may contain a chain transfer agent.
  • the chain transfer agent is defined, for example, in Kobunshi Dictionary, 3rd edition (edited by Kobunshi Gakkai, 2005), pp. 683-684.
  • Chain transfer agents include, for example, a group of compounds having —S—S—, —SO 2 —S—, —NO—, SH, PH, SiH, and GeH in the molecule, RAFT (Reversible Addition Fragmentation Chain Transfer )
  • Dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds and the like having a thiocarbonylthio group used for polymerization are used. They can either donate hydrogen to less active radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals.
  • thiol compounds can be preferably used.
  • chain transfer agent can also use the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219, the contents of which are incorporated herein.
  • the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, preferably 0.01 to 20 parts by mass, based on 100 parts by mass of the total solid content of the resin composition of the present invention. 1 to 10 parts by mass is more preferable, and 0.5 to 5 parts by mass is even more preferable.
  • One type of chain transfer agent may be used, or two or more types may be used. When two or more chain transfer agents are used, the total is preferably within the above range.
  • the resin composition of the present invention preferably contains a photoacid generator.
  • a photoacid generator is a compound that generates at least one of Bronsted acid and Lewis acid upon irradiation with light of 200 nm to 900 nm.
  • the light to be irradiated is preferably light with a wavelength of 300 nm to 450 nm, more preferably light with a wavelength of 330 nm to 420 nm.
  • the photoacid generator is preferably a photoacid generator capable of generating an acid upon exposure.
  • generated acids include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acid, phosphoric monoesters, phosphoric diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, Sulfonamide and the like are preferred.
  • Examples of the photoacid generator used in the resin composition of the present invention include quinone diazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfone compounds, and onium salt compounds.
  • Organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred from the viewpoint of sensitivity and storage stability, and oxime esters are preferred from the viewpoint of the mechanical properties of the film to be formed.
  • quinonediazide compounds include monovalent or polyvalent hydroxy compounds in which quinonediazide sulfonic acids are ester-bonded, monovalent or polyvalent amino compounds in which quinonediazide sulfonic acids are sulfonamide-bonded, and polyhydroxypolyamino compounds with quinonediazide. and/or sulfonic acid having an ester bond and/or a sulfonamide bond.
  • hydroxy compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, t-Bu alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP- PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris-FR -CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML -PFP, DML-PSBP, DML-MTrisPC, TriML
  • amino compounds include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, and the like, but are not limited thereto.
  • polyhydroxypolyamino compounds include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3′-dihydroxybenzidine, but are not limited to these. .
  • the quinonediazide compound preferably contains a phenol compound and an ester with a 4-naphthoquinonediazide sulfonyl group. This makes it possible to obtain higher sensitivity to i-line exposure and higher resolution.
  • the content of the quinonediazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, based on 100 parts by mass of the resin.
  • the content of the quinonediazide compound is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, based on 100 parts by mass of the resin.
  • the photoacid generator is preferably a compound containing an oximesulfonate group (hereinafter also simply referred to as "oximesulfonate compound").
  • the oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group. 105) is preferably an oxime sulfonate compound.
  • X3 represents an alkyl group, an alkoxy group, or a halogen atom. When there are multiple X3's, they may be the same or different.
  • the alkyl group and alkoxy group in X3 above may have a substituent.
  • the alkyl group for X 3 above is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
  • the alkoxy group for X 3 is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
  • halogen atom for X3 a chlorine atom or a fluorine atom is preferable.
  • m3 represents an integer of 0 to 3, preferably 0 or 1.
  • R 34 represents an alkyl group or an aryl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a carbon It is preferably a halogenated alkoxy group of number 1 to 5, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W or an anthranyl group optionally substituted with W.
  • W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms; group, an aryl group having 6 to 20 carbon atoms, and an aryl halide group having 6 to 20 carbon atoms.
  • m3 is 3
  • X 3 is a methyl group
  • the substitution position of X 3 is the ortho position
  • R 34 is a linear alkyl group having 1 to 10 carbon atoms
  • Compounds with a 7-dimethyl-2-oxonorbornylmethyl group or a p-tolyl group are particularly preferred.
  • oxime sulfonate compound represented by formula (OS-1) are described in paragraph numbers 0064 to 0068 of JP-A-2011-209692 and paragraph numbers 0158-0167 of JP-A-2015-194674.
  • the following compounds are exemplified, the contents of which are incorporated herein.
  • R s1 represents an alkyl group, an aryl group or a heteroaryl group
  • R s2 which may be present in plurality, is each independently a hydrogen atom, an alkyl group, or an aryl represents a group or a halogen atom
  • each R s6 which may be present in plurality independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group
  • Xs represents O or S.
  • ns represents 1 or 2
  • ms represents an integer of 0-6.
  • an alkyl group preferably having 1 to 30 carbon atoms
  • an aryl group preferably having 6 to 30 carbon atoms
  • a heteroaryl group preferably having 6 to 30 carbon atoms represented by R s1 Numbers 4 to 30 are preferable
  • R s1 Numbers 4 to 30 may have a known substituent as long as the effects of the present invention can be obtained.
  • R s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms). , a hydrogen atom or an alkyl group.
  • R s2 that may be present in the compound at least two times, one or two are preferably an alkyl group, an aryl group or a halogen atom, and one is more preferably an alkyl group, an aryl group or a halogen atom.
  • one is an alkyl group and the rest are hydrogen atoms.
  • the alkyl group or aryl group represented by R s2 may have a known substituent as long as the effects of the present invention can be obtained.
  • Xs represents O or S, preferably O.
  • the ring containing Xs as a ring member is a 5- or 6-membered ring.
  • ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is 2 is preferred.
  • the alkyl group (preferably having 1 to 30 carbon atoms) and alkyloxy group (preferably having 1 to 30 carbon atoms) represented by R s6 are substituents. may have.
  • ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0 is particularly preferred.
  • the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111).
  • the compound represented by the formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is a compound represented by the following formula (OS -108) or a compound represented by the formula (OS-109).
  • R t1 represents an alkyl group, an aryl group or a heteroaryl group
  • R t7 represents a hydrogen atom or a bromine atom
  • R t8 represents a hydrogen atom, the number of carbon atoms 1 to 8 alkyl group, halogen atom, chloromethyl group, bromomethyl group, bromoethyl group, methoxymethyl group, phenyl group or chlorophenyl group
  • R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group
  • t2 represents a hydrogen atom or a methyl group.
  • R t7 represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.
  • R t8 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group. or represents a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms is more preferred, and a methyl group is particularly preferred.
  • R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, preferably a hydrogen atom.
  • R t2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
  • the oximes may have either one of the three-dimensional structures (E, Z) or may be a mixture.
  • Specific examples of the oxime sulfonate compounds represented by the formulas (OS-103) to (OS-105) include paragraphs 0088 to 0095 of JP-A-2011-209692 and paragraphs of JP-A-2015-194674. Compounds described in numbers 0168-0194 are exemplified, the contents of which are incorporated herein.
  • oximesulfonate compound containing at least one oximesulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).
  • R u9 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, It represents an aryl group or a heteroaryl group.
  • An aspect in which Ru9 is a cyano group or an aryl group is more preferred, and an aspect in which Ru9 is a cyano group, a phenyl group or a naphthyl group is even more preferred.
  • R u2a represents an alkyl group or an aryl group.
  • Xu is -O-, -S-, -NH-, -NR u5 -, -CH 2 -, -CR u6 H- or CR u6 R u7 —, and R u5 to R u7 each independently represent an alkyl group or an aryl group.
  • R u1 to R u4 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group. , an arylcarbonyl group, an amido group, a sulfo group, a cyano group or an aryl group.
  • Two of R u1 to R u4 may each combine to form a ring. At this time, the ring may be condensed to form a condensed ring together with the benzene ring.
  • R u1 to R u4 are preferably hydrogen atoms, halogen atoms or alkyl groups, and an aspect in which at least two of R u1 to R u4 are bonded to each other to form an aryl group is also preferable. Among them, an aspect in which all of R u1 to R u4 are hydrogen atoms is preferable. Any of the substituents described above may further have a substituent.
  • the compound represented by formula (OS-101) is more preferably a compound represented by formula (OS-102).
  • the stereostructures (E, Z, etc.) of the oxime and benzothiazole rings may be either one or a mixture.
  • Specific examples of the compound represented by formula (OS-101) include compounds described in paragraph numbers 0102 to 0106 of JP-A-2011-209692 and paragraph numbers 0195-0207 of JP-A-2015-194674. and the contents of which are incorporated herein.
  • the following b-9, b-16, b-31 and b-33 are preferred.
  • Examples of commercially available products include WPAG-336 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), MBZ-101 (manufactured by Midori Chemical Co., Ltd.), and the like. can be done.
  • organic halogenated compounds include those described by Wakabayashi et al., "Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. 48-36281, JP-A-55-32070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241 , JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, M.P. P. Hutt "Journal of Heterocyclic Chemistry” 1 (No 3), (1970), the contents of which are incorporated herein.
  • Particularly preferred examples include an oxazole compound substituted with a trihalomethyl group: an S-triazine compound. More preferably, s-triazine derivatives having at least one mono-, di-, or trihalogen-substituted methyl group attached to the s-triazine ring, specifically, for example, 2,4,6-tris(monochloromethyl)- s-triazine, 2,4,6-tris(dichloromethyl)-s-triazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)- s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, 2-( ⁇ , ⁇ , ⁇ -trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine , 2-phenyl-4,6-bis(trichloromethyl)-
  • organic borate compounds include JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, and JP-A-9-188710. Publications, JP-A-2000-131837, JP-A-2002-107916, JP-A-2764769, JP-A-2002-116539, etc., and Kunz, Martin "Rad Tech'98. Proceeding April 19-22 , 1998, Chicago", etc., organic boron sulfonium complexes or organic boron oxosulfonium described in JP-A-6-157623, JP-A-6-175564, and JP-A-6-175561.
  • JP-A-6-175554 organic boron-iodonium complexes described in JP-A-6-175553, organic boron-phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-H9 No. 7-128785, JP-A-7-140589, JP-A-7-306527, JP-A-7-292014 and the like organoboron transition metal coordination complexes are mentioned as specific examples. incorporated herein.
  • disulfone compound examples include compounds described in JP-A-61-166544, Japanese Patent Application No. 2001-132318, and diazodisulfone compounds.
  • onium salt compound for example, S.I. I. Schlesinger, Photograph. Sci. Eng. , 18, 387 (1974); S. Bal et al, Polymer, 21,423 (1980), diazonium salts, US Pat. , 055, 4,069,056, EP 104,143, US Pat. 2-150848, iodonium salts described in JP-A-2-296514, European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, U.S. Pat. Nos. 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827 German Patent Nos.
  • Onium salts include onium salts represented by the following general formulas (RI-I) to (RI-III).
  • Ar 11 represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents. ⁇ 12 alkenyl groups, alkynyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryloxy groups having 1 to 12 carbon atoms, halogen atoms, and 1 to 12 carbon atoms.
  • an alkylamino group a dialkylamino group having 2 to 12 carbon atoms, an alkylamide group having an alkyl group having 1 to 12 carbon atoms or an arylamide group having an aryl group having 6 to 20 carbon atoms, a carbonyl group, a carboxy group, a cyano groups, sulfonyl groups, thioalkyl groups having 1 to 12 carbon atoms, and thioaryl groups having 1 to 12 carbon atoms.
  • Z 11 - represents a monovalent anion such as a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, a sulfate ion, and a stable Perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, and sulfinate ion are preferred from the aspect.
  • Ar 21 and Ar 22 each independently represent an aryl group having 1 to 20 carbon atoms which may have 1 to 6 substituents, and preferred substituents are 1 to 12 carbon atoms.
  • an alkyl group having 2 to 12 carbon atoms an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen an atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having an alkyl group having 1 to 12 carbon atoms, an alkylamido group or an arylamide group having an alkyl group having 1 to 12 carbon atoms, carbonyl group, carboxy group, cyano group, sulfonyl group, thioalkyl group having 1 to 12 carbon atoms.
  • Z21 ⁇ represents a monovalent anion, and is a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, reaction Perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, and carboxylate ions are preferred from the viewpoint of their properties.
  • R 31 , R 32 and R 33 each independently represents an aryl group, an alkyl group, an alkenyl group or an alkynyl group having 6 to 20 carbon atoms which may have 1 to 6 substituents. In view of reactivity and stability, it is preferably an aryl group.
  • Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms in each alkyl group, and an alkyl group having 1 to 12 carbon atoms; 1 to 12 alkylamide or arylamido groups, carbonyl groups, carboxy groups, cyano groups, sulfonyl groups, C1 to C12 thioalkyl groups, and C1 to C12 thioaryl groups.
  • Z 31 ⁇ represents a monovalent anion and is a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, From the viewpoint of reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, and carboxylate ion are preferred.
  • preferred photoacid generators include the following.
  • the photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, and 0.5 to 10% by mass, based on the total solid content of the resin composition. It is more preferably used, more preferably 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass.
  • a photo-acid generator may be used individually by 1 type, or may be used in multiple types combination. In the case of a combination of multiple types, the total amount thereof is preferably within the above range.
  • the resin composition of the present invention may contain a base generator.
  • the base generator is a compound capable of generating a base by physical or chemical action.
  • Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators.
  • the resin composition when the resin composition contains a cyclized resin precursor, the resin composition preferably contains a base generator.
  • the base generator may be an ionic base generator or a non-ionic base generator.
  • bases generated from base generators include secondary amines and tertiary amines. There are no particular restrictions on the base generator used in the present invention, and known base generators can be used. Examples of known base generators include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, and amine imides.
  • Nonionic base generator examples include compounds represented by Formula (B1), Formula (B2), or Formula (B3).
  • Rb 1 , Rb 2 and Rb 3 are each independently an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb 1 and Rb 2 are not hydrogen atoms at the same time. Also, none of Rb 1 , Rb 2 and Rb 3 has a carboxy group.
  • the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when forming an amide group together with the nitrogen atom, this is not the case.
  • Rb 1 , Rb 2 and Rb 3 preferably contains a cyclic structure, and more preferably at least two of them contain a cyclic structure.
  • the cyclic structure may be either a single ring or a condensed ring, preferably a single ring or a condensed ring in which two single rings are condensed.
  • the monocyclic ring is preferably a 5- or 6-membered ring, more preferably a 6-membered ring.
  • the monocyclic ring is preferably a cyclohexane ring and a benzene ring, more preferably a cyclohexane ring.
  • Rb 1 and Rb 2 are a hydrogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms). , more preferably 2 to 18, more preferably 3 to 12), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 10), or an arylalkyl group (7 carbon atoms to 25 are preferred, 7 to 19 are more preferred, and 7 to 12 are even more preferred). These groups may have substituents to the extent that the effects of the present invention are exhibited. Rb 1 and Rb 2 may combine with each other to form a ring.
  • the ring to be formed is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring.
  • Rb 1 and Rb 2 are particularly linear, branched or cyclic alkyl groups (having preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms) which may have a substituent.
  • Rb 3 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 10 are more preferred), alkenyl groups (preferably 2 to 24 carbon atoms, more preferably 2 to 12, more preferably 2 to 6), arylalkyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 19 preferably 7 to 12), arylalkenyl groups (preferably 8 to 24 carbon atoms, more preferably 8 to 20, more preferably 8 to 16), alkoxyl groups (preferably 1 to 24 carbon atoms, 2 to 18 is more preferred, and 3 to 12 are even more preferred), an aryloxy group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12), or an arylalkyloxy group (preferably 7 to 12 carbon atoms).
  • an aryl group preferably
  • Rb 3 may further have a substituent as long as the effects of the present invention are exhibited.
  • the compound represented by formula (B1) is preferably a compound represented by formula (B1-1) or formula (B1-2) below.
  • Rb 11 and Rb 12 and Rb 31 and Rb 32 are respectively the same as Rb 1 and Rb 2 in formula (B1).
  • Rb 13 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, 7 to 12 are more preferable), and may have a substituent within the range in which the effects of the present invention are exhibited.
  • Rb 13 is preferably an arylalkyl group.
  • Rb 33 and Rb 34 each independently represents a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms , more preferably 2 to 8, more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10), an arylalkyl group (7 to 23 is preferred, 7 to 19 are more preferred, and 7 to 11 are even more preferred), and a hydrogen atom is preferred.
  • an alkyl group preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 3 carbon atoms
  • an alkenyl group preferably 2 to 12 carbon atoms , more preferably 2 to 8, more preferably 2 to 3
  • an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10
  • Rb 35 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 , 7 to 12 are more preferred), and aryl groups are preferred.
  • the compound represented by formula (B1-1) is also preferably the compound represented by formula (B1-1a).
  • Rb 11 and Rb 12 have the same definitions as Rb 11 and Rb 12 in formula (B1-1).
  • Rb 15 and Rb 16 are hydrogen atoms, alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6, even more preferably 1 to 3), alkenyl groups (preferably 2 to 12 carbon atoms, 2 to 6 more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 10), an arylalkyl group (preferably 7 to 23 carbon atoms, 7 to 19 are more preferred, and 7 to 11 are even more preferred), and a hydrogen atom or a methyl group is preferred.
  • Rb 17 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, 7 to 12 are more preferable), and aryl groups are particularly preferable.
  • an alkyl group preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms
  • an alkenyl group preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred
  • an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12
  • L is a divalent hydrocarbon group having a saturated hydrocarbon group on a connecting chain route connecting adjacent oxygen atoms and carbon atoms, wherein the number of atoms on the connecting chain route is represents a hydrocarbon group of 3 or more.
  • R N1 and R N2 each independently represent a monovalent organic group.
  • the term “connected chain” refers to the shortest (minimum number of atoms) of atomic chains on a path connecting two atoms or groups of atoms to be connected.
  • L is composed of a phenylene ethylene group, has an ethylene group as a saturated hydrocarbon group
  • the linking chain is composed of four carbon atoms, and on the route of the linking chain
  • the number of atoms of (that is, the number of atoms constituting the linked chain, hereinafter also referred to as "linked chain length" or "linked chain length”) is 4.
  • the number of carbon atoms in L (including carbon atoms other than carbon atoms in the connecting chain) in formula (B3) is preferably 3-24.
  • the upper limit is more preferably 12 or less, still more preferably 10 or less, and particularly preferably 8 or less. More preferably, the lower limit is 4 or more.
  • the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and 5 The following are particularly preferred.
  • the linking chain length of L is preferably 4 or 5, most preferably 4.
  • Specific preferred compounds of the base generator include, for example, compounds described in paragraph numbers 0102 to 0168 of WO2020/066416, and compounds described in paragraph numbers 0143 to 0177 of WO2018/038002. mentioned.
  • the base generator preferably contains a compound represented by the following formula (N1).
  • R N1 and R N2 each independently represent a monovalent organic group
  • RC1 represents a hydrogen atom or a protecting group
  • L represents a divalent linking group
  • L is a divalent linking group, preferably a divalent organic group.
  • the linking chain length of the linking group is preferably 1 or more, more preferably 2 or more.
  • the upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less.
  • the linking chain length is the number of atoms present in the atomic arrangement that provides the shortest path between two carbonyl groups in the formula.
  • R N1 and R N2 each independently represent a monovalent organic group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, more preferably 3 to 12 carbon atoms), and a hydrocarbon group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms), specifically, an aliphatic hydrocarbon group (preferably 1 to 24 carbon atoms, 1 to 12 is more preferable, 1 to 10 are more preferable) or an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10), and an aliphatic hydrocarbon groups are preferred.
  • a monovalent organic group preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, more preferably 3 to 12 carbon atoms
  • a hydrocarbon group preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms
  • an aliphatic hydrocarbon group preferably 1 to
  • an aliphatic hydrocarbon group as R N1 and R N2 because the generated base has high basicity.
  • the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group are in the aliphatic hydrocarbon chain or in the aromatic ring, You may have an oxygen atom in the substituent.
  • an aspect in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.
  • Aliphatic hydrocarbon groups constituting R N1 and R N2 include linear or branched chain alkyl groups, cyclic alkyl groups, groups related to combinations of chain alkyl groups and cyclic alkyl groups, and oxygen atoms in the chains.
  • Alkyl groups having The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms.
  • Linear or branched chain alkyl groups are, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl group, isobutyl group, secondary butyl group, tertiary butyl group, isopentyl group, neopentyl group, tertiary pentyl group, isohexyl group and the like.
  • the cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
  • Cyclic alkyl groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.
  • Groups associated with a combination of a chain alkyl group and a cyclic alkyl group preferably have 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms.
  • Groups related to combinations of chain alkyl groups and cyclic alkyl groups include, for example, a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, and an ethylcyclohexylethyl group.
  • the alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
  • An alkyl group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched.
  • R 1 N1 and R 2 N2 are preferably alkyl groups having 5 to 12 carbon atoms.
  • a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.
  • RN1 and RN2 may be linked to each other to form a ring structure.
  • the chain may have an oxygen atom or the like.
  • the cyclic structure formed by R N1 and R N2 may be a monocyclic ring or a condensed ring, but is preferably a monocyclic ring.
  • the cyclic structure to be formed is preferably a 5- or 6-membered ring containing a nitrogen atom in formula (N1), such as pyrrole ring, imidazole ring, pyrazole ring, pyrroline ring, pyrrolidine ring, imidazolidine ring, A pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring and the like can be mentioned, and a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring and a morpholine ring are preferably mentioned.
  • N1 nitrogen atom in formula (N1)
  • R C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.
  • the protective group is preferably a protective group that is decomposed by the action of an acid or a base, and preferably includes a protective group that is decomposed by an acid.
  • protecting groups include chain or cyclic alkyl groups or chain or cyclic alkyl groups having an oxygen atom in the chain.
  • Chain or cyclic alkyl groups include methyl group, ethyl group, isopropyl group, tert-butyl group, cyclohexyl group and the like.
  • the chain alkyl group having an oxygen atom in the chain specifically includes an alkyloxyalkyl group, more specifically a methyloxymethyl (MOM) group, an ethyloxyethyl (EE) group, and the like. mentioned.
  • Cyclic alkyl groups having an oxygen atom in the chain include epoxy group, glycidyl group, oxetanyl group, tetrahydrofuranyl group, tetrahydropyranyl (THP) group and the like.
  • the divalent linking group constituting L is not particularly defined, but is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group.
  • the hydrocarbon group may have substituents and may have atoms of types other than carbon atoms in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group which may have an oxygen atom in the chain, and a divalent aliphatic hydrocarbon which may have an oxygen atom in the chain group, a divalent aromatic hydrocarbon group, or a group related to a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group, A divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is more preferred.
  • the divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms.
  • the divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
  • the divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
  • a group related to a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and 7 to 10 is more preferred.
  • linking group L examples include a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, and an alkylene group having an oxygen atom in the chain.
  • a linear or branched alkenylene group, a cyclic alkenylene group, an arylene group and an arylenealkylene group are preferred.
  • the linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
  • the cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
  • the group associated with the combination of a chain alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms.
  • An alkylene group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched.
  • the alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms.
  • the linear or branched chain alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 3 carbon atoms.
  • the linear or branched chain alkenylene group preferably has 1 to 10 C ⁇ C bonds, more preferably 1 to 6, even more preferably 1 to 3.
  • the cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
  • the number of C ⁇ C bonds in the cyclic alkenylene group is preferably 1-6, more preferably 1-4, even more preferably 1-2.
  • the arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
  • the arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.
  • a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylene alkylene group are preferable, and a 1,2-ethylene group and a propanediyl group (especially 1, 3-propanediyl group), cyclohexanediyl group (especially 1,2-cyclohexanediyl group), vinylene group (especially cis-vinylene group), phenylene group (1,2-phenylene group), phenylenemethylene group (especially 1,2-phenylene methylene group) and ethyleneoxyethylene group (especially 1,2-ethyleneoxy-1,2-ethylene group) are more preferable.
  • base generators include the following, but the present invention should not be construed as being limited thereto.
  • the molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less.
  • the lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
  • Specific preferred compounds of the ionic base generator include, for example, compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.
  • ammonium salts include the following compounds, but the present invention is not limited thereto.
  • iminium salts include the following compounds, but the present invention is not limited thereto.
  • the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition of the present invention.
  • the lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more.
  • the upper limit is more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less.
  • One or two or more base generators can be used. When two or more are used, the total amount is preferably within the above range.
  • the resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent.
  • the solvent is preferably an organic solvent.
  • Organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.
  • Esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone , ⁇ -caprolactone, ⁇ -valerolactone, alkyl alkyloxyacetates (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g.
  • 3-alkyloxypropionic acid alkyl esters e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
  • 2-alkyloxypropionate alkyl esters e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl propyl oxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)
  • 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.
  • ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol Preferred examples include monobutyl ether acetate
  • Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like.
  • Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene.
  • Suitable sulfoxides include, for example, dimethyl sulfoxide.
  • Suitable ureas include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like.
  • Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, diacetone alcohol and the like.
  • a combination of dimethyl sulfoxide and ⁇ -butyrolactone or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly
  • the content of the solvent is preferably an amount such that the total solid concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass. More preferably, the amount is from 10 to 70% by mass, and even more preferably from 20 to 70% by mass.
  • the solvent content may be adjusted according to the desired thickness of the coating and the method of application.
  • the resin composition of the present invention may contain only one type of solvent, or may contain two or more types. When two or more solvents are contained, the total is preferably within the above range.
  • the resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used for electrodes, wiring, and the like.
  • metal adhesion improvers include alkoxysilyl group-containing silane coupling agents, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, and ⁇ -ketoesters. compounds, amino compounds, and the like.
  • silane coupling agent examples include compounds described in paragraph 0167 of WO 2015/199219, compounds described in paragraphs 0062 to 0073 of JP 2014-191002, and paragraphs of WO 2011/080992.
  • Compounds described in 0063-0071, compounds described in paragraphs 0060-0061 of JP-A-2014-191252, compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/097594 Compounds described in paragraph 0055, compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein.
  • silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycid.
  • xypropyltrimethoxysilane 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2 -(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimeth
  • Aluminum-based adhesion aids include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.
  • the content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of the specific resin. It is in the range of 5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the pattern and the metal layer is improved, and when it is at most the above upper limit value, the heat resistance and mechanical properties of the pattern are improved.
  • One type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, the total is preferably within the above range.
  • the resin composition of the present invention preferably further contains a migration inhibitor.
  • a migration inhibitor By including the migration inhibitor, it becomes possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the film.
  • Migration inhibitors are not particularly limited, but heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and sulfanyl groups, hindered phenolic compounds , salicylic acid derivative-based compounds, and hydrazide derivative-based compounds.
  • heterocyclic rings pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring,
  • triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 1H-tetrazole, 5- Tetrazole compounds such as phenyltetrazole and 5-amino-1H-tetrazole can be preferably used.
  • an ion trapping agent that traps anions such as halogen ions can be used.
  • Other migration inhibitors include rust inhibitors described in paragraph 0094 of JP-A-2013-015701, compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, and JP-A-2011-059656.
  • the compound described in paragraph 0052, the compound described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, the compound described in paragraph 0166 of WO 2015/199219, etc. can be used, and these The contents are incorporated herein.
  • migration inhibitors include the following compounds.
  • the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the resin composition of the present invention. , more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass.
  • migration inhibitor Only one type of migration inhibitor may be used, or two or more types may be used. When two or more migration inhibitors are used, the total is preferably within the above range.
  • the resin composition of the present invention preferably contains a polymerization inhibitor.
  • Polymerization inhibitors include phenol compounds, quinone compounds, amino compounds, N-oxyl free radical compound compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, metal compounds and the like.
  • Specific compounds of polymerization inhibitors include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4,4′-thiobis(3-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenyl hydroxylamine cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2, 6-di-tert-butyl-4-methylphenol,
  • the content of the polymerization inhibitor is preferably 0.01 to 20% by mass with respect to the total solid content of the resin composition of the present invention. It is more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.
  • polymerization inhibitor Only one type of polymerization inhibitor may be used, or two or more types may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.
  • the resin composition of the present invention preferably contains an acid scavenger in order to reduce performance changes over time from exposure to heating.
  • the acid scavenger refers to a compound that can scavenge the generated acid when present in the system, and is preferably a compound with low acidity and high pKa.
  • the acid scavenger is preferably a compound having an amino group, preferably a primary amine, secondary amine, tertiary amine, ammonium salt, tertiary amide, etc. Primary amine, secondary amine, tertiary amine, ammonium salt are preferred, and secondary amines, tertiary amines and ammonium salts are more preferred.
  • acid scavengers include compounds having an imidazole structure, diazabicyclo structure, onium structure, trialkylamine structure, aniline structure or pyridine structure, alkylamine derivatives having hydroxyl groups and/or ether bonds, and anilines having hydroxyl groups and/or ether bonds. Derivatives and the like can be mentioned preferably.
  • the acid scavenger is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, etc., and an anion of an acid less acidic than the acid generated by the acid generator. is preferred.
  • acid scavengers having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzimidazole and the like.
  • Acid scavengers having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, 1,8-diazabicyclo[5,4 ,0]undecar-7-ene and the like.
  • Acid scavengers having an onium structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxides having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris ( t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide and the like.
  • acid scavengers having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine.
  • Acid scavengers having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline and N,N-dihexylaniline.
  • acid scavengers having a pyridine structure include pyridine and 4-methylpyridine.
  • alkylamine derivatives having hydroxyl groups and/or ether bonds include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tris(methoxyethoxyethyl)amine and the like.
  • aniline derivatives having hydroxyl groups and/or ether bonds include N,N-bis(hydroxyethyl)aniline.
  • preferred acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N , N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexyl
  • compositions according to the present invention may or may not contain an acid scavenger, but when it does, the content of the acid scavenger is usually from 0.001 to 0.001 based on the total solid content of the composition. 10% by mass, preferably 0.01 to 5% by mass.
  • the acid generator/acid scavenger (molar ratio) is more preferably 5.0-200, still more preferably 7.0-150.
  • the resin composition of the present invention may contain a filler.
  • the filler is preferably thermally conductive.
  • the filler may be electrically insulating, semiconducting, or electrically conductive.
  • the degree of electrical insulation and conductivity is appropriately selected according to the design and purpose.
  • the lower limit of the volume resistivity of the filler is preferably 1.0 ⁇ 10 11 ⁇ cm or more, more preferably 3.0 ⁇ 10 11 ⁇ cm or more. is more preferable, and 1.0 ⁇ 10 12 ⁇ cm or more is particularly preferable.
  • the upper limit of the volume resistivity is not particularly limited, it is preferably 1.0 ⁇ 10 18 or less ⁇ cm, for example.
  • the lower limit of the volume resistivity of the filler is not particularly limited, but practically it is 1.0 ⁇ 10 ⁇ 7 ⁇ cm or more.
  • the upper limit of the volume resistivity is preferably less than 1.0 ⁇ 10 11 ⁇ cm.
  • the thermal diffusivity of the filler is, for example, preferably 5.0 ⁇ 10 ⁇ 7 m 2 s ⁇ 1 or more, more preferably 1.0 ⁇ 10 ⁇ 6 m 2 s ⁇ 1 or more, and more preferably 2.0. It is more preferably 3.0 ⁇ 10 ⁇ 6 m 2 s ⁇ 1 or more, particularly preferably 3.0 ⁇ 10 ⁇ 6 m 2 s ⁇ 1 or more.
  • the upper limit of the thermal diffusivity of the filler is not particularly limited, it is preferably 1.0 ⁇ 10 ⁇ 4 m 2 s ⁇ 1 or less, for example.
  • the density of the filler is, for example, preferably 4.0 g/cm 3 or less, more preferably 3.0 g/cm 3 or less.
  • the lower limit of the density of the filler is not particularly limited, it is preferably 1.0 g/cm 3 or more, for example.
  • the density of the filler in this specification means the density of the solid content among the components constituting the filler. do.
  • the filler contains an electrically insulating material.
  • the electrically insulating filler material is, for example, an electrically insulating ceramic made of a nitrogen compound, an oxygen compound, a silicon compound, a boron compound, a carbon compound, or a composite compound thereof.
  • Nitrogen compounds include, for example, boron nitride, aluminum nitride, and silicon nitride.
  • oxygen compounds include metal oxides such as aluminum oxide (alumina), magnesium oxide (magnesia), zinc oxide, silicon oxide (silica), beryllium oxide, titanium oxide (titania), copper oxide and cuprous oxide.
  • Silicon compounds and carbon compounds include silicon carbide.
  • Boron compounds include, for example, metal borides such as titanium boride.
  • carbon compounds are, for example, carbon matrix materials with predominantly ⁇ bonds, such as diamond.
  • the composite compound include mineral ceramics such as magnesite (magnesium carbonate), perovskite (calcium titanate), talc, mica, kaolin, bentonite, and pyroferrite.
  • the electrically insulating filler material may also be a metal hydroxide such as magnesium hydroxide or aluminum hydroxide.
  • the filler material preferably contains at least one of ceramics made of nitrogen compounds, ceramics made of metal oxides, and metal hydroxides.
  • the filler material preferably contains, for example, boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, zinc oxide, and at least one selected from the group consisting of beryllium oxide and aluminum hydroxide.
  • the filler material particularly preferably contains at least one selected from the group consisting of boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, zinc oxide and beryllium oxide. More preferably, it contains at least one of silicon and aluminum oxide.
  • boron nitride has c-BN (cubic crystal structure), w-BN (wurtzite structure), h-BN (hexagonal crystal structure), r-BN (rhombohedral crystal structure), t-BN (turbulent structure ) or any other structure.
  • Boron nitride has a spherical shape and a scaly shape, and both can be used.
  • the IX-3 series manufactured by Nippon Shokubai Co., Ltd., etc. can be suitably used.
  • Examples of conductive filler materials include carbon substrate materials in which ⁇ bonds are dominant, such as graphite, carbon black, graphite, carbon fibers (pitch-based, PAN-based), carbon nanotubes (CNT), and carbon nanofibers (CNF). is mentioned.
  • Such filler materials may be metals such as silver, copper, iron, nickel, aluminum and titanium, and alloys such as stainless steel (SUS).
  • conductive metal oxides such as zinc oxide doped with different elements and conductive ceramics such as ferrite can also be used as such filler materials.
  • the filler may have a structure in which semiconductor or conductive thermally conductive particles are coated or surface-treated with an electrically insulating material such as silica. According to such an aspect, it becomes easy to control the thermal conductivity and the electrical insulation individually, so that the adjustment of the thermal conductivity and the electrical insulation becomes easy.
  • methods for forming a silica film on the surface include a water glass method and a sol-gel method.
  • fillers can be used singly or in combination of two or more.
  • the shape of the filler is not particularly limited, and various shapes can be used.
  • the filler may be subjected to surface treatment such as silane coupling treatment, titanate coupling treatment, epoxy treatment, urethane treatment, and oxidation treatment.
  • Surface treatment agents used for surface treatment include, for example, polyol, aluminum oxide, aluminum hydroxide, silica (silicon oxide), hydrated silica, alkanolamine, stearic acid, organosiloxane, zirconium oxide, hydrogen dimethicone, silane coupling agent, Titanate coupling agents and the like. Among them, silane coupling agents are preferred.
  • the average particle size of the filler is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, and even more preferably 10 ⁇ m or less.
  • the average particle size of the filler is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, still more preferably 0.1 ⁇ m or more, and particularly preferably 0.3 ⁇ m or more. preferable.
  • the "average particle size" of the filler can be obtained by observing the filler in the polyimide-containing portion with a scanning electron microscope (SEM) and observing the portion (primary particles) where the particles of the filler are not aggregated.
  • the average particle size can be calculated as the average diameter of the smallest enclosing circle for the apparent outline of each particle observed by SEM. Specifically, it can be described by the method described in Examples described later.
  • the filler may contain a particulate mixture in which at least two types of particle groups with different particle sizes are mixed.
  • the "particle size" of a certain particle group is also determined by the same method as the "particle size” of the filler. With this configuration, the smaller particles are embedded between the larger particles, reducing the spacing between the fillers and thus increasing the number of contact points compared to only single-diameter fillers, thus increasing the thermal conductivity. improve sexuality. For example, when two types of particle groups with different particle sizes are mixed, two peaks are observed in the particle size distribution of the filler containing these particle groups. Therefore, by confirming the number of peaks in the particle size distribution of the filler, it is possible to confirm how many types of particle groups with different particle diameters are included in the particulate mixture that is the filler.
  • the peak particle size ratio (the ratio of particle sizes corresponding to peak apexes) between at least two peaks is preferably 1.5 to 50. .
  • the lower limit is preferably 2 or more, more preferably 4 or more.
  • the upper limit is preferably 40 or less, more preferably 20 or less. If the peak ratio is within the above range, it becomes easy for the small-diameter filler to occupy the space between the large-diameter fillers while preventing the large-diameter filler from becoming coarse particles.
  • the peak intensity ratio of the peak with large particle size to the peak with small particle size is preferably 0.2 to 5.0.
  • the lower limit is preferably 0.2 or more, more preferably 0.5 or more.
  • the upper limit is preferably 5.0 or less, more preferably 3.0 or less.
  • the filler content is preferably 10% by mass or more, more preferably 30% by mass or more, relative to the total solid content of the resin composition.
  • the upper limit of the content is not particularly limited, it is preferably 90% by mass or less, more preferably 75% by mass or less, from the viewpoint of processability by lithography.
  • the ratio of the particle group having a particle diameter of 0.5 to 15 ⁇ m in the total filler is preferably 50% by mass or more, more preferably 80% by mass or more.
  • the upper limit of this ratio can be 100% by mass, or can be 99% by mass or less. This ratio is preferably 99% by mass or less, more preferably 95% by mass or less.
  • the filler can be used singly or in combination of two or more.
  • the total amount thereof is preferably within the above range.
  • the resin composition of the present invention may contain various additives such as surfactants, higher fatty acid derivatives, ultraviolet absorbers, organic titanium compounds, antioxidants, Aggregation inhibitors, phenolic compounds, other polymer compounds, plasticizers and other auxiliaries (for example, antifoaming agents, flame retardants, etc.), etc., can be blended. Properties such as film physical properties can be adjusted by appropriately containing these components. These components are described, for example, from paragraph number 0183 of JP-A-2012-003225 (paragraph number 0237 of corresponding US Patent Application Publication No. 2013/0034812), paragraph of JP-A-2008-250074 The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated herein. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.
  • additives such as surfactants, higher fatty acid derivatives, ultraviolet absorbers, organic titanium compounds, antioxidants
  • surfactant various surfactants such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants can be used.
  • the surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
  • the liquid properties (especially fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and liquid saving are further improved. can do. That is, when a film is formed using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved. , the coatability to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with little unevenness in thickness.
  • fluorosurfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (manufactured by DIC Corporation), Florado FC430, FC431, FC171, Novec FC4430, FC4432 (manufactured by 3M Japan Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (Asahi Glass Co., Ltd.
  • Fluorinated surfactants compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327, compounds described in paragraphs 0117-0132 of JP-A-2011-132503 can also be used, the contents of which are incorporated herein.
  • a block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090, the contents of which are incorporated herein.
  • the fluorosurfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meta)
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.
  • the weight average molecular weight of the above compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
  • a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used as a fluorine-based surfactant. Specific examples include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, the contents of which are incorporated herein.
  • Commercially available products include Megafac RS-101, RS-102 and RS-718K manufactured by DIC Corporation.
  • the fluorine content in the fluorine-based surfactant is preferably 3-40% by mass, more preferably 5-30% by mass, and particularly preferably 7-25% by mass.
  • a fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and saving liquid, and has good solubility in the composition.
  • silicone-based surfactants examples include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (the above, Toray Dow Corning Co., Ltd.
  • TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 manufactured by Momentive Performance Materials
  • KP341, KF6001, KF6002 manufactured by Shin-Etsu Silicone Co., Ltd.
  • BYK307, BYK323, and BYK330 manufactured by BYK-Chemie Co., Ltd.
  • Hydrocarbon surfactants include, for example, Pionin A-76, Nucalgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, Pionin D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, Pionin P-4050-T and the like (manufactured by Takemoto Oil & Fat Co., Ltd.), and the like.
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Examples include polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester.
  • cationic surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 77, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.
  • anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.), and Sandet BL (manufactured by Sanyo Kasei Co., Ltd.).
  • the surfactant content is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.
  • the resin composition of the present invention is added with a higher fatty acid derivative such as behenic acid or behenic acid amide, and the resin composition of the present invention is dried in the process of drying after coating. may be unevenly distributed on the surface of the
  • the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition of the present invention. Only one type of higher fatty acid derivative may be used, or two or more types thereof may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.
  • the composition of the present invention may contain an ultraviolet absorber.
  • an ultraviolet absorber As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used.
  • salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate, and the like.
  • benzophenone-based UV absorbers examples include 2,2'-dihydroxy-4- Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- and hydroxy-4-octoxybenzophenone.
  • benzotriazole-based UV absorbers examples include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3 '-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-( 2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2 -(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5' -(1,
  • Examples of substituted acrylonitrile UV absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate.
  • examples of triazine-based UV absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl )-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) -mono(hydroxyphenyl)triazine compounds such as 1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(
  • the above various ultraviolet absorbers may be used singly or in combination of two or more.
  • the composition of the present invention may or may not contain an ultraviolet absorber, but when it does, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid mass of the composition of the present invention. It is preferably at least 1% by mass, more preferably at least 0.01% by mass and not more than 0.1% by mass.
  • the resin composition of this embodiment may contain an organic titanium compound. By including the organic titanium compound in the resin composition, it is possible to form a resin layer having excellent chemical resistance even when cured at a low temperature.
  • Organotitanium compounds that can be used include those in which organic groups are attached to titanium atoms through covalent or ionic bonds. Specific examples of organotitanium compounds are shown below in I) to VII): I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the storage stability of the resin composition is good and a good curing pattern can be obtained.
  • titanium bis(triethanolamine) diisopropoxide titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate ), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like.
  • Tetraalkoxytitanium compounds for example titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide , titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis ⁇ 2,2-(allyloxymethyl) butoxide ⁇ ] and the like.
  • Titanocene compounds for example, pentamethylcyclopentadienyltitanium trimethoxide, bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis( ⁇ 5-2, 4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and the like.
  • Monoalkoxy titanium compounds for example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, and the like.
  • Titanium oxide compounds for example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide and the like.
  • the organotitanium compound at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds provides better chemical resistance. It is preferable from the viewpoint of performance.
  • titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide) and bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H) -pyrrol-1-yl)phenyl)titanium is preferred.
  • the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin.
  • the amount is 0.05 parts by mass or more, the resulting cured pattern exhibits good heat resistance and chemical resistance more effectively. Excellent.
  • compositions of the present invention may contain antioxidants.
  • an antioxidant By containing an antioxidant as an additive, it is possible to improve the elongation properties of the cured film and the adhesion to metal materials.
  • Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound.
  • Preferred phenolic compounds include hindered phenolic compounds.
  • a compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred.
  • a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable as the above substituent.
  • the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule.
  • Phosphorus-based antioxidants can also be suitably used as antioxidants.
  • a phosphorus antioxidant tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl ) oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like.
  • antioxidants examples include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Corporation) and the like.
  • compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used, the contents of which are incorporated herein.
  • the composition of the present invention may also contain latent antioxidants, if desired.
  • the latent antioxidant is a compound in which the site functioning as an antioxidant is protected with a protective group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst.
  • a compound that functions as an antioxidant by removing the protective group by the reaction is exemplified.
  • latent antioxidants include compounds described in WO 2014/021023, WO 2017/030005, and JP 2017-008219, the contents of which are incorporated herein.
  • Commercially available latent antioxidants include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.).
  • Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds of formula (3).
  • R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R 6 represents alkylene having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). represents a group.
  • R 7 represents a monovalent to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom and a nitrogen atom.
  • k represents an integer of 1 to 4;
  • the compound represented by formula (3) suppresses oxidative deterioration of the aliphatic groups and phenolic hydroxyl groups of the resin. In addition, metal oxidation can be suppressed by the antirust action on the metal material.
  • R7 includes an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, combinations thereof, and the like, which may further have a substituent.
  • Examples of compounds represented by general formula (3) include the following, but are not limited to the structures below.
  • the amount of antioxidant to be added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin.
  • the addition amount 0.1 parts by mass or more By making the addition amount 0.1 parts by mass or more, the effect of improving elongation characteristics and adhesion to metal materials can be easily obtained even in a high-temperature and high-humidity environment.
  • the interaction with the agent improves the sensitivity of the resin composition.
  • Only one kind of antioxidant may be used, or two or more kinds thereof may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
  • the resin composition of the present embodiment may contain an anti-aggregation agent as necessary.
  • Anti-aggregating agents include sodium polyacrylate and the like.
  • the aggregation inhibitor may be used alone or in combination of two or more.
  • the composition of the present invention may or may not contain an anti-aggregating agent, but when it is included, the content of the anti-aggregating agent is 0.01% by mass relative to the total solid mass of the composition of the present invention. It is preferably at least 10% by mass, more preferably at least 0.02% by mass and not more than 5% by mass.
  • the resin composition of the present embodiment may contain a phenolic compound as necessary.
  • phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X (these are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR -BIPC-F (these are trade names, manufactured by Asahi Organic Chemicals Industry Co., Ltd.) and the like.
  • one type of phenolic compound may be used alone, or two or more types may be used in combination.
  • the composition of the present invention may or may not contain a phenolic compound, but if it does, the content of the phenolic compound is 0.01% by mass relative to the total solid mass of the composition of the present invention. It is preferably at least 30% by mass, more preferably at least 0.02% by mass and not more than 20% by mass.
  • Other polymer compounds include siloxane resins, (meth)acrylic polymers obtained by copolymerizing (meth)acrylic acid, novolac resins, resole resins, polyhydroxystyrene resins, and copolymers thereof.
  • Other polymer compounds may be modified products into which cross-linking groups such as methylol groups, alkoxymethyl groups and epoxy groups have been introduced.
  • composition of the present invention may or may not contain other polymer compounds, but when it does, the content of the other polymer compound is 0 relative to the total solid mass of the composition of the present invention. It is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.
  • the viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition. From the viewpoint of coating film thickness, it is preferably 1,000 mm 2 /s to 12,000 mm 2 /s, more preferably 2,000 mm 2 /s to 10,000 mm 2 /s, and 2,500 mm 2 /s to 8,000 mm. 2 /s is more preferred. If it is the said range, it will become easy to obtain a coating film with high uniformity. If it is 1,000 mm 2 /s or more , it is easy to apply the film with a film thickness required, for example, as an insulating film for rewiring. A coating is obtained.
  • the water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the moisture content include adjusting the humidity in the storage conditions and reducing the porosity of the storage container during storage.
  • the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm.
  • metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are included, the total of these metals is preferably within the above range.
  • a raw material having a low metal content is selected as a raw material constituting the resin composition of the present invention.
  • the raw material constituting the product is filtered through a filter, or the inside of the apparatus is lined with polytetrafluoroethylene or the like to perform distillation under conditions in which contamination is suppressed as much as possible.
  • the resin composition of the present invention preferably has a halogen atom content of less than 500 ppm by mass, more preferably less than 300 ppm by mass, and less than 200 ppm by mass from the viewpoint of wiring corrosion. is more preferred.
  • those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass.
  • Halogen atoms include chlorine and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms or chlorine ions and bromine ions is within the above ranges.
  • ion exchange treatment and the like are preferably mentioned.
  • a conventionally known container can be used as the container for the resin composition of the present invention.
  • the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resin are used. It is also preferred to use bottles with a seven-layer structure. Examples of such a container include the container described in JP-A-2015-123351.
  • a cured product of this resin composition By curing the resin composition of the present invention, a cured product of this resin composition can be obtained.
  • the cured product of the present invention is a cured product obtained by curing the resin composition of the present invention. Curing of the resin composition is preferably by heating, and the heating temperature is more preferably in the range of 120°C to 400°C, more preferably in the range of 140°C to 380°C, and 170°C. It is particularly preferred to be in the range of -350°C.
  • the form of the cured product of the resin composition is not particularly limited, and can be selected from film-like, rod-like, spherical, pellet-like, etc. according to the application.
  • this cured product is preferably in the form of a film.
  • pattern processing of the resin composition can be used to form protective films on walls, form via holes for conduction, adjust impedance, capacitance or internal stress, and impart heat dissipation functions. You can also choose the shape.
  • the film thickness of the cured product (film made of the cured product) is preferably 0.5 ⁇ m or more and 150 ⁇ m or less.
  • the shrinkage ratio when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less.
  • the imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or higher, more preferably 80% or higher, and even more preferably 90% or higher. If it is 70% or more, a cured product having excellent mechanical properties may be obtained.
  • the elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
  • the glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180° C. or higher, more preferably 210° C. or higher, and even more preferably 230° C. or higher.
  • the manufacturing method of the joined body of the present invention comprises a step of preparing a substrate A having a surface provided with a wiring terminal, a polyimide-containing portion forming step of forming a polyimide-containing portion on the surface of the substrate A provided with the wiring terminal, and a wiring terminal. and a bonding step of bonding the surface of the substrate A having the polyimide-containing portion and the surface of the substrate B having the wiring terminal, wherein the polyimide-containing portion is lower than the bonding temperature in the bonding step.
  • the details of the substrate A, the substrate B, and each step in the method for producing a joined body of the present invention are as follows: , and preferred embodiments are also the same.
  • the conjugate of the present invention is a conjugate obtained by the method for producing a conjugate of the present invention.
  • Preferred aspects of the joined body are the same as the preferred aspects of the joined body in the above-described method for producing a joined body using the composition for forming a polyimide-containing portion of the present invention.
  • a precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
  • the resulting reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of crude polymer.
  • the resulting crude polymer was collected by filtration and dissolved in 200 mL of tetrahydrofuran to obtain a crude polymer solution.
  • the resulting crude polymer solution was dropped into 3 liters of water to precipitate the polymer, and the resulting precipitate was collected by filtration and dried in vacuo to obtain a powdery polymer P-1.
  • the weight average molecular weight (Mw) of this polymer was measured and found to be 23,000.
  • Polymer P-1 is a resin having the following structure. Subscripts in parentheses represent the molar ratio of each repeating unit.
  • each component was mixed as described in Table 1 to prepare a uniform solution.
  • the resulting solution was pressure filtered at a pressure of 0.4 MPa through a filter with a pore width of 20 ⁇ m to obtain a resin composition.
  • the contents of the components described in the table were the amounts (parts by mass) described in the table.
  • the description of "-" indicates that the composition does not contain the corresponding component.
  • ⁇ B-1 Tetraethylene glycol dimethacrylate (manufactured by Arkema)
  • ⁇ B-2 Light acrylate DCP-A (manufactured by Kyoeisha Chemical) *B-3: A compound having the following structure, the subscript in the parenthesis represents the number of repetitions.
  • ⁇ B-4 NK Ester A-TMMT (manufactured by Shin-Nakamura Chemical)
  • H-1 GBL ( ⁇ -butyrolactone)
  • H-2 EL (ethyl lactate)
  • H-3 NMP (N-methylpyrrolidone)
  • H-4 DMSO (dimethyl sulfoxide)
  • Pillar substrates having the following sizes and metal types were produced by plating. a) Pitch: 25 ⁇ m, copper pillar diameter: 10 ⁇ m, copper pillar height: 10 ⁇ m b) Pitch: 45 ⁇ m, copper/tin pillar diameter: 20 ⁇ m, copper/tin pillar height: 2/8 ⁇ mm, silicon wafer, copper, and tin are formed in this order.
  • FIG. 6(a) is a schematic sectional view of the above a) and c).
  • 10 denotes a substrate
  • 12 denotes wiring terminals (pillars) made of copper.
  • the arithmetic mean value of the pillar diameters d in each pillar is the pillar diameter, which is 10 ⁇ m in a) and 20 ⁇ m in c).
  • the arithmetic average value of the pillar spacing p in each pillar is the pitch, which is 10 ⁇ m in a) and 20 ⁇ m in c).
  • FIG. 6(a) the arithmetic mean value of the pillar height h of each pillar is the pillar height, which is 10 ⁇ m in a) and 10 ⁇ m in c).
  • FIG. 6(b) is a schematic sectional view of the above b).
  • 10 denotes a substrate and 12 denotes a wiring terminal.
  • the wiring terminal 12 is formed of a pillar (conducting path) 14 made of tin and a pillar (electrode) 16 made of copper.
  • the arithmetic mean value of the pillar diameters d in each pillar is the pillar diameter, which is 20 ⁇ m in b).
  • FIG. 6(b) the arithmetic mean value of the pillar diameters d in each pillar is the pillar diameter, which is 20 ⁇ m in b).
  • the arithmetic mean value of the pillar spacing p of each pillar is the pitch, which is 45 ⁇ m in b).
  • the arithmetic mean value of the height h1 of the conduction path in each pillar is the tin pillar height, and in b) it is 8 ⁇ m.
  • the arithmetic mean value of the electrode height h2 in each pillar is the copper pillar height, which is 2 ⁇ m in b).
  • Example 15 ⁇ Production of substrate/substrate laminate (bonded body) (Example 15)>
  • Example 15 after preparing two flattened substrates (substrate A and substrate B in the table), only the substrate B was coated with the composition on the surface with RAD3510F/12 (manufactured by LINTEC). Affixed the tape. After that, using DFG8560 (manufactured by DISCO), the back surface (the surface opposite to the composition coated surface) was polished to the substrate B, and after forming the wafer to a thickness of 150 ⁇ m, the substrate was bonded with a bonder 540 manufactured by EVG. Evaluation was carried out in the same manner as in Example 1, except that they were joined together.
  • Example 17 ⁇ Production of substrate/substrate laminate (bonded body) (Example 17)>
  • substrate preparation and evaluation were carried out in the same manner as in Example 1, except that composition 4 was used for substrate B and was applied to a film thickness of 10 ⁇ m.
  • Example 18 ⁇ Production of substrate/substrate laminate (bonded body) (Example 18)>
  • substrate preparation and evaluation were carried out in the same manner as in Example 1, except that the substrate d) was used as the substrate B.
  • Example 20 ⁇ Production of substrate/substrate laminate (bonded body) (Example 20)>
  • substrate preparation and evaluation were carried out in the same manner as in Example 2, except that the substrate B was preheated at 70°C and then bonding was started at 70°C.
  • Substrate A (underlying substrate, daughter chip) 1x silicon wafer 1y substrate provided with polyimide containing portion 1z laminate 2 substrate B (mother chip) 2a surface of the second polyimide-containing portion of substrate B 2x silicon wafer 2y through-hole electrode 31 electrode (metal portion) 31a electrode tip 32 electrode (metal part) 4 Resin composition layer 4a Surface of polyimide-containing portion (before flattening) 4b Surface of polyimide-containing part (after flattening) 41 polyimide-containing portion 42 second polyimide-containing portion 8 electronic circuit region 10 substrate 12 wiring terminal A 14 conductive path 16 electrode 81 electronic circuit 90 semiconductor device 91 bonding film 93 solder electrode (bump) 94 underfill 95 sealing resin 96 wire bonding 97a substrate electrode 97b wire bonding pad 98 base substrate 99 solder ball 100 bonded body 101a to 101d semiconductor element 101 bonded body 102b to 102d through electrode 103a to 103e metal bump 105 rewiring layer 110, 110a, 110b resin layer 115

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Abstract

Provided is a composition for forming a polyimide-containing part, the composition being used in a joined body manufacturing method including: a step of preparing a substrate A; a polyimide-containing part forming step of forming a polyimide-containing part on the surface of the substrate A on which wiring terminals are provided; a step of preparing a substrate B; a joining step of joining the surface having the polyimide-containing part of the substrate A and the surface of the substrate B on which wiring terminals are provided. The polyimide-containing part is a member formed from the composition for forming a polyimide-containing part. The glass transition temperature of the polyimide-containing part is lower than the joining temperature of the joining step. Also provided are a joined body manufacturing method using the composition for forming a polyimide-containing part, a joined body, a device manufacturing method, and a device.

Description

ポリイミド含有部形成用組成物、接合体の製造方法、接合体、デバイスの製造方法、及び、デバイス。A composition for forming a polyimide-containing part, a method for producing a joined body, a joined body, a method for producing a device, and a device.
　本発明はポリイミド含有部形成用組成物、接合体の製造方法、接合体、デバイスの製造方法、及び、デバイスに関する。 The present invention relates to a composition for forming a polyimide-containing part, a method for producing a joined body, a method for producing a joined body, a device, and a device.
　携帯電話やタブレット型の端末などの電子機器はますます小型化し、一方でその機能は多様化している。そのニーズに対応するために、電子機器に組み込まれる電子回路には、さらなる小型化、高集積化、高密度実装が必要になっている。多機能で高いパフォーマンスと信頼性を維持しつつ小型化を実現する技術として、ＳＩＰ(System in Package)、ＭＣＭ（Multi Chip Module）、ＰＯＰ（Package on Package）等の実装技術が注目を集めている。これらの技術によれば、部品点数を減らし半導体製造工程を簡略化できるため、電子機器を低コスト化する観点からも期待されている。 Electronic devices such as mobile phones and tablet terminals are getting smaller and smaller, while their functions are diversifying. To meet these needs, electronic circuits incorporated in electronic devices are required to be further miniaturized, highly integrated, and mounted at high density. Packaging technologies such as SIP (System in Package), MCM (Multi Chip Module), and POP (Package on Package) are attracting attention as technologies that achieve miniaturization while maintaining high performance and reliability with multiple functions. . Since these techniques can reduce the number of parts and simplify the semiconductor manufacturing process, they are also expected to reduce the cost of electronic devices.
　しかし、ＳＩＰではワイヤボンディングにより各チップ間を結ぶため、従来のＳＯＣ（System on Chip）と同等の処理速度を得ることが難しい。また、ワイヤボンディングによる接続は製造工程も煩雑なものとなり、製品コストや製品品質においても改善が望まれていた。このような課題に対応するものとして、ＣＯＣ（Chip on Chip）の実装技術が開発された。ＣＯＣでは、チップ間をフリップチップ接続で結び伝送距離を短くすることができるため、ＳＯＣと同等の高速性能を得ることができる。図１は一般的なＣＯＣの構造を示す断面図である。この例におけるＣＯＣはドーターチップ（第一の基板）１とマザーチップ（第二の基板）２とを具備してなる。マザーチップ２には電子回路（図示せず）およびフリップチップ電極（図示せず）が形成され、はんだ電極（バンプ）９３を介してドーターチップ１が支持されつつ接続されている。はんだ電極９３の周囲はアンダーフィル９４で埋められて絶縁性が確保されている。マザーチップ２はボンディングフィルム９１によってベース基板９８に接着することで絶縁性を維持しつつ搭載されている。その電気的な接続はワイヤボンディングパッド９７ｂ、ワイヤボンディング９６および基板電極９７ａを介して行われる。このようなＣＯＣ構造は封止樹脂９５で封止されて半導体デバイス９０が構成される。この半導体デバイス９０にははんだボール９９が設けられ、これを介して電子機器に組み込まれる。また、このフリップチップ実装の技術をさらに応用して、ＴＳＶ（Through silicon via，スルーシリコンビア）を用いた三次元実装に関する技術およびその材料が検討されている（非特許文献１）。 However, in SIP, since each chip is connected by wire bonding, it is difficult to obtain the same processing speed as the conventional SOC (System on Chip). Moreover, connection by wire bonding complicates the manufacturing process, and improvements in product cost and product quality have been desired. A COC (Chip on Chip) mounting technology has been developed as a solution to such problems. In the COC, chips can be flip-chip-connected to shorten the transmission distance, so high-speed performance equivalent to that of the SOC can be obtained. FIG. 1 is a cross-sectional view showing the structure of a typical COC. The COC in this example comprises a daughter chip (first substrate) 1 and a mother chip (second substrate) 2 . An electronic circuit (not shown) and flip chip electrodes (not shown) are formed on the mother chip 2 , and the daughter chip 1 is supported and connected via solder electrodes (bumps) 93 . The periphery of the solder electrode 93 is filled with an underfill 94 to ensure insulation. The mother chip 2 is mounted on the base substrate 98 while maintaining insulation by being adhered to the base substrate 98 by the bonding film 91 . The electrical connection is made through wire bonding pad 97b, wire bonding 96 and substrate electrode 97a. Such a COC structure is sealed with a sealing resin 95 to form a semiconductor device 90 . The semiconductor device 90 is provided with solder balls 99, through which it is incorporated into electronic equipment. Further, by further applying this flip-chip mounting technique, techniques and materials for three-dimensional mounting using TSV (Through Silicon Via) are being studied (Non-Patent Document 1).
　上記図１のような構造のＣＯＣ構造の素子では、ドーターチップ１とマザーチップ２とをはんだバンプ９３で接続固定した後に、その間隙にアンダーフィル９４が埋入される。したがって、アンダーフィルを構成する材料には流動性のある樹脂が採用され、はんだバンプ間に充填した後に硬化して成形されている。
　ここで、樹脂の接着力によりドーターチップ１とマザーチップ２とが接着されているが、接着性向上の観点から、これら２つの基板の間の最大剥離抗力の向上が求められている。 In the element of the COC structure having the structure shown in FIG. 1, after the daughter chip 1 and the mother chip 2 are connected and fixed by the solder bumps 93, the underfill 94 is filled in the gap. Therefore, a fluid resin is used as the material forming the underfill, and the resin is cured and molded after being filled between the solder bumps.
Here, the daughter chip 1 and the mother chip 2 are bonded together by the adhesive strength of the resin, and from the viewpoint of improving the adhesiveness, it is desired to improve the maximum peeling resistance between these two substrates.
　そこで、本発明は、２つの基板を接合する際に２つの基板の間の最大剥離抗力が大きい接合体が得られるポリイミド含有部形成用組成物、上記ポリイミド含有部形成用組成物を用いた接合体の製造方法、上記製造方法により得られる接合体、上記接合体の製造方法を含むデバイスの製造方法、及び、上記接合体を含むデバイスを提供することを目的とする。 Therefore, the present invention provides a composition for forming a polyimide-containing portion that can provide a bonded body having a large maximum peeling force between two substrates when bonding two substrates, and bonding using the composition for forming a polyimide-containing portion. An object of the present invention is to provide a method for manufacturing a body, a bonded body obtained by the manufacturing method, a method for manufacturing a device including the method for manufacturing the bonded body, and a device including the bonded body.
　本発明の具体的な態様の例を以下に示す。
＜１＞　配線端子を備える面を有する基板Ａを準備する工程、
　上記基板Ａの上記配線端子を備える面上にポリイミド含有部を形成するポリイミド含有部形成工程、
　配線端子を備える面を有する基板Ｂを準備する工程、及び、
　上記基板Ａのポリイミド含有部を有する面と、上記基板Ｂにおける上記配線端子を備える面とを接合する接合工程、を含む接合体の製造方法において使用されるポリイミド含有部形成用組成物であって、
　上記ポリイミド含有部は上記ポリイミド含有部形成用組成物から形成される部材であり、
上記ポリイミド含有部のガラス転移温度が、上記接合工程における接合温度より低い
　ポリイミド含有部形成用組成物。
＜２＞　ポリイミド前駆体及び溶剤を含む、＜１＞に記載のポリイミド含有部形成用組成物。
＜３＞　マイグレーション抑制剤を更に含む、＜１＞又は＜２＞に記載のポリイミド含有部形成用組成物。
＜４＞上記ポリイミド含有部のガラス転移温度が３５０℃以下である、＜１＞～＜３＞のいずれか１つに記載のポリイミド含有部形成用組成物。
＜５＞上記ポリイミド含有部のガラス転移温度が、上記接合工程における接合温度より３０℃以上低い、＜１＞～＜４＞のいずれか１つに記載のポリイミド含有部形成用組成物。
＜６＞　上記接合工程における接合温度が３８０℃以下である、＜１＞～＜５＞のいずれか１つに記載のポリイミド含有部形成用組成物。
＜７＞　上記基板Ａの形態がウエハである、＜１＞～＜６＞のいずれか１つに記載のポリイミド含有部形成用組成物。
＜８＞　上記基板Ｂの形態がチップである、＜１＞～＜７＞のいずれか１つに記載のポリイミド含有部形成用組成物。
＜９＞　上記基板Ｂの形態がウエハである、＜１＞～＜７＞のいずれか１つに記載のポリイミド含有部形成用組成物。
＜１０＞　接合工程において、ポリイミド含有部を備えた基板Ａの温度が７０℃以上に予熱されている、＜１＞～＜９＞のいずれか１つに記載のポリイミド含有部形成用組成物。
＜１１＞　上記ポリイミド含有部形成工程と、上記接合工程との間に、基板Ａのポリイミド含有部の表面を平坦化する平坦化工程を含む、＜１＞～＜１０＞のいずれか１つに記載のポリイミド含有部形成用組成物。
＜１２＞　上記平坦化工程が、物理研磨によって行なわれる、＜１１＞に記載のポリイミド含有部形成用組成物。
＜１３＞　上記平坦化工程が、化学研磨によって行なわれる、＜１１＞に記載のポリイミド含有部形成用組成物。
＜１４＞　上記接合工程において、上記基板Ａのポリイミド含有部を有する面に含まれる電極と、上記基板Ｂにおける上記配線端子を備える面における電極とが直接接するように接合される、＜１＞～＜１３＞のいずれか１つに記載のポリイミド含有部形成用組成物。
＜１５＞　上記接合工程の前に、上記基板Ｂの上記配線端子を備える面上に第２のポリイミド含有部を形成する第２のポリイミド含有部形成工程を更に含む、＜１＞～＜１４＞のいずれか１つに記載のポリイミド含有部形成用組成物。
＜１６＞　感光性化合物を更に含む、＜１＞～＜１５＞のいずれか１つに記載のポリイミド含有部形成用組成物。
＜１７＞　上記ポリイミド含有部形成工程が、基板Ａの上記配線端子を備える面上にポリイミド含有部形成用組成物を適用し、加熱することを含む、＜１＞～＜１６＞のいずれか１つに記載のポリイミド含有部形成用組成物。
＜１８＞　上記加熱における加熱温度が、３７５℃以下である、＜１７＞に記載のポリイミド含有部形成用組成物。
＜１９＞　配線端子を備える面を有する基板Ａを準備する工程、
　上記基板Ａの上記配線端子を備える面上にポリイミド含有部を形成するポリイミド含有部形成工程、
　配線端子を備える面を有する基板Ｂを準備する工程、及び、
　上記基板Ａのポリイミド含有部を有する面と、上記基板Ｂにおける上記配線端子を備える面とを接合する接合工程、を含み、
　上記ポリイミド含有部のガラス転移温度が、上記接合工程における接合温度よりも低い温度である接合体の製造方法。
＜２０＞　＜１９＞に記載の製造方法によって得られる接合体。
＜２１＞　＜１９＞に記載の接合体の製造方法を含む、デバイスの製造方法。
＜２２＞　＜２０＞に記載の接合体を含む、デバイス。 Examples of specific embodiments of the invention are provided below.
<1> A step of preparing a substrate A having a surface provided with wiring terminals;
a polyimide-containing portion forming step of forming a polyimide-containing portion on the surface of the substrate A provided with the wiring terminals;
A step of preparing a substrate B having a surface provided with wiring terminals;
A composition for forming a polyimide-containing portion used in a method for producing a bonded body, which includes a bonding step of bonding the surface of the substrate A having the polyimide-containing portion and the surface of the substrate B having the wiring terminal, ,
The polyimide-containing portion is a member formed from the polyimide-containing portion-forming composition,
A composition for forming a polyimide-containing portion, wherein the glass transition temperature of the polyimide-containing portion is lower than the bonding temperature in the bonding step.
<2> The composition for forming a polyimide-containing part according to <1>, containing a polyimide precursor and a solvent.
<3> The composition for forming a polyimide-containing part according to <1> or <2>, further comprising a migration inhibitor.
<4> The composition for forming a polyimide-containing portion according to any one of <1> to <3>, wherein the polyimide-containing portion has a glass transition temperature of 350° C. or lower.
<5> The composition for forming a polyimide-containing part according to any one of <1> to <4>, wherein the glass transition temperature of the polyimide-containing part is lower than the bonding temperature in the bonding step by 30° C. or more.
<6> The composition for forming a polyimide-containing portion according to any one of <1> to <5>, wherein the bonding temperature in the bonding step is 380° C. or less.
<7> The composition for forming a polyimide-containing portion according to any one of <1> to <6>, wherein the substrate A is in the form of a wafer.
<8> The composition for forming a polyimide-containing part according to any one of <1> to <7>, wherein the form of the substrate B is a chip.
<9> The composition for forming a polyimide-containing part according to any one of <1> to <7>, wherein the substrate B is in the form of a wafer.
<10> The composition for forming a polyimide-containing portion according to any one of <1> to <9>, wherein the temperature of the substrate A having the polyimide-containing portion is preheated to 70° C. or higher in the bonding step.
<11> Any one of <1> to <10>, including a planarization step of planarizing the surface of the polyimide-containing portion of the substrate A between the polyimide-containing portion forming step and the bonding step A composition for forming a polyimide-containing part as described above.
<12> The composition for forming a polyimide-containing portion according to <11>, wherein the planarization step is performed by physical polishing.
<13> The composition for forming a polyimide-containing portion according to <11>, wherein the planarization step is performed by chemical polishing.
<14> In the bonding step, the electrodes included in the surface of the substrate A having the polyimide-containing portion and the electrodes on the surface of the substrate B including the wiring terminals are bonded so as to be in direct contact with each other, <1> to The composition for forming a polyimide-containing portion according to any one of <13>.
<15><1> to <14>, further including a second polyimide-containing portion forming step of forming a second polyimide-containing portion on the surface of the substrate B provided with the wiring terminals before the bonding step. The composition for forming a polyimide-containing portion according to any one of .
<16> The composition for forming a polyimide-containing portion according to any one of <1> to <15>, further comprising a photosensitive compound.
<17> Any one of <1> to <16>, wherein the polyimide-containing portion forming step includes applying a composition for forming a polyimide-containing portion onto the surface of the substrate A provided with the wiring terminal and heating the composition. The composition for forming a polyimide-containing portion according to 1.
<18> The composition for forming a polyimide-containing part according to <17>, wherein the heating temperature in the heating is 375° C. or lower.
<19> A step of preparing a substrate A having a surface provided with wiring terminals;
a polyimide-containing portion forming step of forming a polyimide-containing portion on the surface of the substrate A provided with the wiring terminals;
A step of preparing a substrate B having a surface provided with wiring terminals;
A bonding step of bonding the surface of the substrate A having the polyimide-containing portion and the surface of the substrate B having the wiring terminal,
A method for producing a joined body, wherein the polyimide-containing portion has a glass transition temperature lower than the joining temperature in the joining step.
<20> A joined body obtained by the production method according to <19>.
<21> A method of manufacturing a device, including the method of manufacturing a joined body according to <19>.
<22> A device comprising the conjugate according to <20>.
　本発明によれば、２つの基板を接合する際に２つの基板の間の最大剥離抗力が大きい接合体が得られるポリイミド含有部形成用組成物、及び、上記ポリイミド含有部形成用組成物を用いた接合体の製造方法、上記製造方法により得られる接合体、上記接合体の製造方法を含むデバイスの製造方法、及び、上記接合体を含むデバイスが提供される。 According to the present invention, a composition for forming a polyimide-containing part that can obtain a bonded body having a large maximum peeling force between two substrates when bonding two substrates, and the composition for forming a polyimide-containing part are used. Provided are a method for manufacturing a bonded body, a bonded body obtained by the manufacturing method, a method for manufacturing a device including the method for manufacturing the bonded body, and a device including the bonded body.
ＣＯＣ半導体デバイスの構造を模式的に示す断面図である。1 is a cross-sectional view schematically showing the structure of a COC semiconductor device; FIG. 本発明の一実施形態に係る本発明のポリイミド含有部形成用組成物が用いられる接合体の製造方法で基板を接合するときの工程を模式的な断面図で示した工程説明図である。BRIEF DESCRIPTION OF THE DRAWINGS It is process explanatory drawing which showed the process when joining a board|substrate by the manufacturing method of the joined body using the composition for forming a polyimide containing part of this invention which concerns on one Embodiment of this invention with a schematic sectional drawing. 本発明の一実施形態に係る本発明のポリイミド含有部形成用組成物が用いられる接合体の製造方法で基板を接合するときの工程を模式的な断面図で示した工程説明図である（図２の続き）。FIG. 2 is a process explanatory diagram showing a schematic cross-sectional view of a process of bonding substrates in a method for manufacturing a bonded body using the composition for forming a polyimide-containing portion of the present invention according to one embodiment of the present invention (FIG. 2 continuation). 本発明の一実施形態に係る本発明のポリイミド含有部形成用組成物が用いられる接合体の製造方法で基板を接合するときの工程を模式的な断面図で示した工程説明図である（図３の続き）。FIG. 2 is a process explanatory diagram showing a schematic cross-sectional view of a process of bonding substrates in a method for manufacturing a bonded body using the composition for forming a polyimide-containing portion of the present invention according to one embodiment of the present invention (FIG. 3 continued). ＴＳＶを用いた三次元実装半導体デバイスの一例を模式的に示す断面図である。1 is a cross-sectional view schematically showing an example of a three-dimensionally mounted semiconductor device using TSVs; FIG. 実施例で使用した基板の詳細を示す概略断面図である。It is a schematic cross-sectional view showing details of a substrate used in Examples.
　以下において、本発明の内容について詳細に説明する。
　以下に記載する本発明における構成要素の説明は、本発明の代表的な実施形態に基づいてなされることがあるが、本発明はそのような実施形態に限定されるものではない。
　本明細書における基（原子団）の表記に於いて、置換および無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含するものである。
　本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も露光に含める。また、露光に用いられる光としては、一般的に、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線（ＥＵＶ光）、Ｘ線、電子線等の活性光線または放射線が挙げられる。
　本明細書において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
　本明細書において、「（メタ）アクリレート」は、「アクリレート」および「メタクリレート」の双方、または、いずれかを表し、「（メタ）アクリル」は、「アクリル」および「メタクリル」の双方、または、いずれかを表し、「（メタ）アクリロイル」は、「アクリロイル」および「メタクリロイル」の双方、または、いずれかを表す。
　本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
　本明細書において、固形分とは、組成物の総質量に対する、溶剤を除く他の成分の質量百分率である。また、固形分濃度は、特に述べない限り２５℃における濃度をいう。
　本発明における温度は、特に述べない限り、２５℃とする。
　本明細書において、重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、特に述べない限り、ゲル浸透クロマトグラフィ（ＧＰＣ測定）に従い、ポリスチレン換算値として定義される。本明細書において、重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、例えば、ＨＬＣ－８２２０（東ソー（株）製）を用い、カラムとしてガードカラムＨＺ－Ｌ、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺＭ－Ｍ、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ４０００、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ３０００、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ２０００（東ソー（株）製）のいずれかを用いることによって求めることができる。溶離液は特に述べない限り、ＴＨＦ（テトラヒドロフラン）を用いて測定したものとする。また、検出は特に述べない限り、ＵＶ線（紫外線）の波長２５４ｎｍ検出器を使用したものとする。 The contents of the present invention will be described in detail below.
The description of the constituent elements of the present invention described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the description of a group (atomic group) in the present specification, a description that does not describe substitution or unsubstituted includes not only those without substituents but also those with substituents. For example, an "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
As used herein, the term "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. The light used for exposure generally includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays and electron beams.
In the present specification, a numerical range represented by "to" means a range including the numerical values before and after "to" as lower and upper limits.
As used herein, "(meth)acrylate" represents both or either of "acrylate" and "methacrylate", and "(meth)acrylic" represents both "acrylic" and "methacrylic", or Either is represented, and "(meth)acryloyl" represents both or either of "acryloyl" and "methacryloyl".
As used herein, the term "process" includes not only an independent process, but also when the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. .
As used herein, the solid content is the mass percentage of other components excluding the solvent relative to the total mass of the composition. Further, the solid content concentration refers to the concentration at 25° C. unless otherwise specified.
The temperature in the present invention is 25° C. unless otherwise specified.
In the present specification, weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as polystyrene equivalent values according to gel permeation chromatography (GPC measurement), unless otherwise specified. In the present specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), guard column HZ-L, TSKgel Super HZM-M, TSKgel It can be obtained by using either Super HZ4000, TSKgel Super HZ3000, or TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, THF (tetrahydrofuran) was used as the eluent for measurement. In addition, unless otherwise specified, a UV ray (ultraviolet) wavelength detector of 254 nm is used for detection.
（ポリイミド含有部形成用組成物）
　本発明のポリイミド含有部形成用組成物は、配線端子を備える面を有する基板Ａを準備する工程、上記基板Ａの上記配線端子を備える面上にポリイミド含有部を形成するポリイミド含有部形成工程、配線端子を備える面を有する基板Ｂを準備する工程、及び、上記基板Ａのポリイミド含有部を有する面と、上記基板Ｂにおける上記配線端子を備える面とを接合する接合工程、を含む接合体の製造方法において使用されるポリイミド含有部形成用組成物であって、上記ポリイミド含有部は上記ポリイミド含有部形成用組成物から形成される部材であり、上記ポリイミド含有部のガラス転移温度が、上記接合工程における接合温度より低い。 (Composition for forming polyimide-containing part)
The composition for forming a polyimide-containing portion of the present invention includes: a step of preparing a substrate A having a surface provided with wiring terminals; a step of forming a polyimide-containing portion on the surface of the substrate A provided with the wiring terminals; A joined body comprising: a step of preparing a substrate B having a surface provided with wiring terminals; A composition for forming a polyimide-containing part used in the manufacturing method, wherein the polyimide-containing part is a member formed from the composition for forming a polyimide-containing part, and the glass transition temperature of the polyimide-containing part is the above bonding Lower than the bonding temperature in the process.
　本発明のポリイミド含有部形成用組成物（以下、単に「樹脂組成物」ともいう。）を用いることにより、ウエハとウエハ、ウエハとチップなど２つの基板をポリイミド含有部を介して接合する際に、２つの基板の間の最大剥離抗力が大きい接合体を製造することが可能となる。
　具体的には、接合温度よりもポリイミド含有部のガラス転移温度（Ｔｇ）が低いという構成を採用することにより、接合時にポリイミド含有部の十分な流動性を確保することができるため、接合時の最大剥離抗力を増大することが可能となる。
　本発明において接合温度とは、接合時のポリイミド含有部の温度であり、例えば接合に用いられる装置の設定温度とすることができる。 By using the composition for forming a polyimide-containing part of the present invention (hereinafter also simply referred to as "resin composition"), when bonding two substrates such as a wafer and a wafer or a wafer and a chip through the polyimide-containing part , it is possible to produce a bonded body with a high maximum peel force between the two substrates.
Specifically, by adopting a configuration in which the glass transition temperature (Tg) of the polyimide-containing portion is lower than the bonding temperature, it is possible to ensure sufficient fluidity of the polyimide-containing portion during bonding. It is possible to increase the maximum peel resistance.
In the present invention, the bonding temperature is the temperature of the polyimide-containing portion during bonding, and can be, for example, the set temperature of the device used for bonding.
　また、接合時の温度を高い温度とすることにより、接合時間を短縮でき、接合プロセスのタクトタイムを低減することもできる。
　ここで、上述のような２つの基板を接合する際には、接合時の位置合わせ精度が低く、各基板上の電極等の金属部同士の接合ずれが発生し、配線部分がむき出しになる部分が発生する場合がある。このような場合には、配線部分間のポリイミド含有部には耐電圧性能が求められる。
　ここで、例えば、ポリイミド含有部形成用組成物にマイグレーション抑制剤を含有させた場合には、上記金属部からポリイミド含有部に金属が移行することを抑制することができ、耐電圧性能を向上させることができると考えられる。
　以下、本発明の樹脂組成物の詳細について説明する。 Also, by setting the temperature at the time of bonding to a high temperature, the bonding time can be shortened, and the tact time of the bonding process can also be reduced.
Here, when joining two substrates as described above, the alignment accuracy at the time of joining is low, and the joining gap between the metal parts such as electrodes on each substrate occurs, and the wiring part is exposed. may occur. In such a case, the polyimide-containing portion between the wiring portions is required to have withstand voltage performance.
Here, for example, when the composition for forming the polyimide-containing portion contains a migration inhibitor, it is possible to suppress the migration of the metal from the metal portion to the polyimide-containing portion, thereby improving the withstand voltage performance. It is considered possible.
Details of the resin composition of the present invention are described below.
＜基板Ａを準備する工程＞
　本発明のポリイミド含有部形成用組成物が用いられる接合体の製造方法は、配線端子を備える面を有する基板Ａを準備する工程を含む。
　準備工程においては、基板Ａを公知の方法（例えば、シリコン基板等の基板に対するメッキなど）により製造してもよいし、購入等の手段により入手してもよい。 <Step of preparing substrate A>
A method for producing a bonded body using the composition for forming a polyimide-containing portion of the present invention includes a step of preparing a substrate A having a surface provided with wiring terminals.
In the preparation step, the substrate A may be manufactured by a known method (for example, plating on a substrate such as a silicon substrate), or may be obtained by means such as purchase.
〔基板Ａ〕
　基板Ａは、配線端子を有する面を有する。
　以下、基板Ａにおける配線端子を、配線端子Ａとも記載する。 [Substrate A]
The substrate A has a surface with wiring terminals.
The wiring terminals on the substrate A are also referred to as wiring terminals A hereinafter.
　基板Ａの形態は、ウエハであってもチップであってもよいが、ウエハであることも本発明の好ましい態様の１つである。
　本発明において、ウエハとは半導体を含む基板をいい、複数の半導体等の要素により形成されたパネル等を含む概念である。
　本発明において、チップとは、ダイシング等により形成される半導体を含む個片をいい、片面チップであってもよいし、両面チップであってもよい。 The form of the substrate A may be either a wafer or a chip, but being a wafer is also one of the preferred aspects of the present invention.
In the present invention, a wafer means a substrate containing a semiconductor, and is a concept including a panel or the like formed of a plurality of elements such as semiconductors.
In the present invention, a chip means an individual piece containing a semiconductor formed by dicing or the like, and may be a single-sided chip or a double-sided chip.
　基板Ａの形状は特に限定されないが、例えば、多角形平板状、円板状、多面体状などが挙げられる。
　基板Ａの厚さは、０．１～５ｍｍが好ましく、０．２～１ｍｍがより好ましい。
　基板Ａにおける配線端子Ａは、ピラー電極であることが好ましい。
　また、上記配線端子Ａは、金属を含むことが好ましく、錫（Ｓｎ）、金（Ａｕ）、銀（Ａｇ）、銅（Ｃｕ）、アルミニウム（Ａｌ）、タングステン（Ｗ）、パラジウム（Ｐｄ）、白金（Ｐｔ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、亜鉛（Ｚｎ）、ルテニウム（Ｒｕ）、イリジウム（Ｉｒ）、ロジウム（Ｒｈ）、鉛（Ｐｂ）、ビスマス（Ｂｉ）及び、インジウム（Ｉｎ）よりなる群から選ばれた少なくとも１種の金属を含むことがより好ましく、銅、錫及びニッケルよりなる群から選ばれた少なくとも１種の金属を含むことがより好ましい。本明細書では、金属Ｘ又はその金属を含む合金の少なくとも一方を含むことを総称して単に「金属Ｘを含む」と記載する。なお、合金は上記に例示した以外の元素を含んでいてもよい。例えば銅合金はケイ素原子を含んでコルソン合金を形成していてもよい。また、不可避的に溶存する酸素や、析出時に混在する原料化合物の有機残基等が存在していてもよい。
　上記配線端子Ａは、複数の異なる部材を含んでなる配線端子であってもよい。
　例えば、基板上に銅、銀、金、又はこれらのいずれかまたは複数を含む合金等の金属からなる電極として用いられる部分（以下、「電極」ともいう）を有し、銅等の電極上に、ニッケル、錫、鉛、又はこれらのいずれかまたは複数を含む合金等の金属からなるはんだとして用いられる部分（以下、「導通路」ともいう）が形成されており、電極と、導通路とが直列に存在することにより１つの配線端子Ａを形成していてもよい。
　これらの中でも、上記配線端子Ａは、銅を含む部材、及び、錫を含む部材を少なくとも含んでなる配線端子Ａであることが好ましい。このような配線端子Ａを備える面を有する基板Ａの例としては、本願実施例において使用した基板ｂ）の例が挙げられる。基板ｂ）においては、銅からなる電極の上に、錫からなる導通路が形成されている。 The shape of the substrate A is not particularly limited, but examples thereof include a polygonal plate shape, a disc shape, and a polyhedron shape.
The thickness of the substrate A is preferably 0.1-5 mm, more preferably 0.2-1 mm.
The wiring terminal A on the substrate A is preferably a pillar electrode.
Further, the wiring terminal A preferably contains a metal such as tin (Sn), gold (Au), silver (Ag), copper (Cu), aluminum (Al), tungsten (W), palladium (Pd), Platinum (Pt), Cobalt (Co), Nickel (Ni), Zinc (Zn), Ruthenium (Ru), Iridium (Ir), Rhodium (Rh), Lead (Pb), Bismuth (Bi) and Indium (In) More preferably, it contains at least one metal selected from the group consisting of, more preferably at least one metal selected from the group consisting of copper, tin and nickel. In this specification, inclusion of at least one of metal X or an alloy containing that metal is generically simply referred to as "comprising metal X." The alloy may contain elements other than those exemplified above. For example, a copper alloy may contain silicon atoms to form a Corson alloy. In addition, oxygen that is inevitably dissolved, organic residues of the raw material compound mixed during precipitation, and the like may be present.
The wiring terminal A may be a wiring terminal comprising a plurality of different members.
For example, a substrate has a portion that is used as an electrode (hereinafter also referred to as an “electrode”) made of a metal such as copper, silver, gold, or an alloy containing one or more of these, and on the electrode such as copper , nickel, tin, lead, or an alloy containing one or more of these metals (hereinafter also referred to as a “conducting path”) that is used as solder is formed, and the electrode and the conducting path are formed. One wiring terminal A may be formed by existing in series.
Among these, the wiring terminal A preferably includes at least a member containing copper and a member containing tin. An example of the substrate A having a surface provided with such wiring terminals A is the substrate b) used in the examples of the present application. In substrate b), conductive paths made of tin are formed on electrodes made of copper.
　また、電極に用いられる材料は特に限定されないが、錫、金、銀、銅、アルミニウム、タングステン、パラジウム、白金、コバルト、ニッケル、亜鉛、ルテニウム、イリジウム、ロジウム、又は、これらの合金が挙げられる。なかでも、電極としては銅を含む金属、アルミニウムを含む金属、タングステンを含む金属、ニッケルを含む金属、あるいは金を含む金属が好ましく、銅を含む金属がより好ましく、銅がさらに好ましい。
　電極に用いられる金属としては、接合工程でも溶融しない金属を用いることが好ましい。電極に用いられる金属の融点としては、５００℃以上であることが好ましく、７００℃以上であることがより好ましく、８００℃以上であることがさらに好ましい。上限は特にないが、例えば、３０００℃以下とすることが好ましい。
　導通路に用いられる材料は特に限定されないが、錫、鉛、銀、銅、亜鉛、ビスマス、またはインジウム、あるいはこれらの合金が挙げられる。なかでも、本発明においては錫または錫合金（錫を含む金属）のはんだが好ましい。最近では鉛を使わない無鉛はんだの技術も進歩しており、そのような材料を選定することも好ましい。
　導通路に用いられる金属としては、接合工程で溶融する金属が好ましい。導通路に用いられる金属の融点は４００℃以下であることが好ましく、３００℃以下であることがより好ましく、２５０℃以下であることがさらに好ましい。上記融点の下限は、室温で固体であれば下限は特に限定されないが、例えば、１５０℃以上であることが好ましい。
　また、配線端子Ａは基板Ａ上に複数個形成されていることが好ましい。 Materials used for the electrodes are not particularly limited, but include tin, gold, silver, copper, aluminum, tungsten, palladium, platinum, cobalt, nickel, zinc, ruthenium, iridium, rhodium, and alloys thereof. Among them, the electrode is preferably a metal containing copper, a metal containing aluminum, a metal containing tungsten, a metal containing nickel, or a metal containing gold, more preferably a metal containing copper, and still more preferably copper.
As the metal used for the electrodes, it is preferable to use a metal that does not melt even in the joining process. The melting point of the metal used for the electrodes is preferably 500° C. or higher, more preferably 700° C. or higher, and even more preferably 800° C. or higher. Although there is no particular upper limit, it is preferably 3000° C. or less, for example.
The material used for the conductive path is not particularly limited, but includes tin, lead, silver, copper, zinc, bismuth, or indium, or alloys thereof. Among them, solder of tin or a tin alloy (a metal containing tin) is preferable in the present invention. Recently, the technology of lead-free solder, which does not use lead, is also progressing, and it is also preferable to select such a material.
As the metal used for the conducting path, a metal that melts in the joining process is preferable. The melting point of the metal used for the conducting paths is preferably 400° C. or lower, more preferably 300° C. or lower, and even more preferably 250° C. or lower. The lower limit of the melting point is not particularly limited as long as it is solid at room temperature.
Moreover, it is preferable that a plurality of wiring terminals A are formed on the substrate A. As shown in FIG.
　基板Ａに用いられる材料は特に限定されず、シリコン、窒化シリコン、ポリシリコン、酸化シリコン、アモルファスシリコンなどの半導体作製基板、石英、ガラス、光学フィルム、セラミック材料、蒸着膜、磁性膜、反射膜、Ｎｉ、Ｃｕ、Ｃｒ、Ｆｅなどの金属基板、紙、ＳＯＧ（Ｓｐｉｎ　Ｏｎ　Ｇｌａｓｓ）、ＴＦＴ（薄膜トランジスタ）アレイ基板、プラズマディスプレイパネル（ＰＤＰ）の電極板など特に制約されない。基材にはヘキサメチルジシラザン（ＨＭＤＳ）等による密着層や酸化層などの層が表面に設けられていてもよい。本発明では、特に、半導体作製基板が好ましく、シリコン基板（シリコンウエハ）がより好ましい。基板Ａは電子回路を含む電子回路領域を有していてもよい。また、上記電子回路は、半導体等の素子を有していてもよい。また、上記電子回路は、上記配線端子Ａと電気的に接合されていることが好ましい。
　基板Ａがウエハである場合のサイズとしては、直径（基板Ａが円形でない場合は最大径）を１００ｍｍ以上とすることができる。また、大型の基板としては、例えば、２００ｍｍ以上であることが好ましく、２５０ｍｍ以上であることがより好ましい。上限は特にないが、２，０００ｍｍ以下であることが好ましい。
　基板Ａがチップである場合のサイズとしては、直径（基板Ａが円形でない場合は最大径）を７ｍｍ以上とすることが好ましく、１０ｍｍ以上がより好ましく、２０ｍｍ以上が更に好ましい。上限としては、例えば、５０ｍｍ以下であることが好ましく、４０ｍｍ以下であることがより好ましく、３０ｍｍ以下であることが更に好ましい。 The material used for the substrate A is not particularly limited, and includes semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, deposited films, magnetic films, reflective films, Metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, plasma display panel (PDP) electrode plates, etc. are not particularly limited. The substrate may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface. In the present invention, a semiconductor fabrication substrate is particularly preferred, and a silicon substrate (silicon wafer) is more preferred. Substrate A may have an electronic circuit area containing electronic circuits. Moreover, the electronic circuit may have an element such as a semiconductor. Moreover, it is preferable that the electronic circuit is electrically connected to the wiring terminal A.
When the substrate A is a wafer, the diameter (maximum diameter if the substrate A is not circular) can be 100 mm or more. Moreover, as a large substrate, for example, it is preferably 200 mm or more, and more preferably 250 mm or more. Although there is no particular upper limit, it is preferably 2,000 mm or less.
When the substrate A is a chip, the diameter (maximum diameter if the substrate A is not circular) is preferably 7 mm or more, more preferably 10 mm or more, and even more preferably 20 mm or more. The upper limit is, for example, preferably 50 mm or less, more preferably 40 mm or less, and even more preferably 30 mm or less.
＜ポリイミド含有部形成工程＞
　本発明のポリイミド含有部形成用組成物が用いられる接合体の製造方法は、上記基板Ａの上記配線端子（配線端子Ａ）を備える面上にポリイミド含有部を形成するポリイミド含有部形成工程を含む。
　ポリイミド含有部は、上記配線端子Ａと接するように形成されることが好ましく、配線端子Ａと配線端子Ａの間の凹部を充填するように形成されることがより好ましい。
　また、ポリイミド含有部は、上記配線端子Ａの少なくとも一部の上に形成されればよいが、例えば、上記配線端子Ａの全ての上に形成される態様も、本発明の好ましい態様の１つである。
　上記ポリイミド含有部形成工程は、基板Ａの上記配線端子を備える面上にポリイミド含有部形成用組成物を適用し、加熱することを含むことが好ましい。適用及び加熱の詳細については後述する。 <Polyimide-containing part forming process>
A method for producing a bonded body using the composition for forming a polyimide-containing portion of the present invention includes a polyimide-containing portion forming step of forming a polyimide-containing portion on the surface of the substrate A provided with the wiring terminal (wiring terminal A). .
The polyimide-containing portion is preferably formed so as to be in contact with the wiring terminal A, and more preferably formed so as to fill the concave portion between the wiring terminals A.
In addition, the polyimide-containing portion may be formed on at least a part of the wiring terminals A, but for example, an embodiment in which the polyimide-containing portion is formed on all of the wiring terminals A is also one of the preferred embodiments of the present invention. is.
The polyimide-containing portion forming step preferably includes applying a composition for forming a polyimide-containing portion onto the surface of the substrate A provided with the wiring terminals and heating. Application and heating details are described below.
〔ポリイミド含有部〕
　上記ポリイミド含有部は上記ポリイミド含有部形成用組成物から形成される部材であり、上記ポリイミド含有部形成用組成物を少なくとも加熱して得られる部材であることが好ましい。 [Polyimide-containing portion]
The polyimide-containing portion is a member formed from the polyimide-containing portion-forming composition, and is preferably a member obtained by at least heating the polyimide-containing portion-forming composition.
　ポリイミド含有部は、ポリイミドを含む部材であり、ポリイミド以外の成分を更に含んでもよい。
　ポリイミド以外の成分としては、後述の樹脂組成物に含まれるポリイミド及びその前駆体以外の成分、及び、その成分が加熱により変性（分解、重合、構造変化等）した成分等が挙げられる。 The polyimide-containing portion is a member containing polyimide, and may further contain components other than polyimide.
Examples of components other than polyimide include components other than polyimide and its precursor contained in the resin composition described later, and components modified by heating (decomposition, polymerization, structural change, etc.).
　ポリイミド含有部のガラス転移温度は、接合工程における接合温度よりも低ければよいが、３５０℃以下であることが好ましく、３２０℃以下であることがより好ましく、３００℃以下であることが更に好ましい。
　上記ガラス転移温度の下限は特に限定されないが、耐熱性の観点からは２００℃以上であることが好ましい。
　最大剥離抗力を増大する観点からは、ポリイミド含有部のガラス転移温度は、接合工程における接合温度よりも３０℃以上低いことが好ましく、５０℃以上低いことがより好ましく、７０℃以上低いことが更に好ましい。
　また、ポリイミド含有部のガラス転移温度は、接合工程における接合温度よりも３０℃以上高いことが好ましい。 The glass transition temperature of the polyimide-containing portion may be lower than the bonding temperature in the bonding step, but is preferably 350° C. or lower, more preferably 320° C. or lower, and even more preferably 300° C. or lower.
Although the lower limit of the glass transition temperature is not particularly limited, it is preferably 200° C. or higher from the viewpoint of heat resistance.
From the viewpoint of increasing the maximum peel resistance, the glass transition temperature of the polyimide-containing portion is preferably 30 ° C. or more lower than the bonding temperature in the bonding step, more preferably 50 ° C. or more, and further preferably 70 ° C. or more. preferable.
Also, the glass transition temperature of the polyimide-containing portion is preferably 30° C. or more higher than the bonding temperature in the bonding step.
　ポリイミド含有部の厚さは特に限定されないが、その物性の効果を発揮する観点から、接合工程の直前の厚さ（後述する平坦化工程が行われる場合は、平坦化工程が行われる直前の状態の厚さ）で１００ｎｍ以上であることが好ましく、３００ｎｍ以上であることがより好ましく、５００ｎｍ以上であることがさらに好ましく、１μｍ以上であることが一層好ましく、２μｍ以上であることがより一層好ましい。上限は特にないが、１ｍｍ以下であることが好ましく、５００μｍ以下であることがより好ましく、２００μｍ以下であることがさらに好ましい。膜の厚さは、公知の膜厚測定装置を用いて測定することができる。 The thickness of the polyimide-containing portion is not particularly limited, but from the viewpoint of exhibiting the effect of its physical properties, the thickness immediately before the bonding step (when the planarization step described later is performed, the state immediately before the planarization step is performed) thickness) is preferably 100 nm or more, more preferably 300 nm or more, still more preferably 500 nm or more, still more preferably 1 μm or more, and even more preferably 2 μm or more. Although there is no particular upper limit, it is preferably 1 mm or less, more preferably 500 μm or less, and even more preferably 200 μm or less. The thickness of the film can be measured using a known film thickness measuring device.
　後述する接合体におけるポリイミド含有部の熱拡散率は、２．０×１０－７ｍ２ｓ－１以上であることが好ましく、３．０×１０－７ｍ２ｓ－１以上であることがより好ましく、５．０×１０－７ｍ２ｓ－１以上であることが更に好ましい。
　上記ポリイミド含有部の熱拡散率は、例えば、ポリイミド含有部がフィラーを含む場合はフィラーの材料種、フィラーの粒子径（フィラーを２種以上含む場合はその粒子径の組み合わせ）、フィラーの熱拡散率、フィラーの含有量、ポリイミドの構造、ポリイミドの熱拡散率、ポリイミドの含有量等の設計により調整することができる。 The thermal diffusivity of the polyimide-containing portion in the joined body described later is preferably 2.0×10 −7 m 2 s −1 or more, and more preferably 3.0×10 −7 m 2 s −1 or more. More preferably, it is 5.0×10 −7 m 2 s −1 or more.
The thermal diffusivity of the polyimide-containing part is, for example, when the polyimide-containing part contains a filler, the material type of the filler, the particle size of the filler (a combination of the particle sizes when two or more types of filler are included), and the thermal diffusion of the filler. It can be adjusted by designing factors such as the rate, content of filler, structure of polyimide, thermal diffusivity of polyimide, content of polyimide, and the like.
　ポリイミド含有部は絶縁性の部材であることが好ましい。ポリイミド含有部の絶縁性（電気抵抗）は特に限定されないが、体積抵抗率で１×１０１５Ω・ｃｍ以上であることが好ましく、１×１０１６Ω・ｃｍ以上であることがより好ましい。上限は特にないが、１×１０１９Ω・ｃｍ以下であることが実際的である。絶縁破壊電圧は、１ｋＶ／ｍｍ以上であることが好ましく、１０ｋＶ／ｍｍ以上であることがより好ましい。上限は特に限定されないが１０００ｋＶ／ｍｍ以下であることが実際的である。本明細書において体積抵抗率と絶縁破壊電圧の測定等はＪＩＳ　Ｃ２１５１：２００６、ＪＩＳ　Ｃ２３１８：２００７に準拠するものとする。 The polyimide-containing portion is preferably an insulating member. The insulation (electrical resistance) of the polyimide-containing portion is not particularly limited, but the volume resistivity is preferably 1×10 15 Ω·cm or more, more preferably 1×10 16 Ω·cm or more. Although there is no particular upper limit, it is practical to be 1×10 19 Ω·cm or less. The dielectric breakdown voltage is preferably 1 kV/mm or more, more preferably 10 kV/mm or more. Although the upper limit is not particularly limited, it is practically 1000 kV/mm or less. In this specification, measurements of volume resistivity and dielectric breakdown voltage shall comply with JIS C2151:2006 and JIS C2318:2007.
〔適用工程〕
　ポリイミド含有部形成工程は、本発明のポリイミド含有部形成用組成物（樹脂組成物）を、上記基板Ａの上記配線端子Ａを有する面上に適用すること（適用工程）を含む工程であることが好ましい。 [Applied process]
The polyimide-containing portion forming step is a step including applying the polyimide-containing portion forming composition (resin composition) of the present invention onto the surface of the substrate A having the wiring terminal A (application step). is preferred.
　樹脂組成物を基材Ａ上に適用する手段としては、ディップコート法、エアーナイフコート法、カーテンコート法、ワイヤーバーコート法、グラビアコート法、エクストルージョンコート法、スプレーコート法、スピンコート法、スリットコート法、およびインクジェット法などが例示される。膜の厚さの均一性の観点から、より好ましくはスピンコート法、スリットコート法、スプレーコート法、又は、インクジェット法であり、膜の厚さの均一性の観点および生産性の観点からスピンコート法およびスリットコート法が好ましい。方法に応じて樹脂組成物の固形分濃度や塗布条件を調整することで、所望の厚さの膜を得ることができる。また、基材の形状によっても塗布方法を適宜選択でき、ウエハ等の円形基材であればスピンコート法、スプレーコート法、インクジェット法等が好ましく、矩形基材であればスリットコート法やスプレーコート法、インクジェット法等が好ましい。スピンコート法の場合は、例えば、５００～３，５００ｒｐｍの回転数で、１０秒～３分程度適用することができる。
　また、あらかじめ仮支持体上に上記付与方法によって付与して形成した塗膜を、基材上に転写する方法を適用することもできる。
　転写方法に関しては特開２００６－０２３６９６号公報の段落００２３、００３６～００５１や、特開２００６－０４７５９２号公報の段落００９６～０１０８に記載の作製方法を本発明においても好適に用いることができる。
　また、基材の端部において余分な膜の除去を行なう工程を行なってもよい。このような工程の例には、エッジビードリンス（ＥＢＲ）、バックリンスなどが挙げられる。
　また樹脂組成物を基材に塗布する前に基材を種々の溶剤を塗布し、基材の濡れ性を向上させた後に樹脂組成物を塗布するプリウェット工程を採用しても良い。 Means for applying the resin composition onto the substrate A include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, A slit coat method, an inkjet method, and the like are exemplified. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet method is more preferable, and spin coating from the viewpoint of uniformity of film thickness and productivity. and slit coating methods are preferred. A film having a desired thickness can be obtained by adjusting the solid content concentration and application conditions of the resin composition according to the method. In addition, the coating method can be appropriately selected depending on the shape of the substrate. Spin coating, spray coating, inkjet method, etc. are preferable for circular substrates such as wafers, and slit coating and spray coating are preferable for rectangular substrates. method, inkjet method, and the like are preferred. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.
Alternatively, a method of transferring a coating film, which is formed on a temporary support in advance by the application method described above, onto a base material can be applied.
As for the transfer method, the manufacturing methods described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0096-0108 of JP-A-2006-047592 can also be preferably used in the present invention.
Also, a step of removing excess film at the edge of the substrate may be performed. Examples of such processes include edge bead rinsing (EBR), back rinsing, and the like.
A pre-wetting step may also be employed in which the substrate is coated with various solvents before applying the resin composition to the substrate to improve the wettability of the substrate, and then the resin composition is applied.
　また、樹脂組成物が溶剤を含む場合には、樹脂組成物を基材Ａに適用した後に、樹脂組成物からなる部材（以下、単に「膜」ともいう）を乾燥させる工程（乾燥工程）を含んでもよい。
　乾燥工程における乾燥温度は５０～１５０℃であることが好ましく、７０℃～１３０℃がより好ましく、９０℃～１１０℃が更に好ましい。また、減圧により乾燥を行っても良い。乾燥時間としては、３０秒～２０分が例示され、１分～１０分が好ましく、２分～７分がより好ましい。 Further, when the resin composition contains a solvent, after applying the resin composition to the base material A, a step (drying step) of drying the member (hereinafter also simply referred to as "film") made of the resin composition is performed. may contain.
The drying temperature in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, even more preferably 90 to 110°C. Moreover, you may dry by pressure reduction. The drying time is exemplified from 30 seconds to 20 minutes, preferably from 1 minute to 10 minutes, more preferably from 2 minutes to 7 minutes.
　適用直後の厚さ（乾燥工程を行う場合は、乾燥後の厚さ）は特に限定されず、得られるポリイミド含有部の厚さが後述の厚さとなるよう適宜調整すればよい。 The thickness immediately after application (the thickness after drying when a drying step is performed) is not particularly limited, and may be adjusted as appropriate so that the thickness of the resulting polyimide-containing portion will be the thickness described later.
　ポリイミド含有部形成工程は、樹脂組成物からなる部材をパターニングする工程を含んでもよい。樹脂組成物として後述する光重合開始剤等の感光性化合物を含むものを用いた場合には、このパターニングを露光および現像することで行うことができる。
　ポリイミド含有部形成工程は形成された後、その表面が平坦化されてもよい。平坦化の詳細は後述する。なお、パターニングを行なった場合、現像等によって除去された部分の厚みは後述する膜厚差（Ｔ１－Ｔ２）の算出に用いないこととする。 The polyimide-containing portion forming step may include a step of patterning the member made of the resin composition. When a resin composition containing a photosensitive compound such as a photopolymerization initiator, which will be described later, is used, this patterning can be performed by exposure and development.
After forming the polyimide-containing portion, the surface may be planarized. Details of the planarization will be described later. Note that when patterning is performed, the thickness of the portion removed by development or the like is not used for calculating the film thickness difference (T1-T2) described later.
〔露光工程〕
　上記膜は、膜を選択的に露光する露光工程に供されてもよい。
　すなわち、本発明のポリイミド含有部形成用組成物に係るポリイミド含有部（以下、「硬化物」）ともいう。）の製造方法は、適用工程により形成された膜を選択的に露光する露光工程を含んでもよい。
　選択的に露光するとは、膜の一部を露光することを意味している。また、選択的に露光することにより、膜には露光された領域（露光部）と露光されていない領域（非露光部）が形成される。
　露光量は、本発明の樹脂組成物を硬化できる限り特に定めるものではないが、例えば、波長３６５ｎｍでの露光エネルギー換算で５０～１０，０００ｍＪ／ｃｍ２が好ましく、２００～８，０００ｍＪ／ｃｍ２がより好ましい。 [Exposure process]
The film may be subjected to an exposure step that selectively exposes the film.
That is, it is also referred to as a polyimide-containing portion (hereinafter, “cured product”) related to the composition for forming a polyimide-containing portion of the present invention. ) may include an exposure step of selectively exposing the film formed by the applying step.
Selectively exposing means exposing a portion of the film. Also, by selectively exposing, the film is formed with exposed regions (exposed portions) and non-exposed regions (non-exposed portions).
The amount of exposure is not particularly defined as long as the resin composition of the present invention can be cured . is more preferred.
　露光波長は、１９０～１，０００ｎｍの範囲で適宜定めることができ、２４０～５５０ｎｍが好ましい。 The exposure wavelength can be appropriately determined in the range of 190-1,000 nm, preferably 240-550 nm.
　露光波長は、光源との関係でいうと、（１）半導体レーザー（波長　８３０ｎｍ、５３２ｎｍ、４８８ｎｍ、４０５ｎｍ、３７５ｎｍ、３５５ｎｍ　ｅｔｃ．）、（２）メタルハライドランプ、（３）高圧水銀灯、ｇ線（波長　４３６ｎｍ）、ｈ線（波長　４０５ｎｍ）、ｉ線（波長　３６５ｎｍ）、ブロード（ｇ，ｈ，ｉ線の３波長）、（４）エキシマレーザー、ＫｒＦエキシマレーザー（波長　２４８ｎｍ）、ＡｒＦエキシマレーザー（波長　１９３ｎｍ）、Ｆ２エキシマレーザー（波長　１５７ｎｍ）、（５）極端紫外線；ＥＵＶ（波長　１３．６ｎｍ）、（６）電子線、（７）ＹＡＧレーザーの第二高調波５３２ｎｍ、第三高調波３５５ｎｍ等が挙げられる。本発明の樹脂組成物については、特に高圧水銀灯による露光が好ましく、中でも、ｉ線による露光が好ましい。これにより、特に高い露光感度が得られうる。
　また、露光の方式は特に限定されず、本発明の樹脂組成物からなる膜の少なくとも一部が露光される方式であればよいが、フォトマスクを使用した露光、レーザーダイレクトイメージング法による露光等が挙げられる。 In relation to the light source, the exposure wavelength is (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) ), F2 excimer laser ( wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, etc. mentioned. For the resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is particularly preferred. Thereby, particularly high exposure sensitivity can be obtained.
The method of exposure is not particularly limited as long as at least a part of the film made of the resin composition of the present invention is exposed. Exposure using a photomask, exposure by a laser direct imaging method, etc. mentioned.
＜露光後加熱工程＞
　上記膜は、露光後に加熱する工程（露光後加熱工程）に供されてもよい。
　すなわち、本発明のポリイミド含有部形成用組成物に係る硬化物の製造方法は、露光工程により露光された膜を加熱する露光後加熱工程を含んでもよい。
　露光後加熱工程は、露光工程後、現像工程前に行うことができる。
　露光後加熱工程における加熱温度は、５０℃～１４０℃であることが好ましく、６０℃～１２０℃であることがより好ましい。
　露光後加熱工程における加熱時間は、３０秒間～３００分間が好ましく、１分間～１０分間がより好ましい。
　露光後加熱工程における昇温速度は、加熱開始時の温度から最高加熱温度まで１～１２℃／分が好ましく、２～１０℃／分がより好ましく、３～１０℃／分が更に好ましい。
　また、昇温速度は加熱途中で適宜変更してもよい。
　露光後加熱工程における加熱手段としては、特に限定されず、公知のホットプレート、オーブン、赤外線ヒーター等を用いることができる。
　また、加熱に際し、窒素、ヘリウム、アルゴンなどの不活性ガスを流す等により、低酸素濃度の雰囲気で行うことも好ましい。 <Post-exposure heating process>
The film may be subjected to a step of heating after exposure (post-exposure heating step).
That is, the method for producing a cured product of the composition for forming a polyimide-containing portion of the present invention may include a post-exposure heating step of heating the film exposed in the exposure step.
The post-exposure heating step can be performed after the exposure step and before the development step.
The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C.
The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
The heating rate in the post-exposure heating step is preferably 1 to 12° C./min, more preferably 2 to 10° C./min, still more preferably 3 to 10° C./min, from the temperature at the start of heating to the maximum heating temperature.
Also, the rate of temperature increase may be appropriately changed during heating.
The heating means in the post-exposure heating step is not particularly limited, and known hot plates, ovens, infrared heaters and the like can be used.
Moreover, it is also preferable to carry out the heating in an atmosphere of low oxygen concentration by, for example, flowing an inert gas such as nitrogen, helium or argon.
＜現像工程＞
　露光後の上記膜は、現像液を用いて現像してパターンを形成する現像工程に供されてもよい。
　すなわち、本発明のポリイミド含有部形成用組成物に係る硬化物の製造方法は、露光工程により露光された膜を現像液を用いて現像してパターンを形成する現像工程を含んでもよい。現像を行うことにより、膜の露光部及び非露光部のうち一方が除去され、パターンが形成される。
　ここで、膜の非露光部が現像工程により除去される現像をネガ型現像といい、膜の露光部が現像工程により除去される現像をポジ型現像という。 <Development process>
The film after exposure may be subjected to a development step in which the film is developed using a developer to form a pattern.
That is, the method for producing a cured product of the composition for forming a polyimide-containing portion of the present invention may include a development step of developing a film exposed in the exposure step with a developer to form a pattern. By performing development, one of the exposed and non-exposed portions of the film is removed to form a pattern.
Here, development in which the unexposed portion of the film is removed by the development process is called negative development, and development in which the exposed portion of the film is removed by the development process is called positive development.
〔現像液〕
　現像工程において用いられる現像液としては、アルカリ水溶液、又は、有機溶剤を含む現像液が挙げられる。 [Developer]
Examples of the developer used in the development process include an aqueous alkaline solution and a developer containing an organic solvent.
　現像液がアルカリ水溶液である場合、アルカリ水溶液が含みうる塩基性化合物としては、無機アルカリ類、第一級アミン類、第二級アミン類、第三級アミン類、第四級アンモニウム塩が挙げられ、ＴＭＡＨ（テトラメチルアンモニウムヒドロキシド）、水酸化カリウム、炭酸ナトリウム、水酸化ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウム、アンモニア、エチルアミン、ｎ－プロピルアミン、ジエチルアミン、ジ－ｎ－ブチルアミン、トリエチルアミン、メチルジエチルアミン、ジメチルエタノールアミン、トリエタノールアミン、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドドキシド、テトラブチルアンモニウムヒドロキシド、テトラペンチルアンモニウムヒドロキシド、テトラヘキシルアンモニウムヒドロキシド、テトラオクチルアンモニウムヒドロキシド、エチルトリメチルアンモニウムヒドロキシド、ブチルトリメチルアンモニウムヒドロキシド、メチルトリアミルアンモニウムヒドロキシド、ジブチルジペンチルアンモニウムヒドロキシド、ジメチルビス（２－ヒドロキシエチル）アンモニウムヒドロキシド、トリメチルフェニルアンモニウムヒドロキシド、トリメチルベンジルアンモニウムヒドロキシド、トリエチルベンジルアンモニウムヒドロキシド、ピロール、ピペリジンが好ましく、より好ましくはＴＭＡＨである。現像液における塩基性化合物の含有量は、例えばＴＭＡＨを用いる場合、現像液全質量中０．０１～１０質量％が好ましく、０．１～５質量％がより好ましく、０．３～３質量％が更に好ましい。 When the developer is an alkaline aqueous solution, basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. , TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine , dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide , butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, Pyrrole and piperidine are preferred, and TMAH is more preferred. The content of the basic compound in the developer, for example, when TMAH is used, is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass, based on the total mass of the developer. is more preferred.
　現像液が有機溶剤を含む場合、有機溶剤は、エステル類として、例えば、酢酸エチル、酢酸－ｎ－ブチル、ギ酸アミル、酢酸イソアミル、酢酸イソブチル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、γ－ブチロラクトン、ε－カプロラクトン、δ－バレロラクトン、アルキルオキシ酢酸アルキル（例：アルキルオキシ酢酸メチル、アルキルオキシ酢酸エチル、アルキルオキシ酢酸ブチル（例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等））、３－アルキルオキシプロピオン酸アルキルエステル類（例：３－アルキルオキシプロピオン酸メチル、３－アルキルオキシプロピオン酸エチル等（例えば、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル等））、２－アルキルオキシプロピオン酸アルキルエステル類（例：２－アルキルオキシプロピオン酸メチル、２－アルキルオキシプロピオン酸エチル、２－アルキルオキシプロピオン酸プロピル等（例えば、２－メトキシプロピオン酸メチル、２－メトキシプロピオン酸エチル、２－メトキシプロピオン酸プロピル、２－エトキシプロピオン酸メチル、２－エトキシプロピオン酸エチル））、２－アルキルオキシ－２－メチルプロピオン酸メチル及び２－アルキルオキシ－２－メチルプロピオン酸エチル（例えば、２－メトキシ－２－メチルプロピオン酸メチル、２－エトキシ－２－メチルプロピオン酸エチル等）、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、２－オキソブタン酸メチル、２－オキソブタン酸エチル等、並びに、エーテル類として、例えば、ジエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート等、並びに、ケトン類として、例えば、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、２－ヘプタノン、３－ヘプタノン、Ｎ－メチル－２－ピロリドン等、並びに、環状炭化水素類として、例えば、トルエン、キシレン、アニソール等の芳香族炭化水素類、リモネン等の環式テルペン類、スルホキシド類としてジメチルスルホキシド、並びに、アルコール類として、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、ペンタノール、オクタノール、ジエチレングリコール、プロピレングリコール、メチルイソブチルカルビノール、トリエチレングリコール等、並びに、アミド類として、Ｎ－メチルピロリドン、Ｎ－エチルピロリドン、ジメチルホルムアミド等が好適に挙げられる。 When the developer contains an organic solvent, the organic solvent may be an ester such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, Methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetate (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate , butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionate alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., 3-methoxy methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g. methyl 2-alkyloxypropionate, 2- ethyl alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionic acid ethyl)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g. methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate ethyl, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene Glycol monoethyl ether acetate, propylene Glycol monopropyl ether acetate and the like, and ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and cyclic hydrocarbons such as aromatic hydrocarbons such as toluene, xylene and anisole; cyclic terpenes such as limonene; dimethyl sulfoxide as sulfoxides; Propylene glycol, methyl isobutyl carbinol, triethylene glycol and the like, and amides preferably include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide and the like.
　現像液が有機溶剤を含む場合、有機溶剤は１種又は、２種以上を混合して使用することができる。本発明では特にシクロペンタノン、γ－ブチロラクトン、ジメチルスルホキシド、Ｎ－メチル－２－ピロリドン、及び、シクロヘキサノンよりなる群から選ばれた少なくとも１種を含む現像液が好ましく、シクロペンタノン、γ－ブチロラクトン及びジメチルスルホキシドよりなる群から選ばれた少なくとも１種を含む現像液がより好ましく、シクロペンタノンを含む現像液が最も好ましい。 When the developer contains an organic solvent, the organic solvent can be used singly or in combination of two or more. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, and cyclopentanone and γ-butyrolactone. and dimethylsulfoxide is more preferred, and a developer containing cyclopentanone is most preferred.
　現像液が有機溶剤を含む場合、現像液の全質量に対する有機溶剤の含有量は、５０質量％以上であることが好ましく、７０質量％以上であることがより好ましく、８０質量％以上であることが更に好ましく、９０質量％以上であることが特に好ましい。また、上記含有量は、１００質量％であってもよい。 When the developer contains an organic solvent, the content of the organic solvent relative to the total weight of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, and 80% by mass or more. is more preferable, and 90% by mass or more is particularly preferable. Moreover, the content may be 100% by mass.
　現像液は、他の成分を更に含んでもよい。
　他の成分としては、例えば、公知の界面活性剤や公知の消泡剤等が挙げられる。 The developer may further contain other components.
Other components include, for example, known surfactants and known antifoaming agents.
〔現像液の供給方法〕
　現像液の供給方法は、所望のパターンを形成できれば特に制限は無く、膜が形成された基材を現像液に浸漬する方法、基材上に形成された膜にノズルを用いて現像液を供給するパドル現像、または、現像液を連続供給する方法がある。ノズルの種類は特に制限は無く、ストレートノズル、シャワーノズル、スプレーノズル等が挙げられる。
　現像液の浸透性、非画像部の除去性、製造上の効率の観点から、現像液をストレートノズルで供給する方法、又はスプレーノズルにて連続供給する方法が好ましく、画像部への現像液の浸透性の観点からは、スプレーノズルで供給する方法がより好ましい。
　また、現像液をストレートノズルにて連続供給後、基材をスピンし現像液を基材上から除去し、スピン乾燥後に再度ストレートノズルにて連続供給後、基材をスピンし現像液を基材上から除去する工程を採用してもよく、この工程を複数回繰り返しても良い。
　また現像工程における現像液の供給方法としては、現像液が連続的に基材に供給され続ける工程、基材上で現像液が略静止状態で保たれる工程、基材上で現像液を超音波等で振動させる工程及びそれらを組み合わせた工程などが採用可能である。 [Method of supplying developer]
The method of supplying the developer is not particularly limited as long as the desired pattern can be formed, and a method of immersing the substrate on which the film is formed in the developer, and supplying the developer to the film formed on the substrate using a nozzle. There is a method of puddle development or a method of continuously supplying developer. The type of nozzle is not particularly limited, and straight nozzles, shower nozzles, spray nozzles and the like can be mentioned.
From the viewpoint of permeability of the developer, removability of the non-image area, and efficiency in production, a method of supplying the developer with a straight nozzle or a method of continuously supplying the developer with a spray nozzle is preferable. From the viewpoint of permeability, the method of supplying with a spray nozzle is more preferable.
In addition, after continuously supplying the developer with a straight nozzle, the substrate is spun to remove the developer from the substrate. A step of removing from above may be employed, and this step may be repeated multiple times.
The method of supplying the developer in the development process includes a process in which the developer is continuously supplied to the base material, a process in which the developer is kept substantially stationary on the base material, and a process in which the developer exceeds the developer on the base material. A process of vibrating with sound waves or the like and a process of combining them can be employed.
　現像時間としては、１０秒～１０分間が好ましく、２０秒～５分間がより好ましい。現像時の現像液の温度は、特に定めるものではないが、好ましくは、１０～４５℃、より好ましくは、１８℃～３０℃で行うことができる。 The development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.
　現像工程において、現像液を用いた処理の後、更に、リンス液によるパターンの洗浄（リンス）を行ってもよい。また、パターン上に接する現像液が乾燥しきらないうちにリンス液を供給するなどの方法を採用しても良い。 In the development process, after processing using the developer, the pattern may be washed (rinsed) with a rinse. Alternatively, a method of supplying the rinse liquid before the developer in contact with the pattern is completely dried may be adopted.
〔リンス液〕
　現像液がアルカリ水溶液である場合、リンス液としては、例えば水を用いることができる。現像液が有機溶剤を含む現像液である場合、リンス液としては、例えば、現像液に含まれる溶剤とは異なる溶剤（例えば、水、現像液に含まれる有機溶剤とは異なる有機溶剤）を用いることができる。 [Rinse liquid]
When the developer is an alkaline aqueous solution, water, for example, can be used as the rinse. When the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer) is used as the rinse liquid. be able to.
　リンス液が有機溶剤を含む場合の有機溶剤としては、エステル類として、例えば、酢酸エチル、酢酸－ｎ－ブチル、ギ酸アミル、酢酸イソアミル、酢酸イソブチル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、γ－ブチロラクトン、ε－カプロラクトン、δ－バレロラクトン、アルキルオキシ酢酸アルキル（例：アルキルオキシ酢酸メチル、アルキルオキシ酢酸エチル、アルキルオキシ酢酸ブチル（例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等））、３－アルキルオキシプロピオン酸アルキルエステル類（例：３－アルキルオキシプロピオン酸メチル、３－アルキルオキシプロピオン酸エチル等（例えば、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル等））、２－アルキルオキシプロピオン酸アルキルエステル類（例：２－アルキルオキシプロピオン酸メチル、２－アルキルオキシプロピオン酸エチル、２－アルキルオキシプロピオン酸プロピル等（例えば、２－メトキシプロピオン酸メチル、２－メトキシプロピオン酸エチル、２－メトキシプロピオン酸プロピル、２－エトキシプロピオン酸メチル、２－エトキシプロピオン酸エチル））、２－アルキルオキシ－２－メチルプロピオン酸メチル及び２－アルキルオキシ－２－メチルプロピオン酸エチル（例えば、２－メトキシ－２－メチルプロピオン酸メチル、２－エトキシ－２－メチルプロピオン酸エチル等）、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、２－オキソブタン酸メチル、２－オキソブタン酸エチル等、並びに、エーテル類として、例えば、ジエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート等、並びに、ケトン類として、例えば、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、２－ヘプタノン、３－ヘプタノン、Ｎ－メチル－２－ピロリドン等、並びに、環状炭化水素類として、例えば、トルエン、キシレン、アニソール等の芳香族炭化水素類、リモネン等の環式テルペン類、スルホキシド類としてジメチルスルホキシド、並びに、アルコール類として、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、ペンタノール、オクタノール、ジエチレングリコール、プロピレングリコール、メチルイソブチルカルビノール、トリエチレングリコール等、並びに、アミド類として、Ｎ－メチルピロリドン、Ｎ－エチルピロリドン、ジメチルホルムアミド等が好適に挙げられる。 When the rinse solution contains an organic solvent, the organic solvent includes esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyl butyrate. , methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetates (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g. methyl methoxyacetate, methoxyacetate ethyl, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionate alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., 3- methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g. methyl 2-alkyloxypropionate, 2 -ethyl alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionate ethyl acid)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g. methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate ethyl acetate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran , ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like, and ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and cyclic hydrocarbons such as , Toluene, xylene, aromatic hydrocarbons such as anisole, cyclic terpenes such as limonene, dimethyl sulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol as alcohols. , propylene glycol, methyl isobutyl carbinol, triethylene glycol, and amides such as N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, and the like.
　リンス液が有機溶剤を含む場合、有機溶剤は１種又は、２種以上を混合して使用することができる。本発明では特にシクロペンタノン、γ－ブチロラクトン、ジメチルスルホキシド、Ｎ－メチルピロリドン、シクロヘキサノン、ＰＧＭＥＡ、ＰＧＭＥが好ましく、シクロペンタノン、γ－ブチロラクトン、ジメチルスルホキシド、ＰＧＭＥＡ、ＰＧＭＥがより好ましく、シクロヘキサノン、ＰＧＭＥＡがさらに好ましい。 When the rinse liquid contains an organic solvent, the organic solvent can be used singly or in combination of two or more. In the present invention, cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethylsulfoxide, PGMEA and PGME are more preferred, and cyclohexanone and PGMEA are more preferred. More preferred.
　リンス液が有機溶剤を含む場合、リンス液は、５０質量％以上が有機溶剤であることが好ましく、７０質量％以上が有機溶剤であることがより好ましく、９０質量％以上が有機溶剤であることが更に好ましい。また、リンス液は、１００質量％が有機溶剤であってもよい。 When the rinse liquid contains an organic solvent, the rinse liquid is preferably 50% by mass or more of the organic solvent, more preferably 70% by mass or more of the organic solvent, and 90% by mass or more of the organic solvent. is more preferred. Further, 100% by mass of the rinse liquid may be an organic solvent.
　リンス液は、他の成分を更に含んでもよい。
　他の成分としては、例えば、公知の界面活性剤や公知の消泡剤等が挙げられる。 The rinse solution may further contain other components.
Other components include, for example, known surfactants and known antifoaming agents.
〔リンス液の供給方法〕
　リンス液の供給方法は、所望のパターンを形成できれば特に制限は無く、基材をリンス液に浸漬する方法、基材に液盛りによりリンス液を供給する方法、基材にリンス液をシャワーで供給する方法、基材上にストレートノズル等の手段によりリンス液を連続供給する方法がある。
　リンス液の浸透性、非画像部の除去性、製造上の効率の観点から、リンス液をシャワーノズル、ストレートノズル、スプレーノズルなどで供給する方法があり、スプレーノズルにて連続供給する方法が好ましく、画像部へのリンス液の浸透性の観点からは、スプレーノズルで供給する方法がより好ましい。ノズルの種類は特に制限は無く、ストレートノズル、シャワーノズル、スプレーノズル等が挙げられる。
　すなわち、リンス工程は、リンス液を上記露光後の膜に対してストレートノズルにより供給、又は、連続供給する工程であることが好ましく、リンス液をスプレーノズルにより供給する工程であることがより好ましい。
　またリンス工程におけるリンス液の供給方法としては、リンス液が連続的に基材に供給され続ける工程、基材上でリンス液が略静止状態で保たれる工程、基材上でリンス液を超音波等で振動させる工程及びそれらを組み合わせた工程などが採用可能である。 [Method of supplying rinse solution]
The method of supplying the rinse solution is not particularly limited as long as the desired pattern can be formed, and includes a method of immersing the base material in the rinse solution, a method of supplying the rinse solution to the base material by piling up the base material, and a method of supplying the rinse solution to the base material by showering. and a method of continuously supplying the rinsing liquid onto the substrate by means of a straight nozzle or the like.
From the viewpoint of the permeability of the rinse liquid, the removability of the non-image areas, and the efficiency in manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a straight nozzle, a spray nozzle, etc., and a continuous supply method using a spray nozzle is preferable. From the viewpoint of the permeability of the rinsing liquid to the image area, the method of supplying the rinsing liquid with a spray nozzle is more preferable. The type of nozzle is not particularly limited, and straight nozzles, shower nozzles, spray nozzles and the like can be mentioned.
That is, the rinsing step is preferably a step of supplying the rinse liquid to the film after exposure through a straight nozzle or a step of continuously supplying the same, and more preferably a step of supplying the rinse liquid through a spray nozzle.
The method of supplying the rinse liquid in the rinse step includes a process in which the rinse liquid is continuously supplied to the base material, a process in which the rinse liquid is kept substantially stationary on the base material, and a process in which the rinse liquid is kept on the base material in a substantially stationary state. A process of vibrating with sound waves or the like and a process of combining them can be adopted.
　リンス時間としては、１０秒～１０分間が好ましく、２０秒～５分間がより好ましい。リンス時のリンス液の温度は、特に定めるものではないが、好ましくは、１０～４５℃、より好ましくは、１８℃～３０℃で行うことができる。 The rinse time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid during rinsing is not particularly specified, but is preferably 10 to 45°C, more preferably 18 to 30°C.
＜加熱工程＞
　現像工程により得られたパターン（リンス工程を行う場合は、リンス後のパターン）は、上記現像により得られたパターン（樹脂組成物からなる部材）を加熱する加熱工程に供さることが好ましい。
　すなわち、本発明のポリイミド含有部形成用組成物に係る硬化物の製造方法は、現像工程により得られたパターンを加熱する加熱工程を含んでもよい。　また、本発明のポリイミド含有部形成用組成物に係る硬化物の製造方法は、現像工程を行わずに他の方法で得られたパターン、又は、適用工程により得られた膜を加熱する加熱工程を含むことも好ましく、現像工程を行わずに、適用工程により得られた膜を加熱する加熱工程を含むこともより好ましい。
　加熱工程において、ポリイミド前駆体等の樹脂は環化してポリイミド等の樹脂となる。
　また、特定樹脂、又は特定樹脂以外の架橋剤における未反応の架橋性基の架橋なども進行する。
　加熱工程における加熱温度（最高加熱温度）としては、３７５℃以下が好ましく、３５０℃以下がより好ましく、３００℃以下が一層好ましく、２５０℃以下とすることもできる。
　上記加熱温度の下限は、１６０℃以上であることが好ましく、１７０℃以上であることがより好ましく、１８０℃以上であることが更に好ましい。
　加熱工程における加熱温度、加熱時間等の加熱条件を調整することにより、ポリイミド含有部のガラス転移温度を調整することが可能となる。具体的には、より高温で、より長時間加熱することにより、ポリイミドの閉環率が増大し、ガラス転移温度は高くなると考えられる。 <Heating process>
The pattern obtained by the developing step (the pattern after rinsing when the rinsing step is performed) is preferably subjected to a heating step of heating the pattern obtained by the above developing (the member made of the resin composition).
That is, the method for producing a cured product of the composition for forming a polyimide-containing portion of the present invention may include a heating step of heating the pattern obtained by the developing step. Further, the method for producing a cured product according to the composition for forming a polyimide-containing portion of the present invention includes a pattern obtained by another method without performing the developing step, or a heating step of heating the film obtained by the applying step It is also preferable to include a heating step of heating the film obtained by the applying step without performing the developing step.
In the heating step, a resin such as a polyimide precursor is cyclized into a resin such as polyimide.
In addition, cross-linking of unreacted cross-linkable groups in the specific resin or a cross-linking agent other than the specific resin also progresses.
The heating temperature (maximum heating temperature) in the heating step is preferably 375° C. or lower, more preferably 350° C. or lower, even more preferably 300° C. or lower, and may be 250° C. or lower.
The lower limit of the heating temperature is preferably 160° C. or higher, more preferably 170° C. or higher, and even more preferably 180° C. or higher.
By adjusting heating conditions such as heating temperature and heating time in the heating step, it is possible to adjust the glass transition temperature of the polyimide-containing portion. Specifically, it is thought that heating at a higher temperature for a longer time increases the ring closure rate of the polyimide and raises the glass transition temperature.
　加熱工程は、加熱により、上記塩基発生剤から発生した塩基等の作用により、上記パターン内で上記ポリイミド前駆体の環化反応を促進する工程であることが好ましい。 The heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor in the pattern by the action of the base generated from the base generator by heating.
　加熱工程における加熱は、加熱開始時の温度から最高加熱温度まで１～１２℃／分の昇温速度で行うことが好ましい。上記昇温速度は２～１０℃／分がより好ましく、３～１０℃／分が更に好ましい。昇温速度を１℃／分以上とすることにより、生産性を確保しつつ、酸又は溶剤の過剰な揮発を防止することができ、昇温速度を１２℃／分以下とすることにより、硬化物の残存応力を緩和することができる。
　加えて、急速加熱可能なオーブンの場合、加熱開始時の温度から最高加熱温度まで１～８℃／秒の昇温速度で行うことが好ましく、２～７℃／秒がより好ましく、３～６℃／秒が更に好ましい。 Heating in the heating step is preferably carried out at a temperature rising rate of 1 to 12° C./min from the temperature at the start of heating to the maximum heating temperature. The rate of temperature increase is more preferably 2 to 10°C/min, still more preferably 3 to 10°C/min. By setting the temperature rise rate to 1°C/min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity. The residual stress of the object can be relaxed.
In addition, in the case of an oven capable of rapid heating, it is preferable to increase the temperature from the temperature at the start of heating to the maximum heating temperature at a rate of 1 to 8 ° C./sec, more preferably 2 to 7 ° C./sec, and 3 to 6 °C/sec is more preferred.
　加熱開始時の温度は、２０℃～１５０℃が好ましく、２０℃～１３０℃がより好ましく、２５℃～１２０℃が更に好ましい。加熱開始時の温度は、最高加熱温度まで加熱する工程を開始する際の温度のことをいう。例えば、本発明の樹脂組成物を基材の上に適用した後、乾燥させる場合、この乾燥後の膜（層）の温度であり、例えば、本発明の樹脂組成物に含まれる溶剤の沸点よりも、３０～２００℃低い温度から昇温させることが好ましい。 The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at which the process of heating up to the maximum heating temperature is started. For example, when the resin composition of the present invention is applied onto a substrate and then dried, the temperature of the film (layer) after drying is, for example, the boiling point of the solvent contained in the resin composition of the present invention. Also, it is preferable to raise the temperature from a temperature lower by 30 to 200°C.
　加熱時間（最高加熱温度での加熱時間）は、５～３６０分であることが好ましく、１０～３００分であることがより好ましく、１５～２４０分であることが更に好ましい。 The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, even more preferably 15 to 240 minutes.
　特に多層の積層体を形成する場合、層間の密着性の観点から、加熱温度は３０℃以上であることが好ましく、８０℃以上であることがより好ましく、１００℃以上であることが更に好ましく、１２０℃以上であることが特に好ましい。
　上記加熱温度の上限は、３５０℃以下であることが好ましく、２５０℃以下であることがより好ましく、２４０℃以下であることが更に好ましい。 Especially when forming a multilayer laminate, the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, and further preferably 100° C. or higher, from the viewpoint of adhesion between layers. 120° C. or higher is particularly preferred.
The upper limit of the heating temperature is preferably 350° C. or lower, more preferably 250° C. or lower, and even more preferably 240° C. or lower.
　加熱は段階的に行ってもよい。例として、２５℃から１２０℃まで３℃／分で昇温し、１２０℃にて６０分保持し、１２０℃から１８０℃まで２℃／分で昇温し、１８０℃にて１２０分保持する、といった工程を行ってもよい。また、米国特許第９１５９５４７号明細書に記載のように紫外線を照射しながら処理することも好ましい。このような前処理工程により膜の特性を向上させることが可能である。前処理工程は１０秒間～２時間程度の短い時間で行うとよく、１５秒～３０分間がより好ましい。前処理は２段階以上のステップとしてもよく、例えば１００～１５０℃の範囲で１段階目の前処理工程を行い、その後に１５０～２００℃の範囲で２段階目の前処理工程を行ってもよい。
　更に、加熱後冷却してもよく、この場合の冷却速度としては、１～５℃／分であることが好ましい。 Heating may be done in stages. As an example, the temperature is raised from 25° C. to 120° C. at 3° C./min, held at 120° C. for 60 minutes, heated from 120° C. to 180° C. at 2° C./min, and held at 180° C. for 120 minutes. , may be performed. It is also preferable to carry out the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such a pretreatment process can improve the properties of the film. The pretreatment step is preferably performed for a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, the first pretreatment step may be performed in the range of 100 to 150°C, and then the second pretreatment step may be performed in the range of 150 to 200°C. good.
Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5°C/min.
　加熱工程は、窒素、ヘリウム、アルゴンなどの不活性ガスを流す、減圧下で行う等により、低酸素濃度の雰囲気で行うことが特定樹脂の分解を防ぐ点で好ましい。酸素濃度は、５０ｐｐｍ（体積比）以下が好ましく、２０ｐｐｍ（体積比）以下がより好ましい。
　加熱工程における加熱手段としては、特に限定されないが、例えばホットプレート、赤外炉、電熱式オーブン、熱風式オーブン、赤外線オーブンなどが挙げられる。 The heating step is preferably carried out in an atmosphere of low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium or argon, or under reduced pressure, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.
The heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, an infrared oven and the like.
＜現像後露光工程＞
　現像工程により得られた（リンス工程を行う場合は、リンス後のパターン）は、上記加熱工程に代えて、又は、上記加熱工程に加えて、現像工程後のパターンを露光する現像後露光工程に供されてもよい。
　すなわち、本発明のポリイミド含有部形成用組成物に係る硬化物の製造方法は、現像工程により得られたパターンを露光する現像後露光工程を含んでもよい。本発明のポリイミド含有部形成用組成物に係る硬化物の製造方法は、加熱工程及び現像後露光工程を含んでもよいし、加熱工程及び現像後露光工程の一方のみを含んでもよい。
　現像後露光工程においては、例えば、光塩基発生剤の感光によってポリイミド前駆体等の環化が進行する反応や、光酸発生剤の感光によって酸分解性基の脱離が進行する反応などを促進することができる。
　現像後露光工程においては、現像工程において得られたパターンの少なくとも一部が露光されればよいが、上記パターンの全部が露光されることが好ましい。
　現像後露光工程における露光量は、感光性化合物が感度を有する波長における露光エネルギー換算で、５０～２０，０００ｍＪ／ｃｍ２であることが好ましく、１００～１５，０００ｍＪ／ｃｍ２であることがより好ましい。
　現像後露光工程は、例えば、上述の露光工程における光源を用いて行うことができ、ブロードバンド光を用いることが好ましい。 <Post-development exposure process>
The pattern obtained by the development step (the pattern after rinsing when the rinsing step is performed) is subjected to a post-development exposure step of exposing the pattern after the development step instead of or in addition to the heating step. may be provided.
That is, the method for producing a cured product of the composition for forming a polyimide-containing portion of the present invention may include a post-development exposure step of exposing the pattern obtained in the development step. The method for producing a cured product of the composition for forming a polyimide-containing portion of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.
In the post-development exposure step, for example, a reaction in which cyclization of a polyimide precursor or the like proceeds by exposure of a photobase generator, or a reaction in which elimination of an acid-decomposable group proceeds by exposure of a photoacid generator is promoted. can do.
In the post-development exposure step, at least part of the pattern obtained in the development step may be exposed, but it is preferable to expose the entire pattern.
The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ/cm 2 , more preferably 100 to 15,000 mJ/cm 2 in terms of exposure energy at the wavelength to which the photosensitive compound is sensitive. preferable.
The post-development exposure step can be performed using, for example, the light source used in the exposure step described above, and broadband light is preferably used.
＜基板Ｂを準備する工程＞
　本発明のポリイミド含有部形成用組成物が用いられる接合体の製造方法は、配線端子を備える面を有する基板Ｂを準備する工程を含む。 <Step of preparing substrate B>
A method for manufacturing a bonded body using the composition for forming a polyimide-containing portion of the present invention includes a step of preparing a substrate B having a surface provided with wiring terminals.
　基板Ｂの形態は、ウエハであってもチップであってもよい。これらは、所望する接合体の設計に応じて選択すればよい。 The form of the substrate B may be either a wafer or a chip. These may be selected according to the desired design of the joined body.
〔基板Ｂ〕
　基板Ｂは、配線端子を有する。
　以下、基板Ｂにおける配線端子を、配線端子Ｂとも記載する。 [Substrate B]
The substrate B has wiring terminals.
The wiring terminals on the substrate B are also referred to as wiring terminals B hereinafter.
　基板Ｂの厚さは、０．１～５ｍｍが好ましく、０．２～１ｍｍがより好ましい。
　後述する接合工程により得られる接合体において、上記配線端子Ｂの少なくとも一部が上述の基板Ａにおける配線端子Ａと電気的に接合される。 The thickness of the substrate B is preferably 0.1-5 mm, more preferably 0.2-1 mm.
At least a portion of the wiring terminal B is electrically connected to the wiring terminal A on the substrate A in the bonded body obtained by the bonding step described later.
　基板Ｂに用いられる材料は特に限定されず、上述の基板Ａと同様の材料が好ましく挙げられる。
　また、配線端子Ｂの好ましい態様も、配線端子Ａの好ましい態様と同様である。
　基板Ｂは電子回路を含む電子回路領域を有していてもよい。また、上記電子回路は、半導体等の素子を有していてもよい。また、上記電子回路は、上記配線端子と電気的に接合されていることが好ましい。
　基板Ｂがウエハである場合のサイズとしては、直径（基板Ｂが円形でない場合は最大径）を１００ｍｍ以上とすることができる。また、大型の基板としては、例えば、２００ｍｍ以上であることが好ましく、２５０ｍｍ以上であることがより好ましい。上限は特にないが、２，０００ｍｍ以下であることが好ましい。
　基板Ｂがチップである場合のサイズとしては、直径（基板Ｂが円形でない場合は最大径）を７ｍｍ以上とすることが好ましく、８ｍｍ以上がより好ましく、１０ｍｍ以上が更に好ましい。上限としては、例えば、５０ｍｍ以下であることが好ましく、３０ｍｍ以下であることがより好ましく、２０ｍｍ以下であることが更に好ましい。 The material used for the substrate B is not particularly limited, and the same materials as those for the substrate A described above are preferably used.
Moreover, the preferable aspect of the wiring terminal B is also the same as the preferable aspect of the wiring terminal A.
Substrate B may have an electronic circuit area containing electronic circuits. Moreover, the electronic circuit may have an element such as a semiconductor. Moreover, it is preferable that the electronic circuit is electrically connected to the wiring terminal.
When the substrate B is a wafer, the diameter (maximum diameter if the substrate B is not circular) can be 100 mm or more. Moreover, as a large substrate, for example, it is preferably 200 mm or more, and more preferably 250 mm or more. Although there is no particular upper limit, it is preferably 2,000 mm or less.
When the substrate B is a chip, the diameter (maximum diameter if the substrate B is not circular) is preferably 7 mm or more, more preferably 8 mm or more, and even more preferably 10 mm or more. The upper limit is, for example, preferably 50 mm or less, more preferably 30 mm or less, and even more preferably 20 mm or less.
＜第２のポリイミド含有部形成工程＞
　本発明のポリイミド含有部形成用組成物が用いられる接合体の製造方法は、接合工程の前に、上記基板Ｂの上記配線端子を備える面上に第２のポリイミド含有部を形成する第２のポリイミド含有部形成工程を更に含むことが好ましい。
　第２のポリイミド含有部形成工程は、例えば、上述の基板Ａに対するポリイミド含有部形成工程と同様の方法により行うことができる。
　ここで、第２のポリイミド含有部形成工程においては、本発明のポリイミド含有部形成用組成物を用いてもよいし、他の公知のポリイミド含有部形成用組成物を用いてもよいが、本発明のポリイミド含有部形成用組成物を用いることが好ましい。
　ただし、第２のポリイミド含有部形成工程において本発明のポリイミド含有部形成用組成物を用いる場合、第２のポリイミド含有部形成工程において用いられる本発明のポリイミド含有部形成用組成物の組成と、基板Ａに対するポリイミド含有部形成工程において用いられるポリイミド含有部形成用組成物の組成とは、同一であってもよいし、異なっていてもよい。
　第２のポリイミド含有部の好ましい態様は、上述の基板Ａにおいて形成されるポリイミド含有部の好ましい態様と同様である。
　後述の接合工程において、第２のポリイミド含有部と、上述の基板Ａにおいて形成されるポリイミド含有部とが少なくとも一部で接するように接合することで、接合体における接着性が向上すると考えられる。 <Step of Forming Second Polyimide-Containing Portion>
In the method for producing a bonded body using the composition for forming a polyimide-containing portion of the present invention, before the bonding step, a second polyimide-containing portion is formed on the surface of the substrate B provided with the wiring terminal. It is preferable to further include a polyimide-containing portion forming step.
The second polyimide-containing portion forming step can be performed, for example, by the same method as the polyimide-containing portion forming step for the substrate A described above.
Here, in the second polyimide-containing portion forming step, the composition for forming a polyimide-containing portion of the present invention may be used, or another known composition for forming a polyimide-containing portion may be used. It is preferable to use the polyimide-containing part-forming composition of the invention.
However, when the polyimide-containing portion-forming composition of the present invention is used in the second polyimide-containing portion-forming step, the composition of the polyimide-containing portion-forming composition of the present invention used in the second polyimide-containing portion-forming step, The composition for forming the polyimide-containing portion used in the step of forming the polyimide-containing portion on the substrate A may be the same as or different from the composition.
Preferred aspects of the second polyimide-containing portion are the same as preferred aspects of the polyimide-containing portion formed on the substrate A described above.
It is believed that in the bonding step described later, the second polyimide-containing portion and the polyimide-containing portion formed on the substrate A are bonded so that at least a portion thereof is in contact with each other, thereby improving the adhesiveness of the bonded body.
　また、第２のポリイミド含有部を形成する場合、第２のポリイミド含有部のガラス転移温度は、接合工程における接合温度よりも低いことが好ましい。
　最大剥離抗力を増大する観点からは、第２のポリイミド含有部のガラス転移温度は、接合工程における接合温度よりも３０℃以上低いことが好ましく、５０℃以上低いことがより好ましく、７０℃以上低いことが更に好ましい。
　また、第２のポリイミド含有部のガラス転移温度は、接合工程における接合温度よりも３０℃以上高いことが好ましい。 Moreover, when forming the second polyimide-containing portion, the glass transition temperature of the second polyimide-containing portion is preferably lower than the bonding temperature in the bonding step.
From the viewpoint of increasing the maximum peel resistance, the glass transition temperature of the second polyimide-containing portion is preferably 30 ° C. or more lower than the bonding temperature in the bonding step, more preferably 50 ° C. or more, and 70 ° C. or more. is more preferred.
Also, the glass transition temperature of the second polyimide-containing portion is preferably 30° C. or more higher than the bonding temperature in the bonding step.
〔平坦化工程〕
　本発明のポリイミド含有部形成用組成物が用いられる接合体の製造方法は、上記ポリイミド含有部形成工程と、接合工程との間に、基板Ａのポリイミド含有部の表面を平坦化する平坦化工程を含むことが好ましい。
　後述する接合工程においては、基材Ａにおける平坦化されたポリイミド含有部と、基材Ｂの表面（又は、平坦化されていてもよい第２のポリイミド含有部の表面）とが接触するよう接合されることが好ましい。 [Planarization process]
In the method for producing a bonded body using the composition for forming a polyimide-containing portion of the present invention, a planarization step of planarizing the surface of the polyimide-containing portion of the substrate A is performed between the polyimide-containing portion forming step and the bonding step. It is preferred to include
In the bonding step described later, the flattened polyimide-containing portion of the base material A and the surface of the base material B (or the surface of the second polyimide-containing portion, which may be flattened) are in contact with each other. preferably.
　上記平坦化により、基板Ａにおける配線端子Ａは上記ポリイミド含有部から露出することが好ましい。
　上記平坦化は、カッティング、機械研磨、研削、プラズマ処理、レーザーアブレーション等の物理研磨によって行われてもよいし、ＣＭＰ（Chemical Mechanical Polishing）等の化学研磨により行われてもよい。
　また、カッティング後にＣＭＰを行うなど、これらの方法を組み合わせてもよい。
　具体的には、例えば、ポリイミド含有部の表面をダイヤモンドバイトで切削し、ポリイミド含有部の新たな表面と、配線端子Ａとを露出させる態様が挙げられる。基板Ａにおける配線端子Ａとポリイミド含有部とを、配線端子Ａが露出するように平坦化処理を行なうことで、配線端子Ａとポリイミド含有部の一括平坦化による配線端子Ａの頭出しが可能となる。
　平坦化は、例えばサーフェースプレーナ（Surface Planer）で行うことができる。サーフェースプレーナとしては、例えばスピンドルにダイヤモンドバイトが装着されたものが例示され、ディスコ製のＤＦＳ８９１０、ＤＦＳ８９６０、ＤＡＳ８９２０、ＤＡＳ８９３０（いずれも商品名）が例示される。 It is preferable that the wiring terminal A on the substrate A is exposed from the polyimide-containing portion by the planarization.
The flattening may be performed by physical polishing such as cutting, mechanical polishing, grinding, plasma treatment, laser ablation, or by chemical polishing such as CMP (Chemical Mechanical Polishing).
Also, these methods may be combined, such as performing CMP after cutting.
Specifically, for example, the surface of the polyimide-containing portion is cut with a diamond cutting tool to expose a new surface of the polyimide-containing portion and the wiring terminal A. By flattening the wiring terminal A and the polyimide-containing portion on the substrate A so that the wiring terminal A is exposed, the wiring terminal A and the polyimide-containing portion can be collectively flattened to expose the wiring terminal A. Become.
Planarization can be performed, for example, with a surface planer. Examples of the surface planer include those in which a diamond tool is attached to a spindle, such as DFS8910, DFS8960, DAS8920, and DAS8930 (all trade names) manufactured by Disco.
－ＴＴＶ－
　平坦化工程において、ポリイミド含有部は配線端子Ａと共に平坦化されることが好ましい。上記平坦化の程度としては、ポリイミド含有部及び配線端子ＡのＴＴＶ（Total Thickness Variation：トータルシックネスバリエーション）が１０μｍ以下であることが好ましく、５μｍ以下であることがより好ましく、３μｍ以下であることが更に好ましい。
　本発明において、ＴＴＶとは、ポリイミド含有部のエッジ部から１ｍｍ以上内側の領域を２ｍｍ四方の区画に分割（ポリイミド含有部の面積が微小であるなど、２ｍｍ四方の区画に分割できない場合はポリイミド含有部のエッジ部から１ｍｍ以上内側における全領域を一区画とする）し、各区画ごとに一方の表面と他方の表面との間の最大厚さ（Ｔ１）と、一方の表面と他方の表面との間の最小厚さ（Ｔ２）を測定し、各区画ごとに膜厚差（Ｔ１－Ｔ２）を算出し、膜厚差（Ｔ１－Ｔ２）が大きい順に各区画に序列を設け、最上位区画（最も膜厚差が大きい）から膜厚差の大きい順に総区画数の１０％（小数点以下が存在する場合は切り捨て）に相当する個数の区画群および最下位区画（最も膜厚差が小さい）から膜厚差の小さい順に総区画数の１０％（小数点以下が存在する場合は切り捨て）に相当する個数の区画群を除外し、残った区画群の各膜厚差（Ｔ１－Ｔ２）の算術平均値をいう。
　本明細書においては、ここで定義するポリイミド含有部のＴＴＶを特に意味する場合に、「区画評価ＴＴＶ」と称することがある。ポリイミド含有部のＴＴＶを上記上限値以下とすることにより、膜厚が概ね均一になり、基板Ｂとの接着性が向上する。 -TTV-
In the planarization step, the polyimide-containing portion is preferably planarized together with the wiring terminal A. As for the degree of planarization, the TTV (Total Thickness Variation) of the polyimide-containing portion and the wiring terminal A is preferably 10 μm or less, more preferably 5 μm or less, and 3 μm or less. More preferred.
In the present invention, TTV means that the area 1 mm or more inside from the edge of the polyimide-containing portion is divided into 2 mm square sections (if the area of the polyimide containing portion is small, etc., it cannot be divided into 2 mm square sections, The entire area inside 1 mm or more from the edge of the part is defined as one section), and for each section, the maximum thickness between one surface and the other surface (T1), and the one surface and the other surface Measure the minimum thickness (T2) between, calculate the film thickness difference (T1-T2) for each section, rank each section in descending order of the film thickness difference (T1-T2), the highest section The number of partition groups corresponding to 10% of the total number of partitions (rounded down if there is a decimal point) and the lowest partition (smallest film thickness difference) in descending order of film thickness difference from (largest film thickness difference) 10% of the total number of compartments (rounded down if there is a decimal point) in descending order of film thickness difference from the remaining compartment groups. mean value.
In this specification, when specifically referring to the TTV of a polyimide-containing portion as defined herein, it may be referred to as a "compartment-rated TTV." By setting the TTV of the polyimide-containing portion to the upper limit value or less, the film thickness becomes generally uniform, and the adhesiveness to the substrate B is improved.
－Ｒａ－
　本発明のポリイミド含有部は、基板Ａの表面と接する側とは反対側の面の表面粗さであるＲａが１０ｎｍ以上１．５μｍ以下であることが好ましい。上限としては、１μｍ以下であることが好ましく、５００ｎｍ以下であることがより好ましく、３００ｎｍ以下であることがさらに好ましく、２００ｎｍ以下であることが一層好ましく、１５０ｎｍ以下であることがより一層好ましく、１２０ｎｍ以下であることがさらに一層好ましい。
　ポリイミド含有部の表面粗さを上記下限値以上とすることにより、アンカー効果が働き基板Ｂとの接着性を向上させることができる。
　また、表面粗さを上記上限値以下とすることにより、基板Ｂとの接合時に、泡などを含んで接合してしまうことによるボイド等の欠陥発生を効果的に抑制することができる。 -Ra-
The polyimide-containing portion of the present invention preferably has a surface roughness Ra of 10 nm or more and 1.5 μm or less on the side opposite to the side in contact with the surface of the substrate A. The upper limit is preferably 1 µm or less, more preferably 500 nm or less, still more preferably 300 nm or less, even more preferably 200 nm or less, even more preferably 150 nm or less, and 120 nm. The following are even more preferred.
By setting the surface roughness of the polyimide-containing portion to the above lower limit or more, the anchor effect works and the adhesiveness to the substrate B can be improved.
Further, by setting the surface roughness to the above upper limit or less, it is possible to effectively suppress the occurrence of defects such as voids due to bubbles and the like being included in the bonding with the substrate B.
　基板Ｂ上に第２のポリイミド含有部を形成する場合、上記第２のポリイミド含有部形成工程と、接合工程との間に、第２のポリイミド含有部の表面を平坦化する第２の平坦化工程を含むことが好ましい。
　第２の平坦化工程は、上述の基板Ａにおける平坦化工程と同様の方法により行うことができる。 When forming the second polyimide-containing portion on the substrate B, a second planarization for planarizing the surface of the second polyimide-containing portion is performed between the step of forming the second polyimide-containing portion and the bonding step. It is preferable to include steps.
The second planarization process can be performed by the same method as the planarization process for the substrate A described above.
〔接合工程〕
　本発明のポリイミド含有部形成用組成物が用いられる接合体の製造方法は、上記基板Ａのポリイミド含有部を有する面と、上記基板Ｂにおける上記配線端子を備える面とを接合する接合工程を含む。
　上記基板Ｂが第２のポリイミド含有部を有する場合、接合工程は、上記基板Ａのポリイミド含有部を有する面と、上記基板Ｂにおける上記第２のポリイミド含有部を有する面とを接合する工程である。 [Joining process]
A method for producing a bonded body using the composition for forming a polyimide-containing portion of the present invention includes a bonding step of bonding the surface of the substrate A having the polyimide-containing portion and the surface of the substrate B having the wiring terminal. .
When the substrate B has a second polyimide-containing portion, the bonding step is a step of bonding the surface of the substrate A having the polyimide-containing portion and the surface of the substrate B having the second polyimide-containing portion. be.
　接合により、基板Ａにおける配線端子Ａと、基板Ｂにおける配線端子Ｂとが電気的に接合される。
　上記接合工程において、上記基板Ａのポリイミド含有部を有する面に含まれる電極と、上記基板Ｂにおける上記配線端子を備える面における電極とが直接接するように接合されることも、本発明の好ましい態様の１つである。
　すなわち、配線端子Ａ及び配線端子Ｂのいずれもが、導通路を有しないことも好ましい。本発明においては、ポリイミド含有部のガラス転移温度が接合温度よりも低いことにより、導通路を使用しない場合であっても、基板Ａと基板Ｂとの接着性、電気的な接続性が確保できる。 By bonding, the wiring terminal A on the substrate A and the wiring terminal B on the substrate B are electrically bonded.
In the bonding step, it is also a preferred embodiment of the present invention that the electrodes included in the surface of the substrate A having the polyimide-containing portion and the electrodes on the surface of the substrate B having the wiring terminals are in direct contact with each other. is one of
That is, it is also preferable that neither the wiring terminal A nor the wiring terminal B have a conducting path. In the present invention, the glass transition temperature of the polyimide-containing portion is lower than the bonding temperature, so that the adhesiveness and electrical connectivity between the substrates A and B can be ensured even when no conducting paths are used. .
　接合は、加熱を含む手段により行われることが好ましく、加熱及び加圧を含む手段により行われることがより好ましい。
　接合時の温度（接合温度）は、１００℃以上であることが好ましく、１５０℃以上であることがより好ましく、１８０℃以上であることがさらに好ましい。上限としては、４５０℃以下であることが好ましく、４００℃以下であることがより好ましく、３８０℃以下であることが更に好ましく、３５０℃以下であることが特に好ましく、３００℃以下であることが一層好ましく、２８０℃以下であることがより一層好ましく、２６０℃以下であることがさらに一層好ましく、２５０℃以下であることがさらに一層好ましい。この温度は、上述したように、導通路を溶融させ電極間の接合を可能とすることを考慮して、導通路の融点近傍の温度であることが好ましい。
　接合工程における加熱時間は特に限定されないが、５秒以上であることが好ましく、１分以上であることがより好ましく、２分以上であることがさらに好ましい。上限としては、３０分以下であることが実際的である。
　加熱時の環境は特に限定されないが、減圧雰囲気下、機械的にポリイミド含有部を加圧しながら行なうことが好ましい。雰囲気圧としては、１×１０－５ｍｂａｒ以上であることが好ましく、１×１０－４ｍｂａｒ以上であることがより好ましく、５×１０－４ｍｂａｒ以上であることがさらに好ましい。上限としては、０．１ｍｂａｒ以下であることが好ましく、１×１０－２ｍｂａｒ以下であることがより好ましく、５×１０－３ｍｂａｒ以下であることがさらに好ましい。
　接合は２つの基板（基板Ａ及び基板Ｂ）を挟持して行うことが好ましく、このとき基板に圧力をかけることが好ましい。基板にかける圧力は、１ｋＮ以上であることが好ましく、５ｋＮ以上であることがより好ましく、１０ｋＮ以上であることがさらに好ましい。上限としては、１００ｋＮ以下であることが実際的である。接合工程において用いられる装置は特に限定されないが、電子部品のリフローに用いられる装置を好適に利用することができる。 Bonding is preferably performed by means including heating, more preferably by means including heating and pressure.
The temperature during bonding (bonding temperature) is preferably 100° C. or higher, more preferably 150° C. or higher, and even more preferably 180° C. or higher. The upper limit is preferably 450°C or lower, more preferably 400°C or lower, even more preferably 380°C or lower, particularly preferably 350°C or lower, and preferably 300°C or lower. It is more preferably 280° C. or lower, even more preferably 260° C. or lower, and even more preferably 250° C. or lower. This temperature is preferably a temperature near the melting point of the conductive path, considering that the conductive path is melted and the electrodes can be joined together, as described above.
The heating time in the bonding step is not particularly limited, but is preferably 5 seconds or longer, more preferably 1 minute or longer, and even more preferably 2 minutes or longer. A practical upper limit is 30 minutes or less.
The heating environment is not particularly limited, but it is preferable to perform the heating under a reduced pressure atmosphere while mechanically pressurizing the polyimide-containing portion. The atmospheric pressure is preferably 1×10 −5 mbar or higher, more preferably 1×10 −4 mbar or higher, and even more preferably 5×10 −4 mbar or higher. The upper limit is preferably 0.1 mbar or less, more preferably 1×10 −2 mbar or less, and even more preferably 5×10 −3 mbar or less.
Bonding is preferably performed by sandwiching two substrates (substrate A and substrate B), and at this time, it is preferable to apply pressure to the substrates. The pressure applied to the substrate is preferably 1 kN or more, more preferably 5 kN or more, and even more preferably 10 kN or more. A practical upper limit is 100 kN or less. The device used in the bonding step is not particularly limited, but a device used for reflowing electronic components can be preferably used.
　また、接合工程において、ポリイミド含有部を備えた基板Ａの温度が７０℃以上に予熱されていることも好ましい。
　また、基板Ｂが第２のポリイミド含有部を含む場合、基板Ｂの温度が７０℃以上に予熱されていることも好ましい。
　上記温度は、７０℃以上であることが好ましく、９０℃以上であることがより好ましい。また、上記温度の上限は、特に限定されないが、１３０℃以下であることが好ましい。
　上記態様により、接合プロセスのタクトタイムを低減することができる。
　また、接合時のポリイミド含有部の流動性が向上し、最大剥離抗力が向上する場合もある。 Moreover, in the bonding step, it is also preferable that the temperature of the substrate A provided with the polyimide-containing portion is preheated to 70° C. or higher.
Further, when the substrate B includes the second polyimide-containing part, it is also preferable that the temperature of the substrate B is preheated to 70° C. or higher.
The temperature is preferably 70° C. or higher, more preferably 90° C. or higher. Moreover, although the upper limit of the temperature is not particularly limited, it is preferably 130° C. or less.
According to the above aspect, the tact time of the bonding process can be reduced.
In addition, the fluidity of the polyimide-containing portion during bonding is improved, and the maximum peel resistance may be improved.
〔その他の工程〕
　なお、本発明のポリイミド含有部形成用組成物が用いられる接合体の製造方法は上記に規定される各工程間にその他の工程を介在させることを妨げるものではない。また、接合工程として基板Ａと基板Ｂとを面と面で対峙させて接合する例を中心に説明したが、基板Ａに対して複数の基板Ｂを並列して配置し接着するような形態としてもよい。あるいは、相応の厚みのある基板Ａと基板Ｂとを併設しその側面同士を接合する形態なども挙げられる。 [Other processes]
It should be noted that the method for producing a joined body using the composition for forming a polyimide-containing portion of the present invention does not preclude interposing other steps between the steps defined above. Also, as the bonding process, the example in which the substrate A and the substrate B are faced face-to-face and bonded has been mainly described, but a form in which a plurality of substrates B are arranged in parallel with respect to the substrate A and bonded together has been described. good too. Alternatively, there is a form in which a substrate A and a substrate B having a corresponding thickness are placed side by side and their side surfaces are joined together.
＜接合体の製造方法の例＞
　以下、接合体の製造方法の一例について図を使用して説明する。
　図２は、本発明の一実施形態に係る接合体の製造方法で基板を接着するときの工程（一部）を模式的に断面図で示した工程説明図である。まず、シリコンウエハ１ｘに電子回路領域８が配設され、そこに電極３１（配線端子Ａ）が付された基板Ａ（下地基板）１を準備する（図２（ａ））。基板Ａ１の電子回路領域８の内部にはすでに導体もしくは半導体で構成された電子回路８１が形成されている。電子回路を形成する方法は特に制限されず、定法により形成することができる。また、電子回路の構造や部材も特に限定されず、例えば、トランジスタおよびそれを電極に導通させる配線構造が挙げられる。 <Example of manufacturing method of joined body>
An example of a method for manufacturing a joined body will be described below with reference to the drawings.
FIG. 2 is a process explanatory view schematically showing (a part of) the process of bonding the substrates in the method of manufacturing a joined body according to one embodiment of the present invention, using cross-sectional views. First, a substrate A (underlying substrate) 1 having an electronic circuit region 8 provided on a silicon wafer 1x and electrodes 31 (wiring terminals A) attached thereon is prepared (FIG. 2(a)). An electronic circuit 81 made of a conductor or a semiconductor is already formed inside the electronic circuit area 8 of the substrate A1. A method for forming an electronic circuit is not particularly limited, and it can be formed by a standard method. Also, the structure and members of the electronic circuit are not particularly limited, and examples thereof include a transistor and a wiring structure that electrically connects the transistor to an electrode.
　上記基板Ａ１の電極を配した面（電子回路領域を有する面）Ｐ０に樹脂組成物を適用して樹脂組成物からなる部材（樹脂組成物層）４を形成する（図２（ｂ））。この状態で、樹脂組成物層を加熱し乾燥させてもよい（乾燥工程）。また、乾燥した後、フォトリソグラフィやイオンスパッタリングなどにより樹脂組成物層４をパターニングしてもよい。 A member (resin composition layer) 4 made of the resin composition is formed by applying a resin composition to the surface P0 of the substrate A1 on which the electrodes are arranged (the surface having the electronic circuit region) (FIG. 2(b)). In this state, the resin composition layer may be heated and dried (drying step). After drying, the resin composition layer 4 may be patterned by photolithography, ion sputtering, or the like.
　その後、本実施形態では、樹脂組成物層４を加熱して環化を促し硬化したポリイミド含有部４１とする（図２（ｃ））。これにより、基板Ａ１にポリイミド含有部４１を配設したポリイミド含有部配設基板１ｙを形成する。この例のように、ポリイミド含有部４１は硬化により樹脂組成物層４と比較して収縮してもよい。図面ではやや誇張して示しているが、収縮率は特に限定されず、より小さな収縮率でもよく、あるいは硬化により収縮しなくてもよい。
　また、図に記載の基板Ａは配線端子Ａとして電極３１のみを有しているが、電極３１上に導通路を形成してもよい。導通路は、基板Ａに初めから形成されていてもよいし、ポリイミド含有部を硬化前にパターニングして、パターニング部にめっきなどで導通路を作製しても良い。 After that, in the present embodiment, the resin composition layer 4 is heated to promote cyclization to form a cured polyimide-containing portion 41 (FIG. 2(c)). As a result, a polyimide-containing portion-provided substrate 1y in which the polyimide-containing portion 41 is disposed on the substrate A1 is formed. As in this example, the polyimide-containing portion 41 may shrink compared to the resin composition layer 4 due to curing. Although shown in the drawings in a slightly exaggerated manner, the shrinkage rate is not particularly limited, and a smaller shrinkage rate may be used, or no shrinkage may occur upon curing.
Further, although the substrate A shown in the drawing has only the electrodes 31 as the wiring terminals A, a conductive path may be formed on the electrodes 31 . The conductive path may be formed in the substrate A from the beginning, or the polyimide-containing portion may be patterned before curing, and the conductive path may be formed in the patterned portion by plating or the like.
　本実施形態のポリイミド含有部配設基板１ｙにおいては、電極３１の高さｈ１、ｈ２がばらついている。また、ポリイミド含有部の表面４ａも波を打ったようになり平坦な状態ではない。本実施形態においては、平坦化を行うことにより、このような電極３１の高さのばらつきを解消し、その先端表面を露出させ、ポリイミド含有部の表面も平坦化される。
　このように平坦化を行うことにより、基板の接着性が向上されると考えられる。
　また、導通路を形成しなくとも、配線端子同士の接合性が向上されると考えられる。 In the polyimide-containing portion-disposed substrate 1y of the present embodiment, the heights h1 and h2 of the electrodes 31 vary. The surface 4a of the polyimide-containing portion is also wavy and not flat. In the present embodiment, planarization is performed to eliminate such variations in the height of the electrode 31, expose the tip surface thereof, and planarize the surface of the polyimide-containing portion.
It is considered that the adhesion of the substrate is improved by planarizing in this way.
Also, it is considered that the bondability between the wiring terminals can be improved without forming the conducting path.
　図３は平坦化した後のポリイミド含有部配設基板（積層体）１ｚを示している。このポリイミド含有部の表面４ｂには電極３１の先端３１ａが露出し、ポリイミド含有部の表面４ｂの全体において平坦化されている。 FIG. 3 shows the polyimide-containing portion-disposed substrate (laminate) 1z after flattening. The tip 31a of the electrode 31 is exposed on the surface 4b of the polyimide-containing portion, and the entire surface 4b of the polyimide-containing portion is flattened.
　積層体（平坦化されたポリイミド含有部配設基板）１ｚに対し、基板Ｂを別途準備する（図４（ａ））。基板Ｂ２は、スルーホール電極２ｙを有するシリコンウエハ２ｘ、そこに配設された回路配線８１を有する回路配線領域８、回路配線領域８内に形成された電極３２（配線端子Ｂ）を具備する。
　本実施形態において、基板Ｂにおける配線端子Ｂを有する面にも、第２のポリイミド含有部４２が形成されており、その表面２ａは基板Ａにおけるポリイミド含有部４１の表面と同様に平坦化されている。第２のポリイミド含有部４２の形成及び平坦化は、ポリイミド含有部４１の形成及び平坦化の方法と同様の方法により行うことができる。
　このように、基板Ａのポリイミド含有部４１及び電極３１の表面と、基板Ｂの第２のポリイミド含有部４２及び電極３２の表面とがいずれも平坦化されていることにより、今回の実施形態のように導通路がない場合であっても電気的な接続性が向上する。
　このとき、積層体の電極３１の部分と基板Ｂ２に設けられた電極３２とが接触するようにアライメント（位置合わせ）する。
　ここで、ポリイミド含有部４１及び第２のポリイミド含有部４２の少なくとも一方がマイグレーション抑制剤を含む場合、このアライメントに位置ズレが発生したとしても、電極３１（電極３２）からポリイミド含有部４１（第２のポリイミド含有部４２）に金属が移行することを抑制することができ、耐電圧性能を向上することができる。
　配線端子Ｂにおいても、電極３２上に導通路を形成してもよい。導通路は、基板Ｂに初めから形成されていてもよいし、第２のポリイミド含有部を硬化前にパターニングして、パターニング部にめっきなどで導通路を作製しても良い。 A substrate B is separately prepared for the laminate (flattened polyimide-containing portion-disposed substrate) 1z (FIG. 4A). The substrate B2 includes a silicon wafer 2x having through-hole electrodes 2y, a circuit wiring region 8 having circuit wiring 81 disposed therein, and electrodes 32 (wiring terminals B) formed in the circuit wiring region 8. FIG.
In this embodiment, the second polyimide-containing portion 42 is also formed on the surface of the substrate B having the wiring terminal B, and the surface 2a thereof is planarized in the same manner as the surface of the polyimide-containing portion 41 of the substrate A. there is The formation and flattening of the second polyimide-containing portion 42 can be performed by the same method as the formation and flattening of the polyimide-containing portion 41 .
As described above, the surface of the polyimide-containing portion 41 and the electrode 31 of the substrate A and the surface of the second polyimide-containing portion 42 and the electrode 32 of the substrate B are both flattened. Even if there is no conductive path, the electrical connectivity is improved.
At this time, alignment (alignment) is performed so that the electrodes 31 of the laminate and the electrodes 32 provided on the substrate B2 are in contact with each other.
Here, when at least one of the polyimide-containing portion 41 and the second polyimide-containing portion 42 contains a migration inhibitor, even if a positional deviation occurs in this alignment, the electrode 31 (electrode 32) is separated from the polyimide-containing portion 41 (second polyimide-containing portion 41). It is possible to suppress the migration of metal to the polyimide-containing portion 42) of 2, and to improve the withstand voltage performance.
A conductive path may be formed on the electrode 32 at the wiring terminal B as well. The conducting path may be formed in the substrate B from the beginning, or the second polyimide-containing portion may be patterned before curing, and the patterning portion may be plated to form the conducting path.
　次いで、本実施形態においては、アライメントされた基板Ｂ２と積層体１ｚをポリイミド含有部４１及び第２のポリイミド含有部４２を介して、接合面Ｐ１で当接させて接合する（図４（ｂ））。
　これにより、２つの基板が接合された接合体１００が形成される。接合体１００においては、電極３１と電極３２とが電気的に接合される（接合工程）。
　これと同時に、上記の加熱によりポリイミド含有部４１を軟化させ、積層体１ｚのポリイミド含有部表面４ｂと、基板Ｂの表面（平坦化された第２のポリイミド含有部４２の表面）２ａとを接着させ、接合体１００を形成する。
　本発明においては、ポリイミド含有部のガラス転移温度が、接合工程における接合温度よりも低いため、ポリイミド含有部は十分に軟化し、接着性に優れると考えられる。
　これにより、基板Ａと基板Ｂとの間の電気的な接続を行うとともに、両者の強固な固定状態を実現することができる。 Next, in the present embodiment, the aligned substrate B2 and the laminate 1z are brought into contact with each other via the polyimide-containing portion 41 and the second polyimide-containing portion 42 at the bonding surface P1 and bonded (FIG. 4B). ).
Thereby, a bonded body 100 in which two substrates are bonded is formed. In the joined body 100, the electrodes 31 and 32 are electrically joined (joining step).
At the same time, the polyimide-containing portion 41 is softened by the above heating, and the surface 4b of the polyimide-containing portion of the laminate 1z and the surface 2a of the substrate B (flattened surface of the second polyimide-containing portion 42) are bonded together. to form the bonded body 100 .
In the present invention, since the glass transition temperature of the polyimide-containing portion is lower than the bonding temperature in the bonding step, the polyimide-containing portion is sufficiently softened and is considered to have excellent adhesiveness.
As a result, the substrate A and the substrate B can be electrically connected to each other, and both can be firmly fixed.
　本発明の好ましい実施形態においては、積層体１ｚのポリイミド含有部表面４ｂ及び第２のポリイミド含有部表面２ａの平坦性が高いため、当接面での基板Ｂ２との緻密かつ正確な当接状態を得ることができる。より緻密かつ正確な当接状態を実現することで、当接面に発生しがちなボイドを効果的に抑制することができる。 In a preferred embodiment of the present invention, since the surface 4b of the polyimide-containing portion of the laminate 1z and the surface 2a of the second polyimide-containing portion have high flatness, the contact surfaces are in a precise and accurate contact state with the substrate B2. can be obtained. By realizing a more precise and accurate contact state, it is possible to effectively suppress voids that tend to occur on the contact surface.
（デバイスの製造方法）
　本発明に係るデバイスは、本発明のポリイミド含有部形成用組成物が用いられる接合体の製造方法により得られた接合体を備える。
　本発明の半導体デバイスの製造方法は、本発明の接合体の製造方法を含む。
　本発明に係るデバイスには、半導体デバイス、電子デバイスなどが含まれ、半導体デバイス又は電子デバイスであることが好ましい。
　デバイスとしては、例えば、半導体新技術研究会編「図解　最先端半導体パッケージ技術のすべて」工業調査会ｐｐ．８－１９、１１０－１１４、１６０－１６５、関東学院大学表面光学研究所編「図解　表面処理技術のすべて」工業調査会ｐｐ．３２－４１、５６－５９に記載の各デバイスなどが挙げられる。
　具体的には、上述のポリイミド含有部をチップ間のアンダーフィルに代替する接着フィルムとして用いる態様や、上述のポリイミド含有部をチップを固定するダイボンディングフィルムとして用いる態様が挙げられる。
　その他、ＬＥＤ（light emitting diode）の素子の実装、フラットパネルディスプレイの光学素子の実装、パワー半導体パッケージの実装など、本発明のポリイミド含有部形成用組成物は多岐にわたって応用することができる。
　また、例えば、本発明のポリイミド含有部形成用組成物は貫通電極（ＴＳＶ：Through silicon via，スルーシリコンビア）を設けた半導体素子の三次元実装にも好適に利用することができる。
　図５は三次元実装デバイスを模式的に示す断面図である。本実施形態では複数の半導体素子（半導体チップ）１０１ａ～１０１ｄが積層した積層体１０１が、配線基板１２０上に配置されている。複数の半導体素子１０１ａ～１０１ｄは、いずれもシリコン基板等の半導体ウエハからなる。積層体１０１は、貫通電極を有さない半導体素子１０１ａと、貫通電極１０２ｂ～１０２ｄを有する半導体素子１０１ｂ～１０１ｄとをフリップチップ接続した構造を有している。貫通電極を有する半導体素子側の接続パッドが、はんだバンプ等の金属バンプ１０３ａ、１０３ｂ、１０３ｃで接続されている。各半導体素子１０１ａ～１０１ｄの間隙には、樹脂層１１０が形成されている。この積層体の製造方法として本発明における接合体の製造方法を利用することができる。すなわち、例えば樹脂層１１０のうち少なくとも１つ（好ましくは全て）を、上述の本発明のポリイミド含有部形成用組成物からなるポリイミド含有部とすることができる。配線基板１２０の一方の面には、表面電極１２０ａが設けられている。配線基板１２０と積層体（基板／基板積層体）１０１との間には、再配線層１０５が形成された絶縁層１１５が配置されている。再配線層１０５の一端は、はんだバンプ等の金属バンプ１０３ｄを介して、半導体素子１０１ｄの再配線層１０５側の面に形成された電極パッドに接続されている。また、再配線層１０５の他端は、配線基板の表面電極１２０ａと、はんだバンプ等の金属バンプ１０３ｅを介して接続している。絶縁層１１５と積層体１０１との間には、樹脂層１１０ａが形成されている。この絶縁層１１５と積層体１０１との接合にも、本発明のポリイミド含有部形成用組成物を用いることができる。すなわち、例えば樹脂層１１０ａを、上述のポリイミド含有部とすることができる。また、絶縁層１１５と配線基板１２０との間には、樹脂層１１０ｂが形成されている。この絶縁層１１５と配線基板１２０との接合にも、本発明のポリイミド含有部形成用組成物を用いることができる。すなわち、例えば樹脂層１１０ｂを、上述のポリイミド含有部とすることができる。 (Device manufacturing method)
A device according to the present invention includes a joined body obtained by a method for producing a joined body using the composition for forming a polyimide-containing portion of the present invention.
A method of manufacturing a semiconductor device of the present invention includes the method of manufacturing a bonded body of the present invention.
Devices according to the present invention include semiconductor devices, electronic devices, etc., and are preferably semiconductor devices or electronic devices.
For devices, see, for example, "Illustrated All About State-of-the-Art Semiconductor Package Technology" edited by the Semiconductor New Technology Study Group, pp. 8-19, 110-114, 160-165, edited by Kanto Gakuin University Surface Optical Research Institute, "Illustrated All about Surface Treatment Technology", Kogyo Chokakai pp. 32-41 and 56-59.
Specifically, there are a mode in which the above-described polyimide-containing portion is used as an adhesive film substituting for an underfill between chips, and a mode in which the above-described polyimide-containing portion is used as a die bonding film for fixing chips.
In addition, the composition for forming a polyimide-containing portion of the present invention can be applied to a wide variety of applications such as mounting of LED (light emitting diode) elements, mounting of optical elements for flat panel displays, and mounting of power semiconductor packages.
Further, for example, the composition for forming a polyimide-containing portion of the present invention can be suitably used for three-dimensional mounting of a semiconductor element provided with a through electrode (TSV: Through silicon via).
FIG. 5 is a cross-sectional view schematically showing a three-dimensional mounting device. In this embodiment, a laminate 101 in which a plurality of semiconductor elements (semiconductor chips) 101a to 101d are laminated is arranged on a wiring substrate 120. As shown in FIG. Each of the plurality of semiconductor elements 101a-101d is made of a semiconductor wafer such as a silicon substrate. A laminated body 101 has a structure in which a semiconductor element 101a having no through electrodes and semiconductor elements 101b to 101d having through electrodes 102b to 102d are flip-chip connected. Connection pads on the semiconductor element side having through electrodes are connected by metal bumps 103a, 103b, 103c such as solder bumps. A resin layer 110 is formed between the semiconductor elements 101a to 101d. As a method for manufacturing this laminate, the method for manufacturing a joined body in the present invention can be used. That is, for example, at least one (preferably all) of the resin layers 110 can be a polyimide-containing portion made of the composition for forming a polyimide-containing portion of the present invention. A surface electrode 120 a is provided on one surface of the wiring board 120 . An insulating layer 115 having a rewiring layer 105 formed thereon is arranged between the wiring substrate 120 and the laminate (substrate/substrate laminate) 101 . One end of the rewiring layer 105 is connected to an electrode pad formed on the surface of the semiconductor element 101d facing the rewiring layer 105 via a metal bump 103d such as a solder bump. Further, the other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump. A resin layer 110 a is formed between the insulating layer 115 and the laminate 101 . The composition for forming a polyimide-containing portion of the present invention can also be used to bond the insulating layer 115 and the laminate 101 together. That is, for example, the resin layer 110a can be used as the polyimide-containing portion described above. A resin layer 110 b is formed between the insulating layer 115 and the wiring board 120 . The composition for forming a polyimide-containing portion of the present invention can also be used to bond the insulating layer 115 and the wiring substrate 120 together. That is, for example, the resin layer 110b can be the polyimide-containing portion described above.
（樹脂組成物の詳細）
　以下、本発明のポリイミド含有部形成用組成物に含まれる各成分の詳細について説明する。
　本発明のポリイミド含有部形成用組成物は、ポリイミド及びポリイミド前駆体よりなる群から選ばれた少なくとも１種の樹脂（以下、「特定樹脂」ともいう）、並びに、溶剤を含むことが好ましく、ポリイミド前駆体及び溶剤を含むことが好ましい。
　また、本発明のポリイミド含有部形成用組成物は、感光性化合物を更に含むことが好ましい。感光性化合物としては、光重合開始剤、光酸発生剤等が挙げられ、光重合開始剤が好ましい。 (Details of resin composition)
Hereinafter, details of each component contained in the composition for forming a polyimide-containing portion of the present invention will be described.
The composition for forming a polyimide-containing part of the present invention preferably contains at least one resin selected from the group consisting of polyimides and polyimide precursors (hereinafter also referred to as "specific resin"), and a solvent. It preferably contains a precursor and a solvent.
Moreover, it is preferable that the composition for forming a polyimide-containing part of the present invention further contains a photosensitive compound. The photosensitive compound includes a photopolymerization initiator, a photoacid generator, and the like, and a photopolymerization initiator is preferred.
＜特定樹脂＞
　本発明の樹脂組成物は、ポリイミド及びポリイミド前駆体よりなる群から選ばれた少なくとも１種の樹脂（特定樹脂）を含むことが好ましく、ポリイミド前駆体を含むことがより好ましい。
　また、特定樹脂は重合性基を有することが好ましく、ラジカル重合性基を含むことがより好ましい。
　特定樹脂がラジカル重合性基を有する場合、本発明の樹脂組成物は、後述のラジカル重合開始剤を含むことが好ましく、後述のラジカル重合開始剤を含み、かつ、後述のラジカル架橋剤を含むことがより好ましい。さらに必要に応じて、後述の増感剤を含むことができる。このような本発明の樹脂組成物からは、例えば、ネガ型感光膜が形成される。
　また、特定樹脂は、酸分解性基等の極性変換基を有していてもよい。
　特定樹脂が酸分解性基を有する場合、本発明の樹脂組成物は、後述の光酸発生剤を含むことが好ましい。このような本発明の樹脂組成物からは、例えば、化学増幅型であるポジ型感光膜又はネガ型感光膜が形成される。 <Specific resin>
The resin composition of the present invention preferably contains at least one resin (specific resin) selected from the group consisting of polyimides and polyimide precursors, and more preferably contains a polyimide precursor.
Moreover, the specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group.
When the specific resin has a radically polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator described later, and contains a radical polymerization initiator described later and a radical cross-linking agent described later. is more preferred. Further, if necessary, a sensitizer described later can be included. For example, a negative photosensitive film is formed from the resin composition of the present invention.
Moreover, the specific resin may have a polarity conversion group such as an acid-decomposable group.
When the specific resin has an acid-decomposable group, the resin composition of the present invention preferably contains a photoacid generator, which will be described later. From such a resin composition of the present invention, for example, a chemically amplified positive photosensitive film or negative photosensitive film is formed.
〔ポリイミド前駆体〕
　本発明で用いるポリイミド前駆体は、その種類等特に定めるものではないが、下記式（２）で表される繰返し単位を含むことが好ましい。
Figure JPOXMLDOC01-appb-C000001
　式（２）中、Ａ１及びＡ２は、それぞれ独立に、酸素原子又は－ＮＨ－を表し、Ｒ１１１は、２価の有機基を表し、Ｒ１１５は、４価の有機基を表し、Ｒ１１３及びＲ１１４は、それぞれ独立に、水素原子又は１価の有機基を表す。 [Polyimide precursor]
Although the type of the polyimide precursor used in the present invention is not particularly limited, it preferably contains a repeating unit represented by the following formula (2).
Figure JPOXMLDOC01-appb-C000001
In formula (2), A 1 and A 2 each independently represent an oxygen atom or -NH-, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group.
　式（２）におけるＡ１及びＡ２は、それぞれ独立に、酸素原子又は－ＮＨ－を表し、酸素原子が好ましい。
　式（２）におけるＲ１１１は、２価の有機基を表す。２価の有機基としては、直鎖又は分岐の脂肪族基、環状の脂肪族基及び芳香族基を含む基が例示され、炭素数２～２０の直鎖又は分岐の脂肪族基、炭素数３～２０の環状の脂肪族基、炭素数３～２０の芳香族基、又は、これらの組み合わせからなる基が好ましく、炭素数６～２０の芳香族基を含む基がより好ましい。上記直鎖又は分岐の脂肪族基は鎖中の炭化水素基がヘテロ原子を含む基で置換されていてもよく、上記環状の脂肪族基および芳香族基は環員の炭化水素基がヘテロ原子を含む基で置換されていてもよい。本発明の好ましい実施形態として、－Ａｒ－および－Ａｒ－Ｌ－Ａｒ－で表される基であることが例示され、特に好ましくは－Ａｒ－Ｌ－Ａｒ－で表される基である。但し、Ａｒは、それぞれ独立に、芳香族基であり、Ｌは、単結合、又は、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ２－又は－ＮＨＣＯ－、あるいは、上記の２つ以上の組み合わせからなる基である。これらの好ましい範囲は、上述のとおりである。 A 1 and A 2 in formula (2) each independently represent an oxygen atom or —NH—, preferably an oxygen atom.
R 111 in formula (2) represents a divalent organic group. Examples of divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, linear or branched aliphatic groups having 2 to 20 carbon atoms, A cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. In the straight-chain or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a hetero atom, and in the cyclic aliphatic group and the aromatic group, the ring member hydrocarbon group is a hetero atom. may be substituted with a group containing Groups represented by -Ar- and -Ar-L-Ar- are exemplified as preferred embodiments of the present invention, and groups represented by -Ar-L-Ar- are particularly preferred. However, Ar is each independently an aromatic group, L is a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO -, -S-, -SO 2 - or -NHCO-, or a group consisting of a combination of two or more of the above. Preferred ranges for these are as described above.
　Ｒ１１１は、ジアミンから誘導されることが好ましい。ポリイミド前駆体の製造に用いられるジアミンとしては、直鎖又は分岐の脂肪族、環状の脂肪族又は芳香族ジアミンなどが挙げられる。ジアミンは、１種のみ用いてもよいし、２種以上用いてもよい。
　具体的には、炭素数２～２０の直鎖又は分岐の脂肪族基、炭素数３～２０の環状の脂肪族基、炭素数３～２０の芳香族基、又は、これらの組み合わせからなる基を含むジアミンであることが好ましく、炭素数６～２０の芳香族基を含むジアミンであることがより好ましい。上記直鎖又は分岐の脂肪族基は鎖中の炭化水素基がヘテロ原子を含む基で置換されていてもよく上記環状の脂肪族基および芳香族基は環員の炭化水素基がヘテロ原子を含む基で置換されていてもよい。芳香族基を含む基の例としては、下記が挙げられる。 R 111 is preferably derived from a diamine. Diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.
Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferably a diamine containing, more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. In the straight-chain or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a heteroatom. may be substituted with a group containing Examples of groups containing aromatic groups include:
Figure JPOXMLDOC01-appb-C000002
　式中、Ａは単結合又は２価の連結基を表し、単結合、又は、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－、－ＳＯ２－、－ＮＨＣＯ－、又は、これらの組み合わせから選択される基であることが好ましく、単結合、又は、フッ素原子で置換されていてもよい炭素数１～３のアルキレン基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－、若しくは、－ＳＯ２－から選択される基であることがより好ましく、－ＣＨ２－、－Ｏ－、－Ｓ－、－ＳＯ２－、－Ｃ（ＣＦ３）２－、又は、－Ｃ（ＣＨ３）２－であることが更に好ましい。
　式中、＊は他の構造との結合部位を表す。
Figure JPOXMLDOC01-appb-C000002
In the formula, A represents a single bond or a divalent linking group, a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms optionally substituted with a fluorine atom, -O-, -C (= O)-, -S-, -SO 2 -, -NHCO-, or preferably a group selected from a combination thereof, and has 1 carbon atom optionally substituted with a single bond or a fluorine atom -3 alkylene groups, -O-, -C(=O)-, -S-, or -SO 2 - is more preferred, and -CH 2 -, -O-, - S—, —SO 2 —, —C(CF 3 ) 2 —, or —C(CH 3 ) 2 — are more preferred.
In the formula, * represents a binding site with other structures.
　ジアミンとしては、具体的には、１，２－ジアミノエタン、１，２－ジアミノプロパン、１，３－ジアミノプロパン、１，４－ジアミノブタン又は１，６－ジアミノヘキサン；１，２－又は１，３－ジアミノシクロペンタン、１，２－、１，３－又は１，４－ジアミノシクロヘキサン、１，２－、１，３－又は１，４－ビス（アミノメチル）シクロヘキサン、ビス－（４－アミノシクロヘキシル）メタン、ビス－（３－アミノシクロヘキシル）メタン、４，４’－ジアミノ－３，３’－ジメチルシクロヘキシルメタン又はイソホロンジアミン；ｍ－又はｐ－フェニレンジアミン、ジアミノトルエン、４，４’－又は３，３’－ジアミノビフェニル、４，４’－ジアミノジフェニルエーテル、３，３－ジアミノジフェニルエーテル、４，４’－又は３，３’－ジアミノジフェニルメタン、４，４’－又は３，３’－ジアミノジフェニルスルホン、４，４’－又は３，３’－ジアミノジフェニルスルフィド、４，４’－又は３，３’－ジアミノベンゾフェノン、３，３’－ジメチル－４，４’－ジアミノビフェニル、２，２’－ジメチル－４，４’－ジアミノビフェニル、３，３’－ジメトキシ－４，４’－ジアミノビフェニル、２，２－ビス（４－アミノフェニル）プロパン、２，２－ビス（４－アミノフェニル）ヘキサフルオロプロパン、２，２－ビス（３－ヒドロキシ－４－アミノフェニル）プロパン、２，２－ビス（３－ヒドロキシ－４－アミノフェニル）ヘキサフルオロプロパン、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）プロパン、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパン、ビス（３－アミノ－４－ヒドロキシフェニル）スルホン、ビス（４－アミノ－３－ヒドロキシフェニル）スルホン、４，４’－ジアミノパラテルフェニル、４，４’－ビス（４－アミノフェノキシ）ビフェニル、ビス［４－（４－アミノフェノキシ）フェニル］スルホン、ビス［４－（３－アミノフェノキシ）フェニル］スルホン、ビス［４－（２－アミノフェノキシ）フェニル］スルホン、１，４－ビス（４－アミノフェノキシ）ベンゼン、９，１０－ビス（４－アミノフェニル）アントラセン、３，３’－ジメチル－４，４’－ジアミノジフェニルスルホン、１，３－ビス（４－アミノフェノキシ）ベンゼン、１，３－ビス（３－アミノフェノキシ）ベンゼン、１，３－ビス（４－アミノフェニル）ベンゼン、３，３’－ジエチル－４，４’－ジアミノジフェニルメタン、３，３’－ジメチル－４，４’－ジアミノジフェニルメタン、４，４’－ジアミノオクタフルオロビフェニル、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、９，９－ビス（４－アミノフェニル）－１０－ヒドロアントラセン、３，３’，４，４’－テトラアミノビフェニル、３，３’，４，４’－テトラアミノジフェニルエーテル、１，４－ジアミノアントラキノン、１，５－ジアミノアントラキノン、３，３－ジヒドロキシ－４，４’－ジアミノビフェニル、９，９’－ビス（４－アミノフェニル）フルオレン、４，４’－ジメチル－３，３’－ジアミノジフェニルスルホン、３，３’，５，５’－テトラメチル－４，４’－ジアミノジフェニルメタン、２，４－又は２，５－ジアミノクメン、２，５－ジメチル－ｐ－フェニレンジアミン、アセトグアナミン、２，３，５，６－テトラメチル－ｐ－フェニレンジアミン、２，４，６－トリメチル－ｍ－フェニレンジアミン、ビス（３－アミノプロピル）テトラメチルジシロキサン、ビス（ｐ－アミノフェニル）オクタメチルペンタシロキサン、２，７－ジアミノフルオレン、２，５－ジアミノピリジン、１，２－ビス（４－アミノフェニル）エタン、ジアミノベンズアニリド、ジアミノ安息香酸のエステル、１，５－ジアミノナフタレン、ジアミノベンゾトリフルオライド、１，３－ビス（４－アミノフェニル）ヘキサフルオロプロパン、１，４－ビス（４－アミノフェニル）オクタフルオロブタン、１，５－ビス（４－アミノフェニル）デカフルオロペンタン、１，７－ビス（４－アミノフェニル）テトラデカフルオロヘプタン、２，２－ビス［４－（３－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、２，２－ビス［４－（２－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、２，２－ビス［４－（４－アミノフェノキシ）－３，５－ジメチルフェニル］ヘキサフルオロプロパン、２，２－ビス［４－（４－アミノフェノキシ）－３，５－ビス（トリフルオロメチル）フェニル］ヘキサフルオロプロパン、ｐ－ビス（４－アミノ－２－トリフルオロメチルフェノキシ）ベンゼン、４，４’－ビス（４－アミノ－２－トリフルオロメチルフェノキシ）ビフェニル、４，４’－ビス（４－アミノ－３－トリフルオロメチルフェノキシ）ビフェニル、４，４’－ビス（４－アミノ－２－トリフルオロメチルフェノキシ）ジフェニルスルホン、４，４’－ビス（３－アミノ－５－トリフルオロメチルフェノキシ）ジフェニルスルホン、２，２－ビス［４－（４－アミノ－３－トリフルオロメチルフェノキシ）フェニル］ヘキサフルオロプロパン、３，３’，５，５’－テトラメチル－４，４’－ジアミノビフェニル、４，４’－ジアミノ－２，２’－ビス（トリフルオロメチル）ビフェニル、２，２’，５，５’，６，６’－ヘキサフルオロトリジン及び４，４’－ジアミノクアテルフェニルから選ばれる少なくとも１種のジアミンが挙げられる。 Specific examples of diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 1,6-diaminohexane; ,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4- aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4′-diamino-3,3′-dimethylcyclohexylmethane or isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4′- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diamino diphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2 '-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl ) hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino -4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl) ) sulfone, 4,4′-diaminoparaterphenyl, 4,4′-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy ) phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3′- Dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4- aminophenyl)benzene, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 4,4′-diaminooctafluorobiphenyl, 2,2-bis [4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3′,4,4′-tetraaminobiphenyl, 3,3′,4,4′-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4, 4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4 ,4'-diaminodiphenylmethane, 2,4- or 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2 , 4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2- Bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy) -3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino -2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy) ) biphenyl, 4,4′-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4′-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4′-bis (3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3′,5,5′ -tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolysine and at least one diamine selected from 4,4'-diaminoquaterphenyl.
　また、国際公開第２０１７／０３８５９８号の段落００３０～００３１に記載のジアミン（ＤＡ－１）～（ＤＡ－１８）も好ましい。 Also preferred are the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598.
　また、国際公開第２０１７／０３８５９８号の段落００３２～００３４に記載の２つ以上のアルキレングリコール単位を主鎖にもつジアミンも好ましく用いられる。 Also preferably used are diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598.
　Ｒ１１１は、得られる有機膜の柔軟性の観点から、－Ａｒ－Ｌ－Ａｒ－で表されることが好ましい。但し、Ａｒは、それぞれ独立に、芳香族基であり、Ｌは、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ２－又は－ＮＨＣＯ－、あるいは、上記の２つ以上の組み合わせからなる基である。Ａｒは、フェニレン基が好ましく、Ｌは、フッ素原子で置換されていてもよい炭素数１又は２の脂肪族炭化水素基、－Ｏ－、－ＣＯ－、－Ｓ－又は－ＳＯ２－が好ましい。ここでの脂肪族炭化水素基は、アルキレン基が好ましい。 R 111 is preferably represented by -Ar-L-Ar- from the viewpoint of the flexibility of the resulting organic film. However, Ar is each independently an aromatic group, L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- , —SO 2 — or —NHCO—, or a group consisting of a combination of two or more of the above. Ar is preferably a phenylene group, L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- or -SO 2 - . The aliphatic hydrocarbon group here is preferably an alkylene group.
　また、Ｒ１１１は、ｉ線透過率の観点から、下記式（５１）又は式（６１）で表される２価の有機基であることが好ましい。特に、ｉ線透過率、入手のし易さの観点から、式（６１）で表される２価の有機基であることがより好ましい。
　式（５１）
Figure JPOXMLDOC01-appb-C000003
　式（５１）中、Ｒ５０～Ｒ５７は、それぞれ独立に、水素原子、フッ素原子又は１価の有機基であり、Ｒ５０～Ｒ５７の少なくとも１つは、フッ素原子、メチル基又はトリフルオロメチル基であり、＊はそれぞれ独立に、式（２）中の窒素原子との結合部位を表す。
　Ｒ５０～Ｒ５７の１価の有機基としては、炭素数１～１０（好ましくは炭素数１～６）の無置換のアルキル基、炭素数１～１０（好ましくは炭素数１～６）のフッ化アルキル基等が挙げられる。
Figure JPOXMLDOC01-appb-C000004
　式（６１）中、Ｒ５８及びＲ５９は、それぞれ独立に、フッ素原子、メチル基、又はトリフルオロメチル基であり、＊はそれぞれ独立に、式（２）中の窒素原子との結合部位を表す。
　式（５１）又は（６１）の構造を与えるジアミンとしては、２，２’－ジメチルベンジジン、２，２’－ビス（トリフルオロメチル）－４，４’－ジアミノビフェニル、２，２’－ビス（フルオロ）－４，４’－ジアミノビフェニル、４，４’－ジアミノオクタフルオロビフェニル等が挙げられる。これらは１種で又は２種以上を組み合わせて用いてもよい。 From the viewpoint of i-line transmittance, R 111 is preferably a divalent organic group represented by the following formula (51) or (61). In particular, from the viewpoint of i-line transmittance and availability, a divalent organic group represented by Formula (61) is more preferable.
Equation (51)
Figure JPOXMLDOC01-appb-C000003
In formula (51), R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group or a trifluoro It is a methyl group, and each * independently represents a binding site to the nitrogen atom in formula (2).
The monovalent organic groups represented by R 50 to R 57 include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), A fluorinated alkyl group and the like can be mentioned.
Figure JPOXMLDOC01-appb-C000004
In formula (61), R 58 and R 59 are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * is each independently a bonding site to the nitrogen atom in formula (2) show.
Diamines that give the structure of formula (51) or (61) include 2,2′-dimethylbenzidine, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 2,2′-bis (Fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like. These may be used alone or in combination of two or more.
　式（２）におけるＲ１１５は、４価の有機基を表す。４価の有機基としては、芳香環を含む４価の有機基が好ましく、下記式（５）又は式（６）で表される基がより好ましい。
式（５）又は式（６）中、＊はそれぞれ独立に、他の構造との結合部位を表す。
Figure JPOXMLDOC01-appb-C000005
　式（５）中、Ｒ１１２は単結合又は２価の連結基であり、単結合、又は、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ２－、及び－ＮＨＣＯ－、ならびに、これらの組み合わせから選択される基であることが好ましく、単結合、又は、フッ素原子で置換されていてもよい炭素数１～３のアルキレン基、－Ｏ－、－ＣＯ－、－Ｓ－及び－ＳＯ２－から選択される基であることがより好ましく、－ＣＨ２－、－Ｃ（ＣＦ３）２－、－Ｃ（ＣＨ３）２－、－Ｏ－、－ＣＯ－、－Ｓ－及び－ＳＯ２－からなる群から選択される２価の基であることが更に好ましい。 R 115 in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or (6) is more preferable.
In formula (5) or (6), each * independently represents a binding site to another structure.
Figure JPOXMLDOC01-appb-C000005
In formula (5), R 112 is a single bond or a divalent linking group, a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms optionally substituted with a fluorine atom, —O—, -CO-, -S-, -SO 2 -, and -NHCO-, and preferably a group selected from combinations thereof, and the number of carbon atoms optionally substituted with a single bond or a fluorine atom It is more preferably a group selected from 1 to 3 alkylene groups, -O-, -CO-, -S- and -SO 2 -, and -CH 2 -, -C(CF 3 ) 2 -, - More preferably, it is a divalent group selected from the group consisting of C(CH 3 ) 2 -, -O-, -CO-, -S- and -SO 2 -.
　Ｒ１１５は、具体的には、テトラカルボン酸二無水物から無水物基の除去後に残存するテトラカルボン酸残基などが挙げられる。ポリイミド前駆体は、Ｒ１１５に該当する構造として、テトラカルボン酸二無水物残基を、１種のみ含んでもよいし、２種以上含んでもよい。
　テトラカルボン酸二無水物は、下記式（Ｏ）で表されることが好ましい。
Figure JPOXMLDOC01-appb-C000006
　式（Ｏ）中、Ｒ１１５は、４価の有機基を表す。Ｒ１１５の好ましい範囲は式（２）におけるＲ１１５と同義であり、好ましい範囲も同様である。 Specifically, R 115 includes a tetracarboxylic acid residue remaining after removal of an anhydride group from a tetracarboxylic dianhydride. The polyimide precursor may contain only one type of tetracarboxylic dianhydride residue as a structure corresponding to R115 , or may contain two or more types thereof.
The tetracarboxylic dianhydride is preferably represented by the following formula (O).
Figure JPOXMLDOC01-appb-C000006
In formula (O), R 115 represents a tetravalent organic group. The preferred range of R 115 is synonymous with R 115 in formula (2), and the preferred range is also the same.
　テトラカルボン酸二無水物の具体例としては、ピロメリット酸二無水物（ＰＭＤＡ）、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物、３，３’，４，４’－ジフェニルスルフィドテトラカルボン酸二無水物、３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物、３，３’，４，４’－ジフェニルメタンテトラカルボン酸二無水物、２，２’，３，３’－ジフェニルメタンテトラカルボン酸二無水物、２，３，３’，４’－ビフェニルテトラカルボン酸二無水物、２，３，３’，４’－ベンゾフェノンテトラカルボン酸二無水物、４，４’－オキシジフタル酸二無水物、２，３，６，７－ナフタレンテトラカルボン酸二無水物、１，４，５，７－ナフタレンテトラカルボン酸二無水物、２，２－ビス（３，４－ジカルボキシフェニル）プロパン二無水物、２，２－ビス（２，３－ジカルボキシフェニル）プロパン二無水物、２，２－ビス（３，４－ジカルボキシフェニル）ヘキサフルオロプロパン二無水物、１，３－ジフェニルヘキサフルオロプロパン－３，３，４，４－テトラカルボン酸二無水物、１，４，５，６－ナフタレンテトラカルボン酸二無水物、２，２’，３，３’－ジフェニルテトラカルボン酸二無水物、３，４，９，１０－ペリレンテトラカルボン酸二無水物、１，２，４，５－ナフタレンテトラカルボン酸二無水物、１，４，５，８－ナフタレンテトラカルボン酸二無水物、１，８，９，１０－フェナントレンテトラカルボン酸二無水物、１，１－ビス（２，３－ジカルボキシフェニル）エタン二無水物、１，１－ビス（３，４－ジカルボキシフェニル）エタン二無水物、１，２，３，４－ベンゼンテトラカルボン酸二無水物、ならびに、これらの炭素数１～６のアルキル及び炭素数１～６のアルコキシ誘導体が挙げられる。 Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′- Diphenyl sulfide tetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′ ,4,4′-diphenylmethanetetracarboxylic dianhydride, 2,2′,3,3′-diphenylmethanetetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5 ,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2 , 2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5, 6-naphthalenetetracarboxylic dianhydride, 2,2′,3,3′-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4, 5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2, 3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and these C1-6 alkyl and C1-6 alkoxy derivatives are included.
また、国際公開第２０１７／０３８５９８号の段落００３８に記載のテトラカルボン酸二無水物（ＤＡＡ－１）～（ＤＡＡ－５）も好ましい例として挙げられる。 Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017/038598 are also preferred examples.
　式（２）において、Ｒ１１１とＲ１１５の少なくとも一方がＯＨ基を有することも可能である。より具体的には、Ｒ１１１として、ビスアミノフェノール誘導体の残基が挙げられる。 In formula (2), it is also possible that at least one of R 111 and R 115 has an OH group. More specifically, R 111 includes residues of bisaminophenol derivatives.
　式（２）におけるＲ１１３及びＲ１１４は、それぞれ独立に、水素原子又は１価の有機基を表す。１価の有機基としては、直鎖又は分岐のアルキル基、環状アルキル基、芳香族基、又はポリアルキレンオキシ基を含むことが好ましい。また、Ｒ１１３及びＲ１１４の少なくとも一方が重合性基を含むことが好ましく、両方が重合性基を含むことがより好ましい。Ｒ１１３及びＲ１１４の少なくとも一方が２以上の重合性基を含むことも好ましい。重合性基としては、熱、ラジカル等の作用により、架橋反応することが可能な基であって、ラジカル重合性基が好ましい。重合性基の具体例としては、エチレン性不飽和結合を有する基、アルコキシメチル基、ヒドロキシメチル基、アシルオキシメチル基、エポキシ基、オキセタニル基、ベンゾオキサゾリル基、ブロックイソシアネート基、アミノ基が挙げられる。ポリイミド前駆体が有するラジカル重合性基としては、エチレン性不飽和結合を有する基が好ましい。
　エチレン性不飽和結合を有する基としては、ビニル基、アリル基、イソアリル基、２－メチルアリル基、ビニル基と直接結合した芳香環を有する基（例えば、ビニルフェニル基など）、（メタ）アクリルアミド基、（メタ）アクリロイルオキシ基、下記式（ＩＩＩ）で表される基などが挙げられ、下記式（ＩＩＩ）で表される基が好ましい。 R 113 and R 114 in formula (2) each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. At least one of R 113 and R 114 preferably contains a polymerizable group, more preferably both contain a polymerizable group. It is also preferred that at least one of R 113 and R 114 contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a cross-linking reaction by the action of heat, radicals, or the like, and is preferably a radically polymerizable group. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. be done. As the radically polymerizable group possessed by the polyimide precursor, a group having an ethylenically unsaturated bond is preferred.
Groups having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), and a (meth)acrylamide group. , a (meth)acryloyloxy group, a group represented by the following formula (III), and the like, and a group represented by the following formula (III) is preferable.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　式（ＩＩＩ）において、Ｒ２００は、水素原子、メチル基、エチル基又はメチロール基を表し、水素原子又はメチル基が好ましい。
　式（ＩＩＩ）において、＊は他の構造との結合部位を表す。
　式（ＩＩＩ）において、Ｒ２０１は、炭素数２～１２のアルキレン基、－ＣＨ２ＣＨ（ＯＨ）ＣＨ２－、シクロアルキレン基又はポリアルキレンオキシ基を表す。
　好適なＲ２０１の例は、エチレン基、プロピレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基、オクタメチレン基、ドデカメチレン基等のアルキレン基、１，２－ブタンジイル基、１，３－ブタンジイル基、－ＣＨ２ＣＨ（ＯＨ）ＣＨ２－、ポリアルキレンオキシ基が挙げられ、エチレン基、プロピレン基等のアルキレン基、－ＣＨ２ＣＨ（ＯＨ）ＣＨ２－、シクロヘキシル基、ポリアルキレンオキシ基がより好ましく、エチレン基、プロピレン基等のアルキレン基、又はポリアルキレンオキシ基が更に好ましい。
　本発明において、ポリアルキレンオキシ基とは、アルキレンオキシ基が２以上直接結合した基をいう。ポリアルキレンオキシ基に含まれる複数のアルキレンオキシ基におけるアルキレン基は、それぞれ同一であっても異なっていてもよい。
　ポリアルキレンオキシ基が、アルキレン基が異なる複数種のアルキレンオキシ基を含む場合、ポリアルキレンオキシ基におけるアルキレンオキシ基の配列は、ランダムな配列であってもよいし、ブロックを有する配列であってもよいし、交互等のパターンを有する配列であってもよい。
　上記アルキレン基の炭素数（アルキレン基が置換基を有する場合、置換基の炭素数を含む）は、２以上であることが好ましく、２～１０であることがより好ましく、２～６であることがより好ましく、２～５であることが更に好ましく、２～４であることが一層好ましく、２又は３であることが特に好ましく、２であることが最も好ましい。
　また、上記アルキレン基は、置換基を有していてもよい。好ましい置換基としては、アルキル基、アリール基、ハロゲン原子等が挙げられる。
　また、ポリアルキレンオキシ基に含まれるアルキレンオキシ基の数（ポリアルキレンオキシ基の繰返し数）は、２～２０が好ましく、２～１０がより好ましく、２～６が更に好ましい。
　ポリアルキレンオキシ基としては、溶剤溶解性及び耐溶剤性の観点からは、ポリエチレンオキシ基、ポリプロピレンオキシ基、ポリトリメチレンオキシ基、ポリテトラメチレンオキシ基、又は、複数のエチレンオキシ基と複数のプロピレンオキシ基とが結合した基が好ましく、ポリエチレンオキシ基又はポリプロピレンオキシ基がより好ましく、ポリエチレンオキシ基が更に好ましい。上記複数のエチレンオキシ基と複数のプロピレンオキシ基とが結合した基において、エチレンオキシ基とプロピレンオキシ基とはランダムに配列していてもよいし、ブロックを形成して配列していてもよいし、交互等のパターン状に配列していてもよい。これらの基におけるエチレンオキシ基等の繰返し数の好ましい態様は上述の通りである。 In formula (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, preferably a hydrogen atom or a methyl group.
In formula (III), * represents a binding site with another structure.
In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH(OH)CH 2 —, a cycloalkylene group or a polyalkyleneoxy group.
Suitable examples of R 201 include ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, alkylene groups such as dodecamethylene, 1,2-butanediyl, 1, 3-butanediyl group, —CH 2 CH(OH)CH 2 —, polyalkyleneoxy group, ethylene group, alkylene group such as propylene group, —CH 2 CH(OH)CH 2 —, cyclohexyl group, polyalkylene An oxy group is more preferred, and an alkylene group such as an ethylene group, a propylene group, or a polyalkyleneoxy group is even more preferred.
In the present invention, a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement or a block arrangement. Alternatively, it may be arranged in a pattern such as an alternating pattern.
The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6. is more preferred, 2 to 5 is more preferred, 2 to 4 is even more preferred, 2 or 3 is particularly preferred, and 2 is most preferred.
Moreover, the said alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, and halogen atoms.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (repeating number of polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylene A group to which an oxy group is bonded is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is still more preferable. In the group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, or may be arranged to form blocks. , may be arranged in a pattern such as alternately. Preferred embodiments of the number of repetitions of ethyleneoxy groups and the like in these groups are as described above.
　式（２）において、Ｒ１１３が水素原子である場合、又は、Ｒ１１４が水素原子である場合、ポリイミド前駆体はエチレン性不飽和結合を有する３級アミン化合物と対塩を形成していてもよい。このようなエチレン性不飽和結合を有する３級アミン化合物の例としては、Ｎ，Ｎ－ジメチルアミノプロピルメタクリレートが挙げられる。 In formula (2), when R 113 is a hydrogen atom, or when R 114 is a hydrogen atom, the polyimide precursor may form a tertiary amine compound having an ethylenically unsaturated bond and a counter salt. good. Examples of tertiary amine compounds having such ethylenically unsaturated bonds include N,N-dimethylaminopropyl methacrylate.
　式（２）において、Ｒ１１３及びＲ１１４の少なくとも一方が、酸分解性基等の極性変換基であってもよい。酸分解性基としては、酸の作用で分解して、フェノール性ヒドロキシ基、カルボキシ基等のアルカリ可溶性基を生じるものであれば特に限定されないが、アセタール基、ケタール基、シリル基、シリルエーテル基、第三級アルキルエステル基等が好ましく、露光感度の観点からは、アセタール基又はケタール基がより好ましい。
　酸分解性基の具体例としては、ｔｅｒｔ－ブトキシカルボニル基、イソプロポキシカルボニル基、テトラヒドロピラニル基、テトラヒドロフラニル基、エトキシエチル基、メトキシエチル基、エトキシメチル基、トリメチルシリル基、ｔｅｒｔ－ブトキシカルボニルメチル基、トリメチルシリルエーテル基などが挙げられる。露光感度の観点からは、エトキシエチル基、又は、テトラヒドロフラニル基が好ましい。 In formula (2), at least one of R 113 and R 114 may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxyl group. , a tertiary alkyl ester group and the like are preferable, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferable.
Specific examples of acid-decomposable groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, and tert-butoxycarbonylmethyl. groups, trimethylsilyl ether groups, and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.
　また、ポリイミド前駆体は、構造中にフッ素原子を有することも好ましい。ポリイミド前駆体中のフッ素原子含有量は、１０質量％以上が好ましく、また、２０質量％以下が好ましい。 Also, the polyimide precursor preferably has a fluorine atom in its structure. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
　また、基板との密着性を向上させる目的で、ポリイミド前駆体は、シロキサン構造を有する脂肪族基と共重合していてもよい。具体的には、ジアミンとして、ビス（３－アミノプロピル）テトラメチルジシロキサン、ビス（ｐ－アミノフェニル）オクタメチルペンタシロキサンなどを用いる態様が挙げられる。 In addition, for the purpose of improving adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, there is an embodiment using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like as the diamine.
　式（２）で表される繰返し単位は、式（２－Ａ）で表される繰返し単位であることが好ましい。すなわち、本発明で用いるポリイミド前駆体の少なくとも１種が、式（２－Ａ）で表される繰返し単位を有する前駆体であることが好ましい。ポリイミド前駆体が式（２－Ａ）で表される繰返し単位を含むことにより、露光ラチチュードの幅をより広げることが可能になる。
式（２－Ａ）
Figure JPOXMLDOC01-appb-C000008
　式（２－Ａ）中、Ａ１及びＡ２は、酸素原子を表し、Ｒ１１１及びＲ１１２は、それぞれ独立に、２価の有機基を表し、Ｒ１１３及びＲ１１４は、それぞれ独立に、水素原子又は１価の有機基を表し、Ｒ１１３及びＲ１１４の少なくとも一方は、重合性基を含む基であり、両方が重合性基を含む基であることが好ましい。 The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one polyimide precursor used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by the formula (2-A) in the polyimide precursor, it becomes possible to further widen the width of the exposure latitude.
Formula (2-A)
Figure JPOXMLDOC01-appb-C000008
In formula (2-A), A 1 and A 2 represent an oxygen atom, R 111 and R 112 each independently represent a divalent organic group, R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group, at least one of R 113 and R 114 is a group containing a polymerizable group, and both are preferably groups containing a polymerizable group.
　Ａ１、Ａ２、Ｒ１１１、Ｒ１１３及びＲ１１４は、それぞれ独立に、式（２）におけるＡ１、Ａ２、Ｒ１１１、Ｒ１１３及びＲ１１４と同義であり、好ましい範囲も同様である。
Ｒ１１２は、式（５）におけるＲ１１２と同義であり、好ましい範囲も同様である。 A 1 , A 2 , R 111 , R 113 and R 114 are each independently synonymous with A 1 , A 2 , R 111 , R 113 and R 114 in formula (2), and preferred ranges are also the same. .
R 112 has the same definition as R 112 in formula (5), and the preferred range is also the same.
　ポリイミド前駆体は、式（２）で表される繰返し単位を１種含んでいてもよいが、２種以上で含んでいてもよい。また、式（２）で表される繰返し単位の構造異性体を含んでいてもよい。また、ポリイミド前駆体は、上記式（２）の繰返し単位のほかに、他の種類の繰返し単位をも含んでよいことはいうまでもない。 The polyimide precursor may contain one type of repeating unit represented by formula (2), but may contain two or more types. It may also contain structural isomers of the repeating unit represented by formula (2). It goes without saying that the polyimide precursor may also contain other types of repeating units in addition to the repeating units of formula (2) above.
　本発明におけるポリイミド前駆体の一実施形態として、式（２）で表される繰返し単位の含有量が、全繰返し単位の５０モル％以上である態様が挙げられる。上記合計含有量は、７０モル％以上であることがより好ましく、９０モル％以上であることが更に好ましく、９０モル％超であることが特に好ましい。上記合計含有量の上限は、特に限定されず、末端を除くポリイミド前駆体における全ての繰返し単位が、式（２）で表される繰返し単位であってもよい。 As one embodiment of the polyimide precursor in the present invention, the content of the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units. The total content is more preferably 70 mol % or more, still more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor excluding terminals may be repeating units represented by formula (2).
　ポリイミド前駆体の重量平均分子量（Ｍｗ）は、好ましくは５，０００～１００，０００であり、より好ましくは１０，０００～５０，０００であり、更に好ましくは１５，０００～４０，０００である。また、数平均分子量（Ｍｎ）は、好ましくは２，０００～４０，０００であり、より好ましくは３，０００～３０，０００であり、更に好ましくは４，０００～２０，０００である。
　上記ポリイミド前駆体の分子量の分散度は、１．５以上が好ましく、１．８以上がより好ましく、２．０以上であることが更に好ましい。ポリイミド前駆体の分子量の分散度の上限値は特に定めるものではないが、例えば、７．０以下が好ましく、６．５以下がより好ましく、６．０以下が更に好ましい。
　本明細書において、分子量の分散度とは、重量平均分子量／数平均分子量により算出される値である。
　また、樹脂組成物が特定樹脂として複数種のポリイミド前駆体を含む場合、少なくとも１種のポリイミド前駆体の重量平均分子量、数平均分子量、及び、分散度が上記範囲であることが好ましい。また、上記複数種のポリイミド前駆体を１つの樹脂として算出した重量平均分子量、数平均分子量、及び、分散度が、それぞれ、上記範囲内であることも好ましい。 The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, still more preferably 15,000 to 40,000. Also, the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, still more preferably 4,000 to 20,000.
The polyimide precursor preferably has a molecular weight distribution of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. Although the upper limit of the polyimide precursor's molecular weight dispersity is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
In the present specification, the molecular weight dispersity is a value calculated by weight average molecular weight/number average molecular weight.
Moreover, when the resin composition contains a plurality of polyimide precursors as the specific resin, the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one polyimide precursor are preferably within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated from the plurality of types of polyimide precursors as one resin are within the ranges described above.
〔ポリイミド〕
　本発明に用いられるポリイミドは、アルカリ可溶性ポリイミドであってもよく、有機溶剤を主成分とする現像液に対して可溶なポリイミドであってもよい。
　本明細書において、アルカリ可溶性ポリイミドとは、１００ｇの２．３８質量％テトラメチルアンモニウム水溶液に対し、２３℃で０．１ｇ以上溶解するポリイミドをいい、パターン形成性の観点からは、０．５ｇ以上溶解するポリイミドであることが好ましく、１．０ｇ以上溶解するポリイミドであることが更に好ましい。上記溶解量の上限は特に限定されないが、１００ｇ以下であることが好ましい。
　また、ポリイミドは、得られる有機膜の膜強度及び絶縁性の観点からは、複数個のイミド構造を主鎖に有するポリイミドであることが好ましい。
　本明細書において、「主鎖」とは、樹脂を構成する高分子化合物の分子中で相対的に最も長い結合鎖をいい、「側鎖」とはそれ以外の結合鎖をいう。 [Polyimide]
The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer containing an organic solvent as a main component.
In the present specification, the alkali-soluble polyimide refers to a polyimide that dissolves in 100 g of a 2.38% by mass tetramethylammonium aqueous solution at 23° C. by 0.1 g or more, and from the viewpoint of pattern formation, 0.5 g or more. It is preferably a polyimide that dissolves, and more preferably a polyimide that dissolves 1.0 g or more. Although the upper limit of the dissolved amount is not particularly limited, it is preferably 100 g or less.
Moreover, the polyimide is preferably a polyimide having a plurality of imide structures in its main chain from the viewpoint of the film strength and insulating properties of the resulting organic film.
As used herein, the term "main chain" refers to the relatively longest linking chain in the molecule of the polymer compound that constitutes the resin, and the term "side chain" refers to the other linking chain.
－フッ素原子－
　得られる有機膜の膜強度の観点からは、ポリイミドは、フッ素原子を有することも好ましい。
　フッ素原子は、例えば、後述する式（４）で表される繰返し単位におけるＲ１３２、又は、後述する式（４）で表される繰返し単位におけるＲ１３１に含まれることが好ましく、後述する式（４）で表される繰返し単位におけるＲ１３２、又は、後述する式（４）で表される繰返し単位におけるＲ１３１にフッ化アルキル基として含まれることがより好ましい。
　ポリイミドの全質量に対するフッ素原子の量は、５質量％以上が好ましく、また、２０質量％以下が好ましい。 - Fluorine atom -
From the viewpoint of the film strength of the organic film to be obtained, the polyimide preferably has a fluorine atom.
A fluorine atom is preferably included in, for example, R 132 in a repeating unit represented by formula (4) described later or R 131 in a repeating unit represented by formula (4) described later, and the formula ( It is more preferably contained as a fluorinated alkyl group in R 132 in the repeating unit represented by 4) or R 131 in the repeating unit represented by formula (4) described later.
The amount of fluorine atoms relative to the total mass of polyimide is preferably 5% by mass or more and preferably 20% by mass or less.
－ケイ素原子－
　得られる有機膜の膜強度の観点からは、ポリイミドは、ケイ素原子を有することも好ましい。
　ケイ素原子は、例えば、後述する式（４）で表される繰返し単位におけるＲ１３１に含まれることが好ましく、後述する式（４）で表される繰返し単位におけるＲ１３１に後述する有機変性（ポリ）シロキサン構造として含まれることがより好ましい。
　また、上記ケイ素原子又は上記有機変性（ポリ）シロキサン構造はポリイミドの側鎖に含まれていてもよいが、ポリイミドの主鎖に含まれることが好ましい。
　ポリイミドの全質量に対するケイ素原子の量は、１質量％以上が好ましく、２０質量％以下がより好ましい。 -Silicon atom-
From the viewpoint of the film strength of the organic film to be obtained, the polyimide preferably has a silicon atom.
A silicon atom, for example, is preferably contained in R 131 in a repeating unit represented by formula (4) described later, and R 131 in a repeating unit represented by formula (4) described later is an organically modified (poly ) is more preferably contained as a siloxane structure.
The silicon atom or the organically modified (poly)siloxane structure may be contained in the side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
The amount of silicon atoms relative to the total mass of polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.
－エチレン性不飽和結合－
　得られる有機膜の膜強度の観点からは、ポリイミドは、エチレン性不飽和結合を有することが好ましい。
　ポリイミドは、エチレン性不飽和結合を主鎖末端に有していてもよいし、側鎖に有していてもよいが、側鎖に有することが好ましい。
　上記エチレン性不飽和結合は、ラジカル重合性を有することが好ましい。
　エチレン性不飽和結合は、後述する式（４）で表される繰返し単位におけるＲ１３２、又は、後述する式（４）で表される繰返し単位におけるＲ１３１に含まれることが好ましく、後述する式（４）で表される繰返し単位におけるＲ１３２、又は、後述する式（４）で表される繰返し単位におけるＲ１３１にエチレン性不飽和結合を有する基として含まれることがより好ましい。
　これらの中でも、エチレン性不飽和結合は、後述する式（４）で表される繰返し単位におけるＲ１３１に含まれることが好ましく、後述する式（４）で表される繰返し単位におけるＲ１３１にエチレン性不飽和結合を有する基として含まれることがより好ましい。
　エチレン性不飽和結合を有する基としては、ビニル基、アリル基、ビニルフェニル基等の芳香環に直接結合した、置換されていてもよいビニル基を有する基、（メタ）アクリルアミド基、（メタ）アクリロイルオキシ基、下記式（ＩＶ）で表される基などが挙げられる。 - Ethylenically unsaturated bond -
From the viewpoint of the film strength of the resulting organic film, the polyimide preferably has an ethylenically unsaturated bond.
The polyimide may have an ethylenically unsaturated bond at the end of its main chain or in a side chain, preferably in a side chain.
The ethylenically unsaturated bond preferably has radical polymerizability.
The ethylenically unsaturated bond is preferably contained in R 132 in a repeating unit represented by the formula (4) described later, or R 131 in a repeating unit represented by the formula (4) described later. It is more preferably included as a group having an ethylenically unsaturated bond in R 132 in the repeating unit represented by (4) or R 131 in the repeating unit represented by formula (4) described below.
Among these, the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by formula (4) described later, and ethylene is contained in R 131 in the repeating unit represented by formula (4) described later It is more preferably included as a group having a polyunsaturated bond.
The group having an ethylenically unsaturated bond includes a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acrylamide group, a (meth) Examples include an acryloyloxy group and a group represented by the following formula (IV).
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　式（ＩＶ）中、Ｒ２０は、水素原子、メチル基、エチル基又はメチロール基を表し、水素原子又はメチル基が好ましい。 In formula (IV), R 20 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, preferably a hydrogen atom or a methyl group.
　式（ＩＶ）中、Ｒ２１は、炭素数２～１２のアルキレン基、－Ｏ－ＣＨ２ＣＨ（ＯＨ）ＣＨ２－、－Ｃ（＝Ｏ）Ｏ－、－Ｏ（Ｃ＝Ｏ）ＮＨ－、炭素数２～３０の（ポリ）アルキレンオキシ基（アルキレン基の炭素数は２～１２が好ましく、２～６がより好ましく、２又は３が特に好ましい；繰返し数は１～１２が好ましく、１～６がより好ましく、１～３が特に好ましい）、又はこれらを２以上組み合わせた基を表す。
　また、上記炭素数２～１２のアルキレン基としては、直鎖状、分岐鎖状、環状又はこれらの組み合わせにより表されるアルキレン基のいずれであってもよい。
　上記炭素数２～１２のアルキレン基としては、炭素数２～８のアルキレン基が好ましく、炭素数２～４のアルキレン基がより好ましい。 In formula (IV), R 21 is an alkylene group having 2 to 12 carbon atoms, —O—CH 2 CH(OH)CH 2 —, —C(═O)O—, —O(C═O)NH— , a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, 1 to 6 are more preferable, and 1 to 3 are particularly preferable), or a group in which two or more of these are combined.
In addition, the alkylene group having 2 to 12 carbon atoms may be a linear, branched, cyclic, or a combination of these alkylene groups.
As the alkylene group having 2 to 12 carbon atoms, an alkylene group having 2 to 8 carbon atoms is preferable, and an alkylene group having 2 to 4 carbon atoms is more preferable.
　これらの中でも、Ｒ２１は下記式（Ｒ１）～式（Ｒ３）のいずれかで表される基であることが好ましく、式（Ｒ１）で表される基であることがより好ましい。
Figure JPOXMLDOC01-appb-C000010
　式（Ｒ１）～（Ｒ３）中、Ｌは単結合、又は、炭素数２～１２のアルキレン基、炭素数２～３０の（ポリ）アルキレンオキシ基若しくはこれらを２以上結合した基を表し、Ｘは酸素原子又は硫黄原子を表し、＊は他の構造との結合部位を表し、●は式（ＩＶ）中のＲ２１が結合する酸素原子との結合部位を表す。
　式（Ｒ１）～（Ｒ３）中、Ｌにおける炭素数２～１２のアルキレン基、又は、炭素数２～３０の（ポリ）アルキレンオキシ基の好ましい態様は、上述のＲ２１における、炭素数２～１２のアルキレン基、又は、炭素数２～３０の（ポリ）アルキレンオキシ基の好ましい態様と同様である。
　式（Ｒ１）中、Ｘは酸素原子であることが好ましい。
　式（Ｒ１）～（Ｒ３）中、＊は式（ＩＶ）中の＊と同義であり、好ましい態様も同様である。
　式（Ｒ１）で表される構造は、例えば、フェノール性ヒドロキシ基等のヒドロキシ基を有するポリイミドと、イソシアナト基及びエチレン性不飽和結合を有する化合物（例えば、２－イソシアナトエチルメタクリレート等）とを反応することにより得られる。
　式（Ｒ２）で表される構造は、例えば、カルボキシ基を有するポリイミドと、ヒドロキシ基及びエチレン性不飽和結合を有する化合物（例えば、２－ヒドロキシエチルメタクリレート等）とを反応することにより得られる。
　式（Ｒ３）で表される構造は、例えば、フェノール性ヒドロキシ基等のヒドロキシ基を有するポリイミドと、グリシジル基及びエチレン性不飽和結合を有する化合物（例えば、グリシジルメタクリレート等）とを反応することにより得られる。 Among these, R 21 is preferably a group represented by any one of the following formulas (R1) to (R3), more preferably a group represented by formula (R1).
Figure JPOXMLDOC01-appb-C000010
In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are combined, and X represents an oxygen atom or a sulfur atom, * represents a bonding site with another structure, and ● represents a bonding site with the oxygen atom to which R 21 in formula (IV) bonds.
In formulas (R1) to (R3), a preferred embodiment of an alkylene group having 2 to 12 carbon atoms or a (poly)alkyleneoxy group having 2 to 30 carbon atoms in L is the above-mentioned R 21 having 2 to 12 carbon atoms. It is the same as the preferred embodiment of the 12 alkylene group or the (poly)alkyleneoxy group having 2 to 30 carbon atoms.
In formula (R1), X is preferably an oxygen atom.
In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and preferred embodiments are also the same.
The structure represented by formula (R1) is, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group, and a compound having an isocyanato group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate, etc.). Obtained by reaction.
The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (eg, 2-hydroxyethyl methacrylate, etc.).
The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate, etc.) can get.
　式（ＩＶ）中、＊は他の構造との結合部位を表し、ポリイミドの主鎖との結合部位であることが好ましい。 In formula (IV), * represents a binding site with another structure, preferably a binding site with the main chain of polyimide.
　ポリイミドの全質量に対するエチレン性不飽和結合の量は、０．０００１～０．１ｍｏｌ／ｇであることが好ましく、０．０００５～０．０５ｍｏｌ／ｇであることがより好ましい。 The amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001-0.1 mol/g, more preferably 0.0005-0.05 mol/g.
－エチレン性不飽和結合を有する基以外の重合性基－
　ポリイミドは、エチレン性不飽和結合を有する基以外の重合性基を有していてもよい。
　エチレン性不飽和結合を有する基以外の重合性基としては、エポキシ基、オキセタニル基等の環状エーテル基、メトキシメチル基等のアルコキシメチル基、メチロール基等が挙げられる。
　エチレン性不飽和結合を有する基以外の重合性基は、例えば、後述する式（４）で表される繰返し単位におけるＲ１３１に含まれることが好ましい。
　ポリイミドの全質量に対するエチレン性不飽和結合を有する基以外の重合性基の量は、０．０００１～０．１ｍｏｌ／ｇであることが好ましく、０．００１～０．０５ｍｏｌ／ｇであることがより好ましい。 -Polymerizable Groups Other than Groups Having Ethylenically Unsaturated Bonds-
Polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond.
Polymerizable groups other than groups having an ethylenically unsaturated bond include cyclic ether groups such as an epoxy group and an oxetanyl group, alkoxymethyl groups such as a methoxymethyl group, and methylol groups.
A polymerizable group other than a group having an ethylenically unsaturated bond is preferably included, for example, in R 131 in a repeating unit represented by formula (4) described below.
The amount of the polymerizable group other than the group having an ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, preferably 0.001 to 0.05 mol / g. more preferred.
－極性変換基－
　ポリイミドは、酸分解性基等の極性変換基を有していてもよい。ポリイミドにおける酸分解性基は、上述の式（２）におけるＲ１１３及びＲ１１４において説明した酸分解性基と同様であり、好ましい態様も同様である。
　極性変換基は、例えば、後述する式（４）で表される繰返し単位におけるＲ１３１、Ｒ１３２、ポリイミドの末端などに含まれる。 -Polarity conversion group-
The polyimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide is the same as the acid-decomposable group described for R 113 and R 114 in formula (2) above, and preferred embodiments are also the same.
Polar conversion groups are included, for example, at R 131 and R 132 in the repeating unit represented by formula (4) described later, the terminal of polyimide, and the like.
－酸価－
　ポリイミドがアルカリ現像に供される場合、現像性を向上する観点からは、ポリイミドの酸価は、３０ｍｇＫＯＨ／ｇ以上であることが好ましく、５０ｍｇＫＯＨ／ｇ以上であることがより好ましく、７０ｍｇＫＯＨ／ｇ以上であることが更に好ましい。
　また、上記酸価は５００ｍｇＫＯＨ／ｇ以下であることが好ましく、４００ｍｇＫＯＨ／ｇ以下であることがより好ましく、２００ｍｇＫＯＨ／ｇ以下であることが更に好ましい。
　また、ポリイミドが有機溶剤を主成分とする現像液を用いた現像（例えば、後述する「溶剤現像」）に供される場合、ポリイミドの酸価は、１～３５ｍｇＫＯＨ／ｇが好ましく、２～３０ｍｇＫＯＨ／ｇがより好ましく、５～２０ｍｇＫＯＨ／ｇが更に好ましい。
　上記酸価は、公知の方法により測定され、例えば、ＪＩＳ　Ｋ　００７０：１９９２に記載の方法により測定される。
　また、ポリイミドに含まれる酸基としては、保存安定性及び現像性の両立の観点から、ｐＫａが０～１０である酸基が好ましく、３～８である酸基がより好ましい。
　ｐＫａとは、酸から水素イオンが放出される解離反応を考え、その平衡定数Ｋａをその負の常用対数ｐＫａによって表したものである。本明細書において、ｐＫａは、特に断らない限り、ＡＣＤ／ＣｈｅｍＳｋｅｔｃｈ（登録商標）による計算値とする。又は、日本化学会編「改定５版　化学便覧　基礎編」に掲載の値を参照してもよい。
　また、酸基が例えばリン酸等の多価の酸である場合、上記ｐＫａは第一解離定数である。
　このような酸基として、ポリイミドは、カルボキシ基、及び、フェノール性ヒドロキシ基よりなる群から選ばれた少なくとも１種を含むことが好ましく、フェノール性ヒドロキシ基を含むことがより好ましい。 - Acid value -
When polyimide is subjected to alkali development, the acid value of polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more, from the viewpoint of improving developability. is more preferable.
Moreover, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.
Further, when the polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyimide is preferably 1 to 35 mgKOH/g, and 2 to 30 mgKOH. /g is more preferred, and 5 to 20 mgKOH/g is even more preferred.
The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.
As the acid group contained in the polyimide, an acid group having a pKa of 0 to 10 is preferable, and an acid group having a pKa of 3 to 8 is more preferable, from the viewpoint of both storage stability and developability.
The pKa is a dissociation reaction in which hydrogen ions are released from an acid, and its equilibrium constant Ka is represented by its negative common logarithm pKa. In this specification, unless otherwise specified, pKa is a value calculated by ACD/ChemSketch (registered trademark). Alternatively, it is possible to refer to the values listed in the Chemical Society of Japan, "Fifth Revised Edition, Chemistry Handbook, Fundamentals".
Also, when the acid group is a polyvalent acid such as phosphoric acid, the pKa is the first dissociation constant.
As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, more preferably a phenolic hydroxy group.
－フェノール性ヒドロキシ基－
　アルカリ現像液による現像速度を適切なものとする観点からは、ポリイミドは、フェノール性ヒドロキシ基を有することが好ましい。
　ポリイミドは、フェノール性ヒドロキシ基を主鎖末端に有してもよいし、側鎖に有してもよい。
　フェノール性ヒドロキシ基は、例えば、後述する式（４）で表される繰返し単位におけるＲ１３２、又は、後述する式（４）で表される繰返し単位におけるＲ１３１に含まれることが好ましい。
　ポリイミドの全質量に対するフェノール性ヒドロキシ基の量は、０．１～３０ｍｏｌ／ｇであることが好ましく、１～２０ｍｏｌ／ｇであることがより好ましい。 -Phenolic hydroxy group-
The polyimide preferably has a phenolic hydroxy group from the viewpoint of making the development speed with an alkaline developer appropriate.
The polyimide may have a phenolic hydroxy group at the end of the main chain or in the side chain.
A phenolic hydroxy group is preferably contained in, for example, R 132 in a repeating unit represented by formula (4) described later or R 131 in a repeating unit represented by formula (4) described later.
The amount of phenolic hydroxy groups relative to the total weight of the polyimide is preferably 0.1-30 mol/g, more preferably 1-20 mol/g.
　本発明で用いるポリイミドとしては、イミド構造を有する高分子化合物であれば、特に限定はないが、下記式（４）で表される繰返し単位を含むことが好ましい。
Figure JPOXMLDOC01-appb-C000011
　式（４）中、Ｒ１３１は、２価の有機基を表し、Ｒ１３２は、４価の有機基を表す。
　重合性基を有する場合、重合性基は、Ｒ１３１及びＲ１３２の少なくとも一方に位置していてもよいし、下記式（４－１）又は式（４－２）に示すようにポリイミドの末端に位置していてもよい。
式（４－１）
Figure JPOXMLDOC01-appb-C000012
式（４－１）中、Ｒ１３３は重合性基であり、他の基は式（４）と同義である。
式（４－２）
Figure JPOXMLDOC01-appb-C000013
　Ｒ１３４及びＲ１３５の少なくとも一方は重合性基であり、重合性基でない場合は有機基であり、他の基は式（４）と同義である。 The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it preferably contains a repeating unit represented by the following formula (4).
Figure JPOXMLDOC01-appb-C000011
In formula (4), R 131 represents a divalent organic group and R 132 represents a tetravalent organic group.
When it has a polymerizable group, the polymerizable group may be located on at least one of R 131 and R 132 , and the terminal of the polyimide as shown in the following formula (4-1) or (4-2) may be located in
Formula (4-1)
Figure JPOXMLDOC01-appb-C000012
In formula (4-1), R 133 is a polymerizable group, and other groups are the same as in formula (4).
Formula (4-2)
Figure JPOXMLDOC01-appb-C000013
At least one of R 134 and R 135 is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups are as defined in formula (4).
　重合性基としては、上述のエチレン性不飽和結合を含む基、又は、上述のエチレン性不飽和結合を有する基以外の架橋性基が挙げられる。
　Ｒ１３１は、２価の有機基を表す。２価の有機基としては、式（２）におけるＲ１１１と同様のものが例示され、好ましい範囲も同様である。
　また、Ｒ１３１としては、ジアミンのアミノ基の除去後に残存するジアミン残基が挙げられる。ジアミンとしては、脂肪族、環式脂肪族又は芳香族ジアミンなどが挙げられる。具体的な例としては、ポリイミド前駆体の式（２）中のＲ１１１の例が挙げられる。 Examples of the polymerizable group include a group containing an ethylenically unsaturated bond as described above and a crosslinkable group other than the group having an ethylenically unsaturated bond as described above.
R 131 represents a divalent organic group. Examples of the divalent organic group are the same as those for R 111 in formula (2), and the preferred range is also the same.
R 131 also includes a diamine residue remaining after removal of the amino group of the diamine. Diamines include aliphatic, cycloaliphatic or aromatic diamines. A specific example is the example of R 111 in formula (2) of the polyimide precursor.
　Ｒ１３１は、少なくとも２つのアルキレングリコール単位を主鎖にもつジアミン残基であることが、焼成時における反りの発生をより効果的に抑制する点で好ましい。より好ましくは、エチレングリコール鎖、プロピレングリコール鎖のいずれか又は両方を一分子中にあわせて２つ以上含むジアミン残基であり、更に好ましくは上記ジアミンであって、芳香環を含まないジアミン残基である。 R 131 is preferably a diamine residue having at least two alkylene glycol units in its main chain from the viewpoint of more effectively suppressing warping during baking. More preferably, it is a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and more preferably the above diamine, which does not contain an aromatic ring. is.
　エチレングリコール鎖、プロピレングリコール鎖のいずれか又は両方を一分子中にあわせて２つ以上含むジアミンとしては、ジェファーミン（登録商標）ＫＨ－５１１、ＥＤ－６００、ＥＤ－９００、ＥＤ－２００３、ＥＤＲ－１４８、ＥＤＲ－１７６、Ｄ－２００、Ｄ－４００、Ｄ－２０００、Ｄ－４０００（以上商品名、ＨＵＮＴＳＭＡＮ（株）製）、１－（２－（２－（２－アミノプロポキシ）エトキシ）プロポキシ）プロパン－２－アミン、１－（１－（１－（２－アミノプロポキシ）プロパン－２－イル）オキシ）プロパン－２－アミンなどが挙げられるが、これらに限定されない。 Diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, and EDR. -148, EDR-176, D-200, D-400, D-2000, D-4000 (trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy) propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, and the like.
　Ｒ１３２は、４価の有機基を表す。４価の有機基としては、式（２）におけるＲ１１５と同様のものが例示され、好ましい範囲も同様である。
　例えば、Ｒ１１５として例示される４価の有機基の４つの結合子が、上記式（４）中の４つの－Ｃ（＝Ｏ）－の部分と結合して縮合環を形成する。 R 132 represents a tetravalent organic group. Examples of the tetravalent organic group are the same as those for R 115 in formula (2), and the preferred range is also the same.
For example, four bonds of a tetravalent organic group exemplified as R 115 combine with four —C(═O)— moieties in the above formula (4) to form a condensed ring.
　また、Ｒ１３２は、テトラカルボン酸二無水物から無水物基の除去後に残存するテトラカルボン酸残基などが挙げられる。具体的な例としては、ポリイミド前駆体の式（２）中のＲ１１５の例が挙げられる。有機膜の強度の観点から、Ｒ１３２は１～４つの芳香環を有する芳香族ジアミン残基であることが好ましい。 Further, R 132 includes a tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride. A specific example is the example of R 115 in formula (2) of the polyimide precursor. From the viewpoint of strength of the organic film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.
　Ｒ１３１とＲ１３２の少なくとも一方にＯＨ基を有することも好ましい。より具体的には、Ｒ１３１として、２，２－ビス（３－ヒドロキシ－４－アミノフェニル）プロパン、２，２－ビス（３－ヒドロキシ－４－アミノフェニル）ヘキサフルオロプロパン、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）プロパン、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパン、上記の（ＤＡ－１）～（ＤＡ－１８）が好ましい例として挙げられ、Ｒ１３２として、上記の（ＤＡＡ－１）～（ＤＡＡ－５）がより好ましい例として挙げられる。 It is also preferred that at least one of R 131 and R 132 has an OH group. More specifically, R 131 is 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2- Bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18) are preferred examples. and more preferred examples of R 132 are the above (DAA-1) to (DAA-5).
　また、ポリイミドは、構造中にフッ素原子を有することも好ましい。ポリイミド中のフッ素原子の含有量は１０質量％以上が好ましく、また、２０質量％以下が好ましい。 Also, the polyimide preferably has a fluorine atom in its structure. The content of fluorine atoms in the polyimide is preferably 10% by mass or more, and preferably 20% by mass or less.
　また、基板との密着性を向上させる目的で、ポリイミドは、シロキサン構造を有する脂肪族の基を共重合してもよい。具体的には、ジアミン成分として、ビス（３－アミノプロピル）テトラメチルジシロキサン、ビス（ｐ－アミノフェニル）オクタメチルペンタシロキサンなどが挙げられる。 In addition, for the purpose of improving adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specific examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.
　また、樹脂組成物の保存安定性を向上させるため、ポリイミドの主鎖末端はモノアミン、酸無水物、モノカルボン酸、モノ酸クロリド化合物、モノ活性エステル化合物などの末端封止剤により封止されていることが好ましい。これらのうち、モノアミンを用いることがより好ましく、モノアミンの好ましい化合物としては、アニリン、２－エチニルアニリン、３－エチニルアニリン、４－エチニルアニリン、５－アミノ－８－ヒドロキシキノリン、１－ヒドロキシ－７－アミノナフタレン、１－ヒドロキシ－６－アミノナフタレン、１－ヒドロキシ－５－アミノナフタレン、１－ヒドロキシ－４－アミノナフタレン、２－ヒドロキシ－７－アミノナフタレン、２－ヒドロキシ－６－アミノナフタレン、２－ヒドロキシ－５－アミノナフタレン、１－カルボキシ－７－アミノナフタレン、１－カルボキシ－６－アミノナフタレン、１－カルボキシ－５－アミノナフタレン、２－カルボキシ－７－アミノナフタレン、２－カルボキシ－６－アミノナフタレン、２－カルボキシ－５－アミノナフタレン、２－アミノ安息香酸、３－アミノ安息香酸、４－アミノ安息香酸、４－アミノサリチル酸、５－アミノサリチル酸、６－アミノサリチル酸、２－アミノベンゼンスルホン酸、３－アミノベンゼンスルホン酸、４－アミノベンゼンスルホン酸、３－アミノ－４，６－ジヒドロキシピリミジン、２－アミノフェノール、３－アミノフェノール、４－アミノフェノール、２－アミノチオフェノール、３－アミノチオフェノール、４－アミノチオフェノールなどが挙げられる。これらを２種以上用いてもよく、複数の末端封止剤を反応させることにより、複数の異なる末端基を導入してもよい。 In addition, in order to improve the storage stability of the resin composition, the main chain end of the polyimide is blocked with a terminal blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound. preferably. Among these, it is more preferable to use monoamines, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7 -aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2 -hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6- Aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfone acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3- Aminothiophenol, 4-aminothiophenol and the like can be mentioned. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.
－イミド化率（閉環率）－
　ポリイミドのイミド化率（「閉環率」ともいう）は、得られる有機膜の膜強度、絶縁性等の観点からは、７０％以上であることが好ましく、８０％以上であることがより好ましく、９０％以上であることがより好ましい。
　上記イミド化率の上限は特に限定されず、１００％以下であればよい。
　上記イミド化率は、例えば下記方法により測定される。
　ポリイミドの赤外吸収スペクトルを測定し、イミド構造由来の吸収ピークである１３７７ｃｍ－１付近のピーク強度Ｐ１を求める。次に、そのポリイミドを３５０℃で１時間熱処理した後、再度、赤外吸収スペクトルを測定し、１３７７ｃｍ－１付近のピーク強度Ｐ２を求める。得られたピーク強度Ｐ１、Ｐ２を用い、下記式に基づいて、ポリイミドのイミド化率を求めることができる。
　イミド化率（％）＝（ピーク強度Ｐ１／ピーク強度Ｐ２）×１００ -Imidation rate (ring closure rate)-
The imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, insulating properties, etc. of the resulting organic film. More preferably, it is 90% or more.
The upper limit of the imidization rate is not particularly limited, and may be 100% or less.
The imidization rate is measured, for example, by the method described below.
The infrared absorption spectrum of the polyimide is measured, and the peak intensity P1 near 1377 cm −1 , which is the absorption peak derived from the imide structure, is obtained. Next, after heat-treating the polyimide at 350° C. for 1 hour, the infrared absorption spectrum is measured again to obtain the peak intensity P2 near 1377 cm −1 . Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be determined according to the following formula.
Imidation rate (%) = (peak intensity P1/peak intensity P2) x 100
　ポリイミドは、すべてが１種のＲ１３１又はＲ１３２を含む上記式（４）で表される繰返し単位を含んでいてもよく、２つ以上の異なる種類のＲ１３１又はＲ１３２を含む上記式（４）で表される繰返し単位を含んでいてもよい。また、ポリイミドは、上記式（４）で表される繰返し単位のほかに、他の種類の繰返し単位をも含んでいてもよい。他の種類の繰返し単位としては、例えば、上述の式（２）で表される繰返し単位等が挙げられる。 The polyimide may contain repeating units represented by the above formula (4) that all contain one type of R 131 or R 132 , and the above formula ( 4) may contain a repeating unit. Moreover, the polyimide may contain other types of repeating units in addition to the repeating units represented by the above formula (4). Other types of repeating units include, for example, repeating units represented by formula (2) above.
　ポリイミドは、例えば、低温中でテトラカルボン酸二無水物とジアミン（一部をモノアミンである末端封止剤に置換）を反応させる方法、低温中でテトラカルボン酸二無水物（一部を酸無水物又はモノ酸クロリド化合物又はモノ活性エステル化合物である末端封止剤に置換）とジアミンを反応させる方法、テトラカルボン酸二無水物とアルコールとによりジエステルを得、その後ジアミン（一部をモノアミンである末端封止剤に置換）と縮合剤の存在下で反応させる方法、テトラカルボン酸二無水物とアルコールとによりジエステルを得、その後残りのジカルボン酸を酸クロリド化し、ジアミン（一部をモノアミンである末端封止剤に置換）と反応させる方法などの方法を利用して、ポリイミド前駆体を得、これを、既知のイミド化反応法を用いて完全イミド化させる方法、又は、途中でイミド化反応を停止し、一部イミド構造を導入する方法、更には、完全イミド化したポリマーと、そのポリイミド前駆体をブレンドする事によって、一部イミド構造を導入する方法を利用して合成することができる。また、その他公知のポリイミドの合成方法を適用することもできる。 For polyimide, for example, a method of reacting a tetracarboxylic dianhydride and a diamine (partially replaced with a monoamine terminal blocker) at a low temperature, a method of reacting a tetracarboxylic dianhydride (partially with an acid anhydride) at a low temperature a monoacid chloride compound or a monoactive ester compound) and a diamine, a diester is obtained by a tetracarboxylic dianhydride and an alcohol, and then a diamine (a part of which is a monoamine A method of reacting in the presence of a condensing agent) with a condensing agent, a diester is obtained by tetracarboxylic acid dianhydride and alcohol, then the remaining dicarboxylic acid is acid chloride, diamine (part of which is a monoamine Using a method such as a method of reacting with a terminal blocking agent) to obtain a polyimide precursor, which is completely imidized using a known imidization reaction method, or an imidization reaction in the middle can be synthesized using a method of partially introducing an imide structure by stopping the , or a method of partially introducing an imide structure by blending a completely imidized polymer and its polyimide precursor. . Other known methods for synthesizing polyimide can also be applied.
　ポリイミドの重量平均分子量（Ｍｗ）は、好ましくは５，０００～１００，０００であり、より好ましくは１０，０００～５０，０００であり、更に好ましくは１５，０００～４０，０００である。重量平均分子量を５，０００以上とすることにより、硬化後の膜の耐折れ性を向上させることができる。機械特性（例えば、破断伸び）に優れた有機膜を得るため、重量平均分子量は、１５，０００以上が特に好ましい。
　また、ポリイミドの数平均分子量（Ｍｎ）は、好ましくは２，０００～４０，０００であり、より好ましくは３，０００～３０，０００であり、更に好ましくは４，０００～２０，０００である。
　上記ポリイミドの分子量の分散度は、１．５以上が好ましく、１．８以上がより好ましく、２．０以上であることが更に好ましい。ポリイミドの分子量の分散度の上限値は特に定めるものではないが、例えば、７．０以下が好ましく、６．５以下がより好ましく、６．０以下が更に好ましい。
　また、樹脂組成物が特定樹脂として複数種のポリイミドを含む場合、少なくとも１種のポリイミドの重量平均分子量、数平均分子量、及び、分散度が上記範囲であることが好ましい。また、上記複数種のポリイミドを１つの樹脂として算出した重量平均分子量、数平均分子量、及び、分散度が、それぞれ、上記範囲内であることも好ましい。 The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, still more preferably 15,000 to 40,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. A weight-average molecular weight of 15,000 or more is particularly preferable in order to obtain an organic film having excellent mechanical properties (e.g., elongation at break).
Also, the number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, still more preferably 4,000 to 20,000.
The polyimide has a molecular weight distribution of preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. Although the upper limit of the polyimide molecular weight dispersion is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
Moreover, when the resin composition contains a plurality of types of polyimide as the specific resin, the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polyimide are preferably within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated using the above plural kinds of polyimides as one resin are within the ranges described above.
〔ポリイミド前駆体等の製造方法〕
　ポリイミド前駆体等は、例えば、低温中でテトラカルボン酸二無水物とジアミンを反応させる方法、低温中でテトラカルボン酸二無水物とジアミンを反応させてポリアミック酸を得、縮合剤又はアルキル化剤を用いてエステル化する方法、テトラカルボン酸二無水物とアルコールとによりジエステルを得て、その後ジアミンと縮合剤の存在下で反応させる方法、テトラカルボン酸二無水物とアルコールとによりジエステルを得、その後残りのジカルボン酸をハロゲン化剤を用いて酸ハロゲン化し、ジアミンと反応させる方法、などの方法を利用して得ることができる。上記製造方法のうち、テトラカルボン酸二無水物とアルコールとによりジエステルを得、その後残りのジカルボン酸をハロゲン化剤を用いて酸ハロゲン化し、ジアミンと反応させる方法がより好ましい。
　上記縮合剤としては、例えばジシクロヘキシルカルボジイミド、ジイソプロピルカルボジイミド、１－エトキシカルボニル－２－エトキシ－１，２－ジヒドロキノリン、１，１－カルボニルジオキシ－ジ－１，２，３－ベンゾトリアゾール、Ｎ，Ｎ’－ジスクシンイミジルカーボネート、無水トリフルオロ酢酸等が挙げられる。
　上記アルキル化剤としては、Ｎ，Ｎ－ジメチルホルムアミドジメチルアセタール、Ｎ，Ｎ－ジメチルホルムアミドジエチルアセタール、Ｎ，Ｎ－ジアルキルホルムアミドジアルキルアセタール、オルトギ酸トリメチル、オルトギ酸トリエチル等が挙げられる。
　上記ハロゲン化剤としては、塩化チオニル、塩化オキサリル、オキシ塩化リン等が挙げられる。
　ポリイミド前駆体等の製造方法では、反応に際し、有機溶剤を用いることが好ましい。有機溶剤は１種でもよいし、２種以上でもよい。
　有機溶剤としては、原料に応じて適宜定めることができるが、ピリジン、ジエチレングリコールジメチルエーテル（ジグリム）、Ｎ－メチルピロリドン、Ｎ－エチルピロリドン、プロピオン酸エチル、ジメチルアセトアミド、ジメチルホルムアミド、テトラヒドロフラン、γ－ブチロラクトン等が例示される。
　ポリイミド前駆体等の製造方法では、反応に際し、塩基性化合物を添加することが好ましい。塩基性化合物は１種でもよいし、２種以上でもよい。
　塩基性化合物は、原料に応じて適宜定めることができるが、トリエチルアミン、ジイソプロピルエチルアミン、ピリジン、１，８－ジアザビシクロ［５．４．０］ウンデカ－７－エン、Ｎ，Ｎ－ジメチル－４－アミノピリジン等が例示される。 [Method for producing polyimide precursor, etc.]
Polyimide precursors and the like, for example, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature to obtain a polyamic acid, a condensing agent or an alkylating agent A method of esterification using a tetracarboxylic dianhydride and an alcohol to obtain a diester, followed by a reaction with a diamine in the presence of a condensing agent, a method of reacting a tetracarboxylic dianhydride and an alcohol to obtain a diester, After that, the remaining dicarboxylic acid can be acid-halogenated using a halogenating agent and reacted with a diamine. Among the above production methods, the method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and reacting it with a diamine is more preferred.
Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N'-disuccinimidyl carbonate, trifluoroacetic anhydride and the like can be mentioned.
Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate and triethyl orthoformate.
Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphorus oxychloride and the like.
In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction. One type of organic solvent may be used, or two or more types may be used.
The organic solvent can be appropriately determined depending on the raw material, but pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, and the like. are exemplified.
In the method for producing a polyimide precursor or the like, it is preferable to add a basic compound during the reaction. One type of basic compound may be used, or two or more types may be used.
The basic compound can be appropriately determined depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-amino Pyridine and the like are exemplified.
－末端封止剤－
　ポリイミド前駆体等の製造方法に際し、保存安定性をより向上させるため、ポリイミド前駆体等の樹脂末端に残存するカルボン酸無水物、酸無水物誘導体、或いは、アミノ基を封止することが好ましい。樹脂末端に残存するカルボン酸無水物、及び酸無水物誘導体を封止する際、末端封止剤としては、モノアルコール、フェノール、チオール、チオフェノール、モノアミン等が挙げられ、反応性、膜の安定性から、モノアルコール、フェノール類やモノアミンを用いることがより好ましい。モノアルコールの好ましい化合物としては、メタノール、エタノール、プロパノール、ブタノール、ヘキサノール、オクタノール、ドデシノール、ベンジルアルコール、２－フェニルエタノール、２－メトキシエタノール、２－クロロメタノール、フルフリルアルコール等の１級アルコール、イソプロパノール、２－ブタノール、シクロヘキシルアルコール、シクロペンタノール、１－メトキシ－２－プロパノール等の２級アルコール、ｔ－ブチルアルコール、アダマンタンアルコール等の３級アルコールが挙げられる。フェノール類の好ましい化合物としては、フェノール、メトキシフェノール、メチルフェノール、ナフタレン－１－オール、ナフタレン－２－オール、ヒドロキシスチレン等のフェノール類などが挙げられる。また、モノアミンの好ましい化合物としては、アニリン、２－エチニルアニリン、３－エチニルアニリン、４－エチニルアニリン、５－アミノ－８－ヒドロキシキノリン、１－ヒドロキシ－７－アミノナフタレン、１－ヒドロキシ－６－アミノナフタレン、１－ヒドロキシ－５－アミノナフタレン、１－ヒドロキシ－４－アミノナフタレン、２－ヒドロキシ－７－アミノナフタレン、２－ヒドロキシ－６－アミノナフタレン、２－ヒドロキシ－５－アミノナフタレン、１－カルボキシ－７－アミノナフタレン、１－カルボキシ－６－アミノナフタレン、１－カルボキシ－５－アミノナフタレン、２－カルボキシ－７－アミノナフタレン、２－カルボキシ－６－アミノナフタレン、２－カルボキシ－５－アミノナフタレン、２－アミノ安息香酸、３－アミノ安息香酸、４－アミノ安息香酸、４－アミノサリチル酸、５－アミノサリチル酸、６－アミノサリチル酸、２－アミノベンゼンスルホン酸、３－アミノベンゼンスルホン酸、４－アミノベンゼンスルホン酸、３－アミノ－４，６－ジヒドロキシピリミジン、２－アミノフェノール、３－アミノフェノール、４－アミノフェノール、２－アミノチオフェノール、３－アミノチオフェノール、４－アミノチオフェノールなどが挙げられる。これらを２種以上用いてもよく、複数の末端封止剤を反応させることにより、複数の異なる末端基を導入してもよい。
　また、樹脂末端のアミノ基を封止する際、アミノ基と反応可能な官能基を有する化合物で封止することが可能である。アミノ基に対する好ましい封止剤は、カルボン酸無水物、カルボン酸クロリド、カルボン酸ブロミド、スルホン酸クロリド、無水スルホン酸、スルホン酸カルボン酸無水物などが好ましく、カルボン酸無水物、カルボン酸クロリドがより好ましい。カルボン酸無水物の好ましい化合物としては、無水酢酸、無水プロピオン酸、無水シュウ酸、無水コハク酸、無水マレイン酸、無水フタル酸、無水安息香酸、５－ノルボルネン－２，３－ジカルボン酸無水物などが挙げられる。また、カルボン酸クロリドの好ましい化合物としては、塩化アセチル、アクリル酸クロリド、プロピオニルクロリド、メタクリル酸クロリド、ピバロイルクロリド、シクロヘキサンカルボニルクロリド、２－エチルヘキサノイルクロリド、シンナモイルクロリド、１－アダマンタンカルボニルクロリド、ヘプタフルオロブチリルクロリド、ステアリン酸クロリド、ベンゾイルクロリド、などが挙げられる。 -Terminal blocking agent-
In the production method of polyimide precursors, etc., in order to further improve the storage stability, it is preferable to seal the carboxylic anhydride, acid anhydride derivative, or amino group remaining at the end of the resin such as polyimide precursors. When blocking carboxylic acid anhydrides and acid anhydride derivatives remaining at the ends of resins, terminal blocking agents include monoalcohols, phenols, thiols, thiophenols, monoamines, and the like. It is more preferable to use monoalcohols, phenols and monoamines from the viewpoint of their properties. Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol and furfuryl alcohol, and isopropanol. , 2-butanol, cyclohexyl alcohol, cyclopentanol and 1-methoxy-2-propanol, and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. Preferable phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6- aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1- Carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-amino naphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4 -aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. is mentioned. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.
Moreover, when blocking the amino group at the terminal of the resin, it is possible to block with a compound having a functional group capable of reacting with the amino group. Preferred capping agents for amino groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromide, sulfonic acid chlorides, sulfonic anhydrides, sulfonic acid carboxylic acid anhydrides, etc., more preferably carboxylic acid anhydrides and carboxylic acid chlorides. preferable. Preferred carboxylic anhydride compounds include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and the like. is mentioned. Preferred compounds of carboxylic acid chlorides include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, and 1-adamantanecarbonyl chloride. , heptafluorobutyryl chloride, stearic acid chloride, benzoyl chloride, and the like.
－固体析出－
　ポリイミド前駆体等の製造に際し、固体を析出する工程を含んでいてもよい。具体的には、反応液中に共存している脱水縮合剤の吸水副生物を必要に応じて濾別した後、水、脂肪族低級アルコール、又はその混合液等の貧溶媒に、得られた重合体成分を投入し、重合体成分を析出させることで、固体として析出させ、乾燥させることでポリイミド前駆体等を得ることができる。精製度を向上させるために、ポリイミド前駆体等を再溶解、再沈析出、乾燥等の操作を繰返してもよい。さらに、イオン交換樹脂を用いてイオン性不純物を除去する工程を含んでいてもよい。 -Solid precipitation-
A step of depositing a solid may be included in the production of the polyimide precursor or the like. Specifically, after filtering off the water absorption by-products of the dehydration condensation agent coexisting in the reaction solution as necessary, water, aliphatic lower alcohol, or a poor solvent such as a mixture thereof, the obtained A polyimide precursor or the like can be obtained by adding a polymer component and depositing the polymer component, depositing it as a solid, and drying it. In order to improve the degree of purification, operations such as redissolution, reprecipitation, drying, etc. of the polyimide precursor may be repeated. Furthermore, a step of removing ionic impurities using an ion exchange resin may be included.
〔含有量〕
　本発明の樹脂組成物における特定樹脂の含有量は、樹脂組成物の全固形分に対し２０質量％以上であることが好ましく、３０質量％以上であることがより好ましく、４０質量％以上であることが更に好ましく、５０質量％以上であることが一層好ましい。また、本発明の樹脂組成物における樹脂の含有量は、樹脂組成物の全固形分に対し、９９．５質量％以下であることが好ましく、９９質量％以下であることがより好ましく、９８質量％以下であることが更に好ましく、９７質量％以下であることが一層好ましく、９５質量％以下であることがより一層好ましい。
　本発明の樹脂組成物は、特定樹脂を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 〔Content〕
The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more with respect to the total solid content of the resin composition. is more preferable, and 50% by mass or more is even more preferable. Further, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, more preferably 98% by mass, based on the total solid content of the resin composition. % or less, more preferably 97 mass % or less, and even more preferably 95 mass % or less.
The resin composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
　また、本発明の樹脂組成物は、少なくとも２種の樹脂を含むことも好ましい。
　具体的には、本発明の樹脂組成物は、特定樹脂と、後述する他の樹脂とを合計で２種以上含んでもよいし、特定樹脂を２種以上含んでいてもよいが、特定樹脂を２種以上含むことが好ましい。
　本発明の樹脂組成物が特定樹脂を２種以上含む場合、例えば、ポリイミド前駆体であって、二無水物由来の構造（上述の式（２）でいうＲ１１５）が異なる２種以上のポリイミド前駆体を含むことが好ましい。 Also, the resin composition of the present invention preferably contains at least two resins.
Specifically, the resin composition of the present invention may contain a total of two or more of the specific resin and other resins described later, or may contain two or more of the specific resins. It is preferable to include two or more kinds.
When the resin composition of the present invention contains two or more specific resins, for example, two or more polyimides that are polyimide precursors and have different dianhydride-derived structures (R 115 in the above formula (2)) It preferably contains a precursor.
＜他の樹脂＞
　本発明の樹脂組成物は、上述した特定樹脂と、特定樹脂とは異なる他の樹脂（以下、単に「他の樹脂」ともいう）とを含んでもよい。
　他の樹脂としては、フェノール樹脂、ポリアミド、エポキシ樹脂、ポリシロキサン、シロキサン構造を含む樹脂、（メタ）アクリル樹脂、（メタ）アクリルアミド樹脂、ウレタン樹脂、ブチラール樹脂、スチリル樹脂、ポリエーテル樹脂、ポリエステル樹脂等が挙げられる。
　例えば、（メタ）アクリル樹脂を更に加えることにより、塗布性に優れた樹脂組成物が得られ、また、耐溶剤性に優れたパターン（硬化物）が得られる。
　例えば、後述する重合性化合物に代えて、又は、後述する重合性化合物に加えて、重量平均分子量が２０，０００以下の重合性基価の高い（例えば、樹脂１ｇにおける重合性基の含有モル量が１×１０－３モル／ｇ以上である）（メタ）アクリル樹脂を樹脂組成物に添加することにより、樹脂組成物の塗布性、パターン（硬化物）の耐溶剤性等を向上させることができる。
　また、他の樹脂をフィラーの分散剤として樹脂組成物に添加することもできる。このような態様において、他の樹脂としては、公知のフィラーの分散剤を特に制限なく使用することができる。 <Other resins>
The resin composition of the present invention may contain the specific resin described above and other resins different from the specific resin (hereinafter also simply referred to as "other resins").
Other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. etc.
For example, by further adding a (meth)acrylic resin, a resin composition having excellent applicability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
For example, instead of the polymerizable compound described later, or in addition to the polymerizable compound described later, a high polymerizable group value having a weight average molecular weight of 20,000 or less (for example, the molar amount of the polymerizable group in 1 g of the resin is 1×10 −3 mol/g or more), the coating properties of the resin composition, the solvent resistance of the pattern (cured product), etc. can be improved. can.
Other resins can also be added to the resin composition as dispersants for fillers. In such an embodiment, as the other resin, a known filler dispersant can be used without particular limitation.
　本発明の樹脂組成物が他の樹脂を含む場合、他の樹脂の含有量は、樹脂組成物の全固形分に対し、０．０１質量％以上であることが好ましく、０．０５質量％以上であることがより好ましく、１質量％以上であることが更に好ましく、２質量％以上であることが一層好ましく、５質量％以上であることがより一層好ましく、１０質量％以上であることが更に一層好ましい。
　また、本発明の樹脂組成物における、他の樹脂の含有量は、樹脂組成物の全固形分に対し、８０質量％以下であることが好ましく、７５質量％以下であることがより好ましく、７０質量％以下であることが更に好ましく、６０質量％以下であることが一層好ましく、５０質量％以下であることがより一層好ましい。
　また、本発明の樹脂組成物の好ましい一態様として、他の樹脂の含有量が低含有量である態様とすることもできる。上記態様において、他の樹脂の含有量は、樹脂組成物の全固形分からに対し、２０質量％以下であることが好ましく、１５質量％以下であることがより好ましく、１０質量％以下であることが更に好ましく、５質量％以下であることが一層好ましく、１質量％以下であることがより一層好ましい。上記含有量の下限は特に限定されず、０質量％以上であればよい。
　本発明の樹脂組成物は、他の樹脂を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, and 0.05% by mass or more, relative to the total solid content of the resin composition. More preferably, it is more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and further preferably 10% by mass or more. More preferred.
In addition, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, based on the total solid content of the resin composition. It is more preferably 60% by mass or less, even more preferably 50% by mass or less.
In addition, as a preferred embodiment of the resin composition of the present invention, the content of other resins may be low. In the above aspect, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less, relative to the total solid content of the resin composition. is more preferable, 5% by mass or less is even more preferable, and 1% by mass or less is even more preferable. The lower limit of the content is not particularly limited as long as it is 0% by mass or more.
The resin composition of the present invention may contain only one kind of other resin, or may contain two or more kinds thereof. When two or more types are included, the total amount is preferably within the above range.
＜重合性化合物＞
　本発明の樹脂組成物は、重合性化合物を含むことが好ましい。
　重合性化合物としては、ラジカル架橋剤、又は、他の架橋剤が挙げられる。 <Polymerizable compound>
The resin composition of the present invention preferably contains a polymerizable compound.
Polymerizable compounds include radical cross-linking agents or other cross-linking agents.
〔ラジカル架橋剤〕
　本発明の樹脂組成物は、ラジカル架橋剤を含むことが好ましい。
　ラジカル架橋剤は、ラジカル重合性基を有する化合物である。ラジカル重合性基としては、エチレン性不飽和結合を含む基が好ましい。上記エチレン性不飽和結合を含む基としては、ビニル基、アリル基、ビニルフェニル基、（メタ）アクリロイル基、マレイミド基、（メタ）アクリルアミド基などのエチレン性不飽和結合を有する基が挙げられる。
　これらの中でも、上記エチレン性不飽和結合を含む基としては、（メタ）アクリロイル基、（メタ）アクリルアミド基、ビニルフェニル基が好ましく、反応性の観点からは、（メタ）アクリロイル基がより好ましい。 [Radical cross-linking agent]
The resin composition of the present invention preferably contains a radical cross-linking agent.
A radical cross-linking agent is a compound having a radically polymerizable group. As the radically polymerizable group, a group containing an ethylenically unsaturated bond is preferred. Examples of the group containing an ethylenically unsaturated bond include groups containing an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
Among these, the group containing an ethylenically unsaturated bond is preferably a (meth)acryloyl group, a (meth)acrylamide group, or a vinylphenyl group, and more preferably a (meth)acryloyl group from the viewpoint of reactivity.
　ラジカル架橋剤は、エチレン性不飽和結合を１個以上有する化合物であることが好ましいが、２個以上有する化合物であることがより好ましい。ラジカル架橋剤は、エチレン性不飽和結合を３個以上有していてもよい。
　上記エチレン性不飽和結合を２個以上有する化合物としては、エチレン性不飽和結合を２～１５個有する化合物が好ましく、エチレン性不飽和結合を２～１０個有する化合物がより好ましく、２～６個有する化合物が更に好ましい。
　また、得られるパターン（硬化物）の膜強度の観点からは、本発明の樹脂組成物は、エチレン性不飽和結合を２個有する化合物と、上記エチレン性不飽和結合を３個以上有する化合物とを含むことも好ましい。 The radical cross-linking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more. The radical cross-linking agent may have 3 or more ethylenically unsaturated bonds.
The compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and 2 to 6. More preferred are compounds having
Further, from the viewpoint of the film strength of the resulting pattern (cured product), the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferred to include
　ラジカル架橋剤の分子量は、２，０００以下が好ましく、１，５００以下がより好ましく、９００以下が更に好ましい。ラジカル架橋剤の分子量の下限は、１００以上が好ましい。 The molecular weight of the radical cross-linking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical cross-linking agent is preferably 100 or more.
　ラジカル架橋剤の具体例としては、不飽和カルボン酸（例えば、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、イソクロトン酸、マレイン酸など）やそのエステル類、アミド類が挙げられ、好ましくは、不飽和カルボン酸と多価アルコール化合物とのエステル、及び不飽和カルボン酸と多価アミン化合物とのアミド類である。また、ヒドロキシ基やアミノ基、スルファニル基等の求核性置換基を有する不飽和カルボン酸エステル又はアミド類と、単官能若しくは多官能イソシアネート類又はエポキシ類との付加反応物や、単官能若しくは多官能のカルボン酸との脱水縮合反応物等も好適に使用される。また、イソシアネート基やエポキシ基等の親電子性置換基を有する不飽和カルボン酸エステル又はアミド類と、単官能若しくは多官能のアルコール類、アミン類、チオール類との付加反応物、更に、ハロゲノ基やトシルオキシ基等の脱離性置換基を有する不飽和カルボン酸エステル又はアミド類と、単官能若しくは多官能のアルコール類、アミン類、チオール類との置換反応物も好適である。また、別の例として、上記の不飽和カルボン酸の代わりに、不飽和ホスホン酸、スチレン等のビニルベンゼン誘導体、ビニルエーテル、アリルエーテル等に置き換えた化合物群を使用することも可能である。具体例としては、特開２０１６－０２７３５７号公報の段落０１１３～０１２２の記載を参酌でき、これらの内容は本明細書に組み込まれる。 Specific examples of the radical cross-linking agent include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. They are esters of saturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxy group, an amino group, or a sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, or monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and halogeno groups Also suitable are substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a tosyloxy group and monofunctional or polyfunctional alcohols, amines, and thiols. As another example, it is also possible to use a group of compounds in which the unsaturated carboxylic acid is replaced with unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, or the like. As specific examples, paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated herein.
　また、ラジカル架橋剤は、常圧下で１００℃以上の沸点を持つ化合物も好ましい。その例としては、ポリエチレングリコールジ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（アクリロイルオキシプロピル）エーテル、トリ（アクリロイルオキシエチル）イソシアヌレート、グリセリンやトリメチロールエタン等の多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後、（メタ）アクリレート化した化合物、特公昭４８－０４１７０８号公報、特公昭５０－００６０３４号公報、特開昭５１－０３７１９３号各公報に記載されているようなウレタン（メタ）アクリレート類、特開昭４８－０６４１８３号、特公昭４９－０４３１９１号、特公昭５２－０３０４９０号各公報に記載されているポリエステルアクリレート類、エポキシ樹脂と（メタ）アクリル酸との反応生成物であるエポキシアクリレート類等の多官能のアクリレートやメタクリレート及びこれらの混合物を挙げることができる。また、特開２００８－２９２９７０号公報の段落０２５４～０２５７に記載の化合物も好適である。また、多官能カルボン酸にグリシジル（メタ）アクリレート等の環状エーテル基とエチレン性不飽和結合を有する化合物を反応させて得られる多官能（メタ）アクリレートなども挙げることができる。 Also, the radical cross-linking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, glycerin, trimethylolethane, etc. Compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylated, described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Publication No. 51-037193. Urethane (meth)acrylates such as those described in JP-A-48-064183, JP-B-49-043191, JP-B-52-030490, polyester acrylates, epoxy resins and (meth) Polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products with acrylic acid, and mixtures thereof can be mentioned. Compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, polyfunctional (meth)acrylate obtained by reacting polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth)acrylate and an ethylenically unsaturated bond can also be used.
　また、上述以外の好ましいラジカル架橋剤として、特開２０１０－１６０４１８号公報、特開２０１０－１２９８２５号公報、特許第４３６４２１６号公報等に記載される、フルオレン環を有し、エチレン性不飽和結合を有する基を２個以上有する化合物や、カルド樹脂も使用することが可能である。 Further, as preferred radical cross-linking agents other than those described above, JP-A-2010-160418, JP-A-2010-129825, JP-A-4364216, etc. have a fluorene ring and an ethylenically unsaturated bond. It is also possible to use compounds having two or more groups and cardo resins.
　更に、その他の例としては、特公昭４６－０４３９４６号公報、特公平０１－０４０３３７号公報、特公平０１－０４０３３６号公報に記載の特定の不飽和化合物や、特開平０２－０２５４９３号公報に記載のビニルホスホン酸系化合物等もあげることができる。また、特開昭６１－０２２０４８号公報に記載のペルフルオロアルキル基を含む化合物を用いることもできる。更に日本接着協会誌　ｖｏｌ．２０、Ｎｏ．７、３００～３０８ページ（１９８４年）に光重合性モノマー及びオリゴマーとして紹介されているものも使用することができる。 Furthermore, other examples include specific unsaturated compounds described in JP-B-46-043946, JP-B-01-040337, JP-B-01-040336, and JP-A-02-025493. vinyl phosphonic acid compounds and the like can also be mentioned. Compounds containing perfluoroalkyl groups described in JP-A-61-022048 can also be used. Furthermore, the journal of the Japan Adhesive Association vol. 20, No. 7, pp. 300-308 (1984) as photopolymerizable monomers and oligomers can also be used.
　上記のほか、特開２０１５－０３４９６４号公報の段落００４８～００５１に記載の化合物、国際公開第２０１５／１９９２１９号の段落００８７～０１３１に記載の化合物も好ましく用いることができ、これらの内容は本明細書に組み込まれる。 In addition to the above, compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964, compounds described in paragraphs 0087 to 0131 of WO 2015/199219 can also be preferably used, the contents of which are herein incorporated into the book.
　また、特開平１０－０６２９８６号公報において式（１）及び式（２）としてその具体例と共に記載の、多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後に（メタ）アクリレート化した化合物も、ラジカル架橋剤として用いることができる。 Further, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylated, which are described together with specific examples as formulas (1) and (2) in JP-A-10-062986, It can be used as a radical cross-linking agent.
　更に、特開２０１５－１８７２１１号公報の段落０１０４～０１３１に記載の化合物もラジカル架橋剤として用いることができ、これらの内容は本明細書に組み込まれる。 Furthermore, compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as radical cross-linking agents, and the contents of these are incorporated herein.
　ラジカル架橋剤としては、ジペンタエリスリトールトリアクリレート（市販品としては　ＫＡＹＡＲＡＤ　Ｄ－３３０（日本化薬（株）製））、ジペンタエリスリトールテトラアクリレート（市販品としては　ＫＡＹＡＲＡＤ　Ｄ－３２０（日本化薬（株）製）、Ａ－ＴＭＭＴ（新中村化学工業（株）製））、ジペンタエリスリトールペンタ（メタ）アクリレート（市販品としては　ＫＡＹＡＲＡＤ　Ｄ－３１０（日本化薬（株）製））、ジペンタエリスリトールヘキサ（メタ）アクリレート（市販品としては　ＫＡＹＡＲＡＤ　ＤＰＨＡ（日本化薬（株）製）、Ａ－ＤＰＨ（新中村化学工業社製））、及びこれらの（メタ）アクリロイル基がエチレングリコール残基又はプロピレングリコール残基を介して結合している構造が好ましい。これらのオリゴマータイプも使用できる。 As a radical cross-linking agent, dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (Nippon Kayaku ( Ltd.), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipenta Erythritol hexa(meth)acrylate (commercially available products are KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), and their (meth)acryloyl groups are ethylene glycol residues or Structures that are linked via a propylene glycol residue are preferred. These oligomeric types can also be used.
　ラジカル架橋剤の市販品としては、例えばサートマー社製のエチレンオキシ鎖を４個有する４官能アクリレートであるＳＲ－４９４、エチレンオキシ鎖を４個有する２官能メタクリレートであるサートマー社製のＳＲ－２０９、２３１、２３９、日本化薬（株）製のペンチレンオキシ鎖を６個有する６官能アクリレートであるＤＰＣＡ－６０、イソブチレンオキシ鎖を３個有する３官能アクリレートであるＴＰＡ－３３０、ウレタンオリゴマーＵＡＳ－１０、ＵＡＢ－１４０（日本製紙社製）、ＮＫエステルＭ－４０Ｇ、ＮＫエステル４Ｇ、ＮＫエステルＭ－９３００、ＮＫエステルＡ－９３００、ＵＡ－７２００（新中村化学工業社製）、ＤＰＨＡ－４０Ｈ（日本化薬（株）製）、ＵＡ－３０６Ｈ、ＵＡ－３０６Ｔ、ＵＡ－３０６Ｉ、ＡＨ－６００、Ｔ－６００、ＡＩ－６００（以上、共栄社化学社製）、ブレンマーＰＭＥ４００（日油（株）製）などが挙げられる。 Examples of commercially available radical cross-linking agents include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, SR-209, a bifunctional methacrylate having four ethyleneoxy chains, manufactured by Sartomer. 231, 239, Nippon Kayaku Co., Ltd. DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains, TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS-10 , UAB-140 (manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Japan Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blenmer PME400 (manufactured by NOF Corporation) etc.
　ラジカル架橋剤としては、特公昭４８－０４１７０８号公報、特開昭５１－０３７１９３号公報、特公平０２－０３２２９３号公報、特公平０２－０１６７６５号公報に記載されているようなウレタンアクリレート類や、特公昭５８－０４９８６０号公報、特公昭５６－０１７６５４号公報、特公昭６２－０３９４１７号公報、特公昭６２－０３９４１８号公報に記載のエチレンオキサイド系骨格を有するウレタン化合物類も好適である。更に、ラジカル架橋剤として、特開昭６３－２７７６５３号公報、特開昭６３－２６０９０９号公報、特開平０１－１０５２３８号公報に記載される、分子内にアミノ構造やスルフィド構造を有する化合物を用いることもできる。 Examples of radical cross-linking agents include urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, JP-B-02-016765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also suitable. Furthermore, as a radical cross-linking agent, compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 are used. can also
　ラジカル架橋剤は、カルボキシ基、リン酸基等の酸基を有するラジカル架橋剤であってもよい。酸基を有するラジカル架橋剤は、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルが好ましく、脂肪族ポリヒドロキシ化合物の未反応のヒドロキシ基に非芳香族カルボン酸無水物を反応させて酸基を持たせたラジカル架橋剤がより好ましい。特に好ましくは、脂肪族ポリヒドロキシ化合物の未反応のヒドロキシ基に非芳香族カルボン酸無水物を反応させて酸基を持たせたラジカル架橋剤において、脂肪族ポリヒドロキシ化合物がペンタエリスリトール又はジペンタエリスリトールである化合物である。市販品としては、例えば、東亞合成（株）製の多塩基酸変性アクリルオリゴマーとして、Ｍ－５１０、Ｍ－５２０などが挙げられる。 The radical cross-linking agent may be a radical cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group. A radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. is more preferable. Particularly preferably, in a radical cross-linking agent obtained by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol is a compound. Examples of commercially available products include polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd. such as M-510 and M-520.
　酸基を有するラジカル架橋剤の好ましい酸価は、０．１～３００ｍｇＫＯＨ／ｇであり、特に好ましくは１～１００ｍｇＫＯＨ／ｇである。ラジカル架橋剤の酸価が上記範囲であれば、製造上の取扱性に優れ、更には、現像性に優れる。また、重合性が良好である。上記酸価は、ＪＩＳ　Ｋ　００７０：１９９２の記載に準拠して測定される。 The acid value of the radical cross-linking agent having an acid group is preferably 0.1-300 mgKOH/g, particularly preferably 1-100 mgKOH/g. If the acid value of the radical cross-linking agent is within the above range, the handleability in production is excellent, and furthermore the developability is excellent. Moreover, the polymerizability is good. The acid value is measured according to JIS K 0070:1992.
　樹脂組成物は、パターンの解像性と膜の伸縮性の観点から、２官能のメタアクリレート又はアクリレートを用いることが好ましい。
　具体的な化合物としては、トリエチレングリコールジアクリレート、トリエチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、テトラエチレングリコールジアクリレート、ＰＥＧ（ポリエチレングリコール）２００ジアクリレート、ＰＥＧ２００ジメタクリレート、ＰＥＧ６００ジアクリレート、ＰＥＧ６００ジメタクリレート、ポリテトラエチレングリコールジアクリレート、ポリテトラエチレングリコールジメタクリレート、ネオペンチルグリコールジアクリレート、ネオペンチルグリコールジメタクリレート、３－メチル-１，５-ペンタンジオールジアクリレート、１，６－ヘキサンジオールジアクリレート、１，６ヘキサンジオールジメタクリレート、ジメチロール－トリシクロデカンジアクリレート、ジメチロール－トリシクロデカンジメタクリレート、ビスフェノールＡのＥＯ（エチレンオキシド）付加物ジアクリレート、ビスフェノールＡのＥＯ付加物ジメタクリレート、ビスフェノールＡのＰＯ（プロピレンオキシド）付加物ジアクリレート、ビスフェノールＡのＰＯ付加物ジメタクリレート、２－ヒドロキシー３－アクリロイロキシプロピルメタクリレート、イソシアヌル酸ＥＯ変性ジアクリレート、イソシアヌル酸変性ジメタクリレート、その他ウレタン結合を有する２官能アクリレート、ウレタン結合を有する２官能メタクリレートを使用することができる。これらは必要に応じ、２種以上を混合し使用することができる。
　なお、例えばＰＥＧ２００ジアクリレートとは、ポリエチレングリコールジアクリレートであって、ポリエチレングリコール鎖の式量が２００程度のものをいう。
　本発明の樹脂組成物は、パターン（硬化物）の弾性率制御に伴う反り抑制の観点から、ラジカル架橋剤として、単官能ラジカル架橋剤を好ましく用いることができる。単官能ラジカル架橋剤としては、ｎ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、カルビトール（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、Ｎ－メチロール（メタ）アクリルアミド、グリシジル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート等の（メタ）アクリル酸誘導体、Ｎ－ビニルピロリドン、Ｎ－ビニルカプロラクタム等のＮ－ビニル化合物類、アリルグリシジルエーテル等が好ましく用いられる。単官能ラジカル架橋剤としては、露光前の揮発を抑制するため、常圧下で１００℃以上の沸点を持つ化合物も好ましい。
　その他、２官能以上のラジカル架橋剤としては、ジアリルフタレート、トリアリルトリメリテート等のアリル化合物類が挙げられる。 From the viewpoint of pattern resolution and film stretchability, the resin composition preferably uses a bifunctional methacrylate or acrylate.
Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, and PEG600 diacrylate. methacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO ( Propylene oxide) adduct diacrylate, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates having urethane bonds, Bifunctional methacrylates with urethane bonds can be used. These can be used in combination of two or more as needed.
For example, PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula weight of about 200.
In the resin composition of the present invention, a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent from the viewpoint of suppressing warpage associated with the elastic modulus control of the pattern (cured product). Monofunctional radical cross-linking agents include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, ) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. (meth) Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl glycidyl ether are preferably used. As the monofunctional radical cross-linking agent, a compound having a boiling point of 100° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
Other di- or higher functional radical cross-linking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.
　ラジカル架橋剤を含有する場合、その含有量は、本発明の樹脂組成物の全固形分に対して、０質量％超６０質量％以下であることが好ましい。下限は５質量％以上がより好ましい。上限は、５０質量％以下であることがより好ましく、３０質量％以下であることが更に好ましい。 When a radical cross-linking agent is contained, its content is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the resin composition of the present invention. More preferably, the lower limit is 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.
　ラジカル架橋剤は１種を単独で用いてもよいが、２種以上を混合して用いてもよい。２種以上を併用する場合にはその合計量が上記の範囲となることが好ましい。 A single radical cross-linking agent may be used alone, or two or more may be used in combination. When two or more are used in combination, the total amount is preferably within the above range.
〔他の架橋剤〕
　本発明の樹脂組成物は、上述したラジカル架橋剤とは異なる、他の架橋剤を含むことも好ましい。
　本発明において、他の架橋剤とは、上述したラジカル架橋剤以外の架橋剤をいい、上述の光酸発生剤、又は、光塩基発生剤の感光により、組成物中の他の化合物又はその反応生成物との間で共有結合を形成する反応が促進される基を分子内に複数個有する化合物であることが好ましく、組成物中の他の化合物又はその反応生成物との間で共有結合を形成する反応が酸又は塩基の作用によって促進される基を分子内に複数個有する化合物が好ましい。
　上記酸又は塩基は、露光工程において、光酸発生剤又は光塩基発生剤から発生する酸又は塩基であることが好ましい。
　他の架橋剤としては、アシルオキシメチル基、メチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも１種の基を有する化合物が好ましく、アシルオキシメチル基、メチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも１種の基が窒素原子に直接結合した構造を有する化合物がより好ましい。
　他の架橋剤としては、例えば、メラミン、グリコールウリル、尿素、アルキレン尿素、ベンゾグアナミンなどのアミノ基含有化合物にホルムアルデヒド又はホルムアルデヒドとアルコールを反応させ、上記アミノ基の水素原子をアシルオキシメチル基、メチロール基又はアルコキシメチル基で置換した構造を有する化合物が挙げられる。これらの化合物の製造方法は特に限定されず、上記方法により製造された化合物と同様の構造を有する化合物であればよい。また、これらの化合物のメチロール基同士が自己縮合してなるオリゴマーであってもよい。
　上記のアミノ基含有化合物として、メラミンを用いた架橋剤をメラミン系架橋剤、グリコールウリル、尿素又はアルキレン尿素を用いた架橋剤を尿素系架橋剤、アルキレン尿素を用いた架橋剤をアルキレン尿素系架橋剤、ベンゾグアナミンを用いた架橋剤をベンゾグアナミン系架橋剤という。
　これらの中でも、本発明の樹脂組成物は、尿素系架橋剤及びメラミン系架橋剤よりなる群から選ばれた少なくとも１種の化合物を含むことが好ましく、後述するグリコールウリル系架橋剤及びメラミン系架橋剤よりなる群から選ばれた少なくとも１種の化合物を含むことがより好ましい。 [Other cross-linking agents]
It is also preferable that the resin composition of the present invention contains another cross-linking agent different from the radical cross-linking agent described above.
In the present invention, the other cross-linking agent refers to a cross-linking agent other than the above-described radical cross-linking agent, and the above-described photoacid generator or photobase generator reacts with other compounds in the composition or reacts with them. It is preferable that the compound has a plurality of groups in the molecule that promote the reaction forming covalent bonds with the product, and covalent bonds are formed with other compounds in the composition or reaction products thereof. Compounds having a plurality of groups in the molecule, the reaction of which is promoted by the action of an acid or base, are preferred.
The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
As other cross-linking agents, compounds having at least one group selected from the group consisting of acyloxymethyl groups, methylol groups and alkoxymethyl groups are preferred, and the compounds are preferably selected from the group consisting of acyloxymethyl groups, methylol groups and alkoxymethyl groups. More preferred is a compound having a structure in which at least one group is directly bonded to a nitrogen atom.
Other cross-linking agents include, for example, an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, and benzoguanamine, which is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is converted to an acyloxymethyl group, methylol group, or A compound having a structure substituted with an alkoxymethyl group can be mentioned. The method for producing these compounds is not particularly limited as long as they have the same structure as the compounds produced by the above methods. Oligomers formed by self-condensation of methylol groups of these compounds may also be used.
As the amino group-containing compound, a melamine-based crosslinking agent is a melamine-based crosslinking agent, a glycoluril, urea or alkyleneurea-based crosslinking agent is a urea-based crosslinking agent, and an alkyleneurea-based crosslinking agent is an alkyleneurea-based crosslinking agent. A cross-linking agent using benzoguanamine is called a benzoguanamine-based cross-linking agent.
Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based cross-linking agents and melamine-based cross-linking agents. More preferably, it contains at least one compound selected from the group consisting of agents.
　本発明におけるアルコキシメチル基及びアシルオキシメチル基の少なくとも１つを含有する化合物としては、アルコキシメチル基又はアシルオキシメチル基が、直接芳香族基や下記ウレア構造の窒素原子上に、又は、トリアジン上に置換した化合物を構造例として挙げることができる。
　上記化合物が有するアルコキシメチル基又はアシルオキシメチル基は、炭素数２～５が好ましく、炭素数２又は３が好ましく、炭素数２がより好ましい。
　上記化合物が有するアルコキシメチル基及びアシルオキシメチル基の総数は１～１０が好ましく、より好ましくは２～８、特に好ましくは３～６である。
　上記化合物の分子量は好ましくは１５００以下であり、１８０～１２００が好ましい。 As a compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention, an alkoxymethyl group or an acyloxymethyl group is directly substituted on the nitrogen atom of an aromatic group or the following urea structure, or on a triazine. can be given as structural examples.
The alkoxymethyl group or acyloxymethyl group of the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.
The total number of alkoxymethyl groups and acyloxymethyl groups in the above compound is preferably 1-10, more preferably 2-8, and particularly preferably 3-6.
The molecular weight of the compound is preferably 1500 or less, preferably 180-1200.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　Ｒ１００は、アルキル基又はアシル基を表す。
　Ｒ１０１及びＲ１０２は、それぞれ独立に、一価の有機基を表し、互いに結合して環を形成してもよい。 R 100 represents an alkyl group or an acyl group.
R 101 and R 102 each independently represent a monovalent organic group and may combine with each other to form a ring.
　アルコキシメチル基又はアシルオキシメチル基が直接芳香族基に置換した化合物としては、例えば下記一般式の様な化合物を挙げることができる。 Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted by an aromatic group include compounds represented by the following general formula.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　式中、Ｘは単結合又は２価の有機基を示し、個々のＲ１０４はそれぞれ独立にアルキル基又はアシル基を示し、Ｒ１０３は、水素原子、アルキル基、アルケニル基、アリール基、アラルキル基、又は、酸の作用により分解し、アルカリ可溶性基を生じる基（例えば、酸の作用により脱離する基、－Ｃ（Ｒ４）２ＣＯＯＲ５で表される基（Ｒ４はそれぞれ独立に、水素原子又は炭素数１～４のアルキル基を表し、Ｒ５は酸の作用により脱離する基を表す。））を示す。
　Ｒ１０５は各々独立にアルキル基又はアルケニル基を示し、ａ、ｂ及びｃは各々独立に１～３であり、ｄは０～４であり、ｅは０～３であり、ｆは０～３であり、ａ＋ｄは５以下であり、ｂ＋ｅは４以下であり、ｃ＋ｆは４以下である。
　酸の作用により分解し、アルカリ可溶性基を生じる基、酸の作用により脱離する基、－Ｃ（Ｒ４）２ＣＯＯＲ５で表される基におけるＲ５については、例えば、－Ｃ（Ｒ３６）（Ｒ３７）（Ｒ３８）、－Ｃ（Ｒ３６）（Ｒ３７）（ＯＲ３９）、－Ｃ（Ｒ０１）（Ｒ０２）（ＯＲ３９）等を挙げることができる。
　式中、Ｒ３６～Ｒ３９は、各々独立に、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。Ｒ３６とＲ３７とは、互いに結合して環を形成してもよい。
　上記アルキル基としては、炭素数１～１０のアルキル基が好ましく、炭素数１～５のアルキル基がより好ましい。
　上記アルキル基は、直鎖状、分岐鎖状のいずれであってもよい。
　上記シクロアルキル基としては、炭素数３～１２のシクロアルキル基が好ましく、炭素数３～８のシクロアルキル基がより好ましい。
　上記シクロアルキル基は単環構造であってもよいし、縮合環等の多環構造であってもよい。
　上記アリール基は炭素数６～３０の芳香族炭化水素基であることが好ましく、フェニル基であることがより好ましい。
　上記アラルキル基としては、炭素数７～２０のアラルキル基が好ましく、炭素数７～１６のアラルキル基がより好ましい。
　上記アラルキル基はアルキル基により置換されたアリール基を意図しており、これらのアルキル基及びアリール基の好ましい態様は、上述のアルキル基及びアリール基の好ましい態様と同様である。
　上記アルケニル基は炭素数３～２０のアルケニル基が好ましく、炭素数３～１６のアルケニル基がより好ましい。
　また、これらの基は本発明の効果が得られる範囲内で、公知の置換基を更に有していてもよい。 In the formula, X represents a single bond or a divalent organic group, each R 104 independently represents an alkyl group or an acyl group, R 103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group , or a group that decomposes under the action of an acid to produce an alkali-soluble group (e.g., a group that leaves under the action of an acid, a group represented by —C(R 4 ) 2 COOR 5 (R 4 is independently It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 represents a group that leaves under the action of an acid.)).
R 105 each independently represents an alkyl group or alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3 , a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less.
For R 5 in the group represented by —C(R 4 ) 2 COOR 5 , a group that is decomposed by the action of an acid to produce an alkali-soluble group, a group that is eliminated by the action of an acid, and —C(R 36 )(R 37 )(R 38 ), —C(R 36 )(R 37 )(OR 39 ), —C(R 01 )(R 02 )(OR 39 ), and the like.
In the formula, R 36 to R 39 each independently represent an alkyl group, cycloalkyl group, aryl group, aralkyl group or alkenyl group. R 36 and R 37 may combine with each other to form a ring.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
The alkyl group may be linear or branched.
As the cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable.
The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring.
The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a phenyl group.
As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable.
The aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as the preferred embodiments of the alkyl and aryl groups described above.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, more preferably an alkenyl group having 3 to 16 carbon atoms.
Moreover, these groups may further have a known substituent within the range in which the effects of the present invention can be obtained.
　Ｒ０１及びＲ０２は、各々独立に、水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。 R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
　酸の作用により分解し、アルカリ可溶性基を生じる基、または酸の作用により脱離する基としては好ましくは、第３級アルキルエステル基、アセタール基、クミルエステル基、エノールエステル基等である。更に好ましくは、第３級アルキルエステル基、アセタール基である。 The group that is decomposed by the action of an acid to form an alkali-soluble group or the group that is eliminated by the action of an acid is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, or the like. More preferred are tertiary alkyl ester groups and acetal groups.
　アルコキシメチル基を有する化合物としては具体的に以下の構造を挙げることができる。アシルオキシメチル基を有する化合物は下記化合物のアルコキシメチル基をアシルオキシメチル基に変更した化合物を挙げることができる。アルコキシメチル基又はアシルオキシメチルを分子内に有する化合物としては以下の様な化合物を挙げることができるが、これらに限定されるものではない。 Specific examples of compounds having an alkoxymethyl group include the following structures. Examples of the compound having an acyloxymethyl group include compounds obtained by changing the alkoxymethyl group of the following compounds to an acyloxymethyl group. Compounds having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　アルコキシメチル基及びアシルオキシメチル基の少なくとも１つを含有する化合物は、市販のものを用いても、公知の方法により合成したものを用いてもよい。
　耐熱性の観点で、アルコキシメチル基又はアシルオキシメチル基が、直接芳香環やトリアジン環上に置換した化合物が好ましい。 As the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available one or a compound synthesized by a known method may be used.
From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.
　メラミン系架橋剤の具体例としては、ヘキサメトキシメチルメラミン、ヘキサエトキシメチルメラミン、ヘキサプロポキシメチルメラミン、ヘキサブトキシブチルメラミンなどが挙げられる。 Specific examples of melamine-based cross-linking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.
　尿素系架橋剤の具体例としては、例えば、モノヒドロキシメチル化グリコールウリル、ジヒドロキシメチル化グリコールウリル、トリヒドロキシメチル化グリコールウリル、テトラヒドロキシメチル化グリコールウリル、モノメトキシメチル化グリコールウリル、ジメトキシメチル化グリコールウリル、トリメトキシメチル化グリコールウリル、テトラメトキシメチル化グリコールウリル、モノエトキシメチル化グリコールウリル、ジエトキシメチル化グリコールウリル、トリエトキシメチル化グリコールウリル、テトラエトキシメチル化グリコールウリル、モノプロポキシメチル化グリコールウリル、ジプロポキシメチル化グリコールウリル、トリプロポキシメチル化グリコールウリル、テトラプロポキシメチル化グリコールウリル、モノブトキシメチル化グリコールウリル、ジブトキシメチル化グリコールウリル、トリブトキシメチル化グリコールウリル、又は、テトラブトキシメチル化グリコールウリルなどのグリコールウリル系架橋剤；
　ビスメトキシメチル尿素、ビスエトキシメチル尿素、ビスプロポキシメチル尿素、ビスブトキシメチル尿素等の尿素系架橋剤、
　モノヒドロキシメチル化エチレン尿素又はジヒドロキシメチル化エチレン尿素、モノメトキシメチル化エチレン尿素、ジメトキシメチル化エチレン尿素、モノエトキシメチル化エチレン尿素、ジエトキシメチル化エチレン尿素、モノプロポキシメチル化エチレン尿素、ジプロポキシメチル化エチレン尿素、モノブトキシメチル化エチレン尿素、又は、ジブトキシメチル化エチレン尿素などのエチレン尿素系架橋剤、
　モノヒドロキシメチル化プロピレン尿素、ジヒドロキシメチル化プロピレン尿素、モノメトキシメチル化プロピレン尿素、ジメトキシメチル化プロピレン尿素、モノエトキシメチル化プロピレン尿素、ジエトキシメチル化プロピレン尿素、モノプロポキシメチル化プロピレン尿素、ジプロポキシメチル化プロピレン尿素、モノブトキシメチル化プロピレン尿素、又は、ジブトキシメチル化プロピレン尿素などのプロピレン尿素系架橋剤、
　１，３－ジ（メトキシメチル）４，５－ジヒドロキシ－２－イミダゾリジノン、１，３－ジ（メトキシメチル）－４，５－ジメトキシ－２－イミダゾリジノンなどが挙げられる。 Specific examples of urea-based cross-linking agents include monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, and dimethoxymethylated glycol. Uril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril , dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, or tetrabutoxymethylated glycoluril glycoluril-based crosslinkers such as uril;
urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea;
monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethyl ethylene urea-based cross-linking agents such as ethylene urea, monobutoxymethyl ethylene urea, or dibutoxymethyl ethylene urea;
Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethyl propylene urea-based cross-linking agents such as propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea;
1,3-di(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone and the like.
　ベンゾグアナミン系架橋剤の具体例としては、例えばモノヒドロキシメチル化ベンゾグアナミン、ジヒドロキシメチル化ベンゾグアナミン、トリヒドロキシメチル化ベンゾグアナミン、テトラヒドロキシメチル化ベンゾグアナミン、モノメトキシメチル化ベンゾグアナミン、ジメトキシメチル化ベンゾグアナミン、トリメトキシメチル化ベンゾグアナミン、テトラメトキシメチル化ベンゾグアナミン、モノエトキシメチル化ベンゾグアナミン、ジエトキシメチル化ベンゾグアナミン、トリエトキシメチル化ベンゾグアナミン、テトラエトキシメチル化ベンゾグアナミン、モノプロポキシメチル化ベンゾグアナミン、ジプロポキシメチル化ベンゾグアナミン、トリプロポキシメチル化ベンゾグアナミン、テトラプロポキシメチル化ベンゾグアナミン、モノブトキシメチル化ベンゾグアナミン、ジブトキシメチル化ベンゾグアナミン、トリブトキシメチル化ベンゾグアナミン、テトラブトキシメチル化ベンゾグアナミンなどが挙げられる。 Specific examples of benzoguanamine-based cross-linking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine. , tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetra propoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, and the like.
　その他、メチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも１種の基を有する化合物としては、芳香環（好ましくはベンゼン環）にメチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも１種の基が直接結合した化合物も好適に用いられる。
　このような化合物の具体例としては、ベンゼンジメタノール、ビス（ヒドロキシメチル）クレゾール、ビス（ヒドロキシメチル）ジメトキシベンゼン、ビス（ヒドロキシメチル）ジフェニルエーテル、ビス（ヒドロキシメチル）ベンゾフェノン、ヒドロキシメチル安息香酸ヒドロキシメチルフェニル、ビス（ヒドロキシメチル）ビフェニル、ジメチルビス（ヒドロキシメチル）ビフェニル、ビス（メトキシメチル）ベンゼン、ビス（メトキシメチル）クレゾール、ビス（メトキシメチル）ジメトキシベンゼン、ビス（メトキシメチル）ジフェニルエーテル、ビス（メトキシメチル）ベンゾフェノン、メトキシメチル安息香酸メトキシメチルフェニル、ビス（メトキシメチル）ビフェニル、ジメチルビス（メトキシメチル）ビフェニル、４，４’，４’’－エチリデントリス［２，６－ビス（メトキシメチル）フェノール］、５，５’－［２，２，２‐トリフルオロ‐１‐（トリフルオロメチル）エチリデン］ビス［２‐ヒドロキシ‐１，３‐ベンゼンジメタノール］、３，３’，５，５’－テトラキス（メトキシメチル）－１，１’－ビフェニル－４，４’－ジオール等が挙げられる。 In addition, the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group includes at least one group selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring). Compounds to which a seed group is directly attached are also preferably used.
Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate. , bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl) Benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4′,4″-ethylidene tris[2,6-bis(methoxymethyl)phenol], 5 ,5′-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3′,5,5′-tetrakis ( methoxymethyl)-1,1'-biphenyl-4,4'-diol and the like.
　他の架橋剤としては市販品を用いてもよく、好適な市販品としては、４６ＤＭＯＣ、４６ＤＭＯＥＰ（以上、旭有機材工業社製）、ＤＭＬ－ＰＣ、ＤＭＬ－ＰＥＰ、ＤＭＬ－ＯＣ、ＤＭＬ－ＯＥＰ、ＤＭＬ－３４Ｘ、ＤＭＬ－ＰＴＢＰ、ＤＭＬ－ＰＣＨＰ、ＤＭＬ－ＯＣＨＰ、ＤＭＬ－ＰＦＰ、ＤＭＬ－ＰＳＢＰ、ＤＭＬ－ＰＯＰ、ＤＭＬ－ＭＢＯＣ、ＤＭＬ－ＭＢＰＣ、ＤＭＬ－ＭＴｒｉｓＰＣ、ＤＭＬ－ＢｉｓＯＣ－Ｚ、ＤＭＬ－ＢｉｓＯＣＨＰ－Ｚ、ＤＭＬ－ＢＰＣ、ＤＭＬＢｉｓＯＣ－Ｐ、ＤＭＯＭ－ＰＣ、ＤＭＯＭ－ＰＴＢＰ、ＤＭＯＭ－ＭＢＰＣ、ＴｒｉＭＬ－Ｐ、ＴｒｉＭＬ－３５ＸＬ、ＴＭＬ－ＨＱ、ＴＭＬ－ＢＰ、ＴＭＬ－ｐｐ－ＢＰＦ、ＴＭＬ－ＢＰＥ、ＴＭＬ－ＢＰＡ、ＴＭＬ－ＢＰＡＦ、ＴＭＬ－ＢＰＡＰ、ＴＭＯＭ－ＢＰ、ＴＭＯＭ－ＢＰＥ、ＴＭＯＭ－ＢＰＡ、ＴＭＯＭ－ＢＰＡＦ、ＴＭＯＭ－ＢＰＡＰ、ＨＭＬ－ＴＰＰＨＢＡ、ＨＭＬ－ＴＰＨＡＰ、ＨＭＯＭ－ＴＰＰＨＢＡ、ＨＭＯＭ－ＴＰＨＡＰ（以上、本州化学工業社製）、ニカラック（登録商標、以下同様）ＭＸ－２９０、ニカラックＭＸ－２８０、ニカラックＭＸ－２７０、ニカラックＭＸ－２７９、ニカラックＭＷ－１００ＬＭ、ニカラックＭＸ－７５０ＬＭ（以上、三和ケミカル社製）などが挙げられる。 Commercial products may be used as other cross-linking agents, and suitable commercial products include 46DMOC, 46DMOEP (manufactured by Asahi Organic Chemicals Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, and DML-OEP. , DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP -Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML -BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (Honshu Chemical Industry Co., Ltd.), Nikalac (registered trademark, hereinafter the same) MX-290, Nikalac MX-280, Nikalac MX-270, Nikalac MX-279, Nikalac MW-100LM, Nikalac MX-750LM (manufactured by Sanwa Chemical Co., Ltd.) ) and the like.
　また、本発明の樹脂組成物は、他の架橋剤として、エポキシ化合物、オキセタン化合物、及び、ベンゾオキサジン化合物よりなる群から選ばれた少なくとも１種の化合物を含むことも好ましい。 In addition, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds as another cross-linking agent.
－エポキシ化合物（エポキシ基を有する化合物）－
　エポキシ化合物としては、一分子中にエポキシ基を２以上有する化合物であることが好ましい。エポキシ基は、２００℃以下で架橋反応し、かつ、架橋に由来する脱水反応が起こらないため膜収縮が起きにくい。このため、エポキシ化合物を含有することは、本発明の樹脂組成物の低温硬化及び反りの抑制に効果的である。 - Epoxy compound (compound having an epoxy group) -
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a cross-linking reaction at 200° C. or less and does not undergo a dehydration reaction resulting from the cross-linking, so film shrinkage does not easily occur. Therefore, containing an epoxy compound is effective for low-temperature curing and suppression of warpage of the resin composition of the present invention.
　エポキシ化合物は、ポリエチレンオキサイド基を含有することが好ましい。これにより、より弾性率が低下し、また反りを抑制することができる。ポリエチレンオキサイド基は、エチレンオキサイドの繰返し単位数が２以上のものを意味し、繰返し単位数が２～１５であることが好ましい。 　The epoxy compound preferably contains a polyethylene oxide group. As a result, the elastic modulus is further lowered, and warping can be suppressed. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2-15.
　エポキシ化合物の例としては、ビスフェノールＡ型エポキシ樹脂；ビスフェノールＦ型エポキシ樹脂；プロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、エチレングリコールジグリシジルエーテル、ブチレングリコールジグリシジルエーテル、ヘキサメチレングリコールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル等のアルキレングリコール型エポキシ樹脂又は多価アルコール炭化水素型エポキシ樹脂；ポリプロピレングリコールジグリシジルエーテル等のポリアルキレングリコール型エポキシ樹脂；ポリメチル（グリシジロキシプロピル）シロキサン等のエポキシ基含有シリコーンなどを挙げることができるが、これらに限定されない。具体的には、エピクロン（登録商標）８５０－Ｓ、エピクロン（登録商標）ＨＰ－４０３２、エピクロン（登録商標）ＨＰ－７２００、エピクロン（登録商標）ＨＰ－８２０、エピクロン（登録商標）ＨＰ－４７００、エピクロン（登録商標）ＨＰ－４７７０、エピクロン（登録商標）ＥＸＡ－８３０ＬＶＰ、エピクロン（登録商標）ＥＸＡ－８１８３、エピクロン（登録商標）ＥＸＡ－８１６９、エピクロン（登録商標）Ｎ－６６０、エピクロン（登録商標）Ｎ－６６５－ＥＸＰ－Ｓ、エピクロン（登録商標）Ｎ－７４０（以上商品名、ＤＩＣ（株）製）、リカレジン（登録商標）ＢＥＯ－２０Ｅ、リカレジン（登録商標）ＢＥＯ－６０Ｅ、リカレジン（登録商標）ＨＢＥ－１００、リカレジン（登録商標）ＤＭＥ－１００、リカレジン（登録商標）Ｌ－２００（商品名、新日本理化（株）製）、ＥＰ－４００３Ｓ、ＥＰ－４０００Ｓ、ＥＰ－４０８８Ｓ、ＥＰ－３９５０Ｓ（以上商品名、（株）ＡＤＥＫＡ製）、セロキサイド（登録商標）２０２１Ｐ、セロキサイド（登録商標）２０８１、セロキサイド（登録商標）２０００、ＥＨＰＥ３１５０、エポリード（登録商標）ＧＴ４０１、エポリード（登録商標）ＰＢ４７００、エポリード（登録商標）ＰＢ３６００（以上商品名、（株）ダイセル製）、ＮＣ－３０００、ＮＣ－３０００－Ｌ、ＮＣ－３０００－Ｈ、ＮＣ－３０００－ＦＨ－７５Ｍ、ＮＣ－３１００、ＣＥＲ－３０００－Ｌ、ＮＣ－２０００－Ｌ、ＸＤ－１０００、ＮＣ－７０００Ｌ、ＮＣ－７３００Ｌ、ＥＰＰＮ－５０１Ｈ、ＥＰＰＮ－５０１ＨＹ、ＥＰＰＮ－５０２Ｈ、ＥＯＣＮ－１０２０、ＥＯＣＮ－１０２Ｓ、ＥＯＣＮ－１０３Ｓ、ＥＯＣＮ－１０４Ｓ、ＣＥＲ－１０２０、ＥＰＰＮ－２０１、ＢＲＥＮ－Ｓ、ＢＲＥＮ－１０Ｓ（以上商品名、日本化薬（株）製）などが挙げられる。また以下の化合物も好適に用いられる。  Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether. , alkylene glycol type epoxy resins such as trimethylolpropane triglycidyl ether or polyhydric alcohol hydrocarbon type epoxy resins; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; epoxy groups such as polymethyl (glycidyloxypropyl) siloxane Examples include, but are not limited to, containing silicones and the like. Specifically, Epiclon (registered trademark) 850-S, Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-830LVP, Epiclon (registered trademark) EXA-8183, Epiclon (registered trademark) EXA-8169, Epiclon (registered trademark) N-660, Epiclon (registered trademark) N-665-EXP-S, Epiclon (registered trademark) N-740 (trade name, manufactured by DIC Corporation), Ricaresin (registered trademark) BEO-20E, Ricaresin (registered trademark) BEO-60E, Ricaresin (registered trademark) ) HBE-100, Ricaresin (registered trademark) DME-100, Ricaresin (registered trademark) L-200 (trade name, manufactured by Shin Nippon Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (Trade names above, manufactured by ADEKA Co., Ltd.), Celoxide (registered trademark) 2021P, Celoxide (registered trademark) 2081, Celoxide (registered trademark) 2000, EHPE3150, Epolead (registered trademark) GT401, Epolead (registered trademark) PB4700, Epolead (registered trademark) PB3600 (trade name, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L , NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020 , EPPN-201, BREN-S, and BREN-10S (these are trade names, manufactured by Nippon Kayaku Co., Ltd.). The following compounds are also preferably used. 
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　式中ｎは１～５の整数、ｍは１～２０の整数である。 where n is an integer of 1-5 and m is an integer of 1-20.
　上記構造の中でも、耐熱性と伸度向上を両立する点から、ｎは１～２、ｍは３～７であることが好ましい。 Among the above structures, it is preferable that n is 1 to 2 and m is 3 to 7 from the viewpoint of achieving both heat resistance and elongation improvement.
－オキセタン化合物（オキセタニル基を有する化合物）－
　オキセタン化合物としては、一分子中にオキセタン環を２つ以上有する化合物、３－エチル－３－ヒドロキシメチルオキセタン、１，４－ビス｛［（３－エチル－３－オキセタニル）メトキシ］メチル｝ベンゼン、３－エチル－３－（２－エチルヘキシルメチル）オキセタン、１，４－ベンゼンジカルボン酸－ビス［（３－エチル－３－オキセタニル）メチル］エステル等を挙げることができる。具体的な例としては、東亞合成（株）製のアロンオキセタンシリーズ（例えば、ＯＸＴ－１２１、ＯＸＴ－２２１）が好適に使用することができ、これらは単独で、又は２種以上混合してもよい。 -Oxetane compound (compound having an oxetanyl group)-
Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester and the like can be mentioned. As a specific example, Aron oxetane series manufactured by Toagosei Co., Ltd. (eg, OXT-121, OXT-221) can be suitably used, and these can be used alone or in combination of two or more. good.
－ベンゾオキサジン化合物（ベンゾオキサゾリル基を有する化合物）－
　ベンゾオキサジン化合物は、開環付加反応に由来する架橋反応のため、硬化時に脱ガスが発生せず、更に熱収縮を小さくして反りの発生が抑えられることから好ましい。 -Benzoxazine compound (compound having a benzoxazolyl group)-
A benzoxazine compound is preferable because it is a cross-linking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and thermal shrinkage is reduced to suppress the occurrence of warping.
　ベンゾオキサジン化合物の好ましい例としては、Ｐ－ｄ型ベンゾオキサジン、Ｆ－ａ型ベンゾオキサジン（以上、商品名、四国化成工業社製）、ポリヒドロキシスチレン樹脂のベンゾオキサジン付加物、フェノールノボラック型ジヒドロベンゾオキサジン化合物が挙げられる。これらは単独で用いるか、又は２種以上混合してもよい。 Preferable examples of benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (these are trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, phenol novolac-type dihydrobenzoxazines, oxazine compounds. These may be used alone or in combination of two or more.
　他の架橋剤の含有量は、本発明の樹脂組成物の全固形分に対し０．１～３０質量％であることが好ましく、０．１～２０質量％であることがより好ましく、０．５～１５質量％であることが更に好ましく、１．０～１０質量％であることが特に好ましい。他の架橋剤は１種のみ含有していてもよいし、２種以上含有していてもよい。他の架橋剤を２種以上含有する場合は、その合計が上記範囲であることが好ましい。 The content of the other cross-linking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. It is more preferably 5 to 15% by mass, particularly preferably 1.0 to 10% by mass. Other cross-linking agents may be contained alone, or may be contained in two or more. When two or more other cross-linking agents are contained, the total is preferably within the above range.
〔重合開始剤〕
　本発明の樹脂組成物は、光及び／又は熱により重合を開始させることができる重合開始剤を含むことが好ましい。特に光重合開始剤を含むことが好ましい。
　光重合開始剤は、光ラジカル重合開始剤であることが好ましい。光ラジカル重合開始剤としては、特に制限はなく、公知の光ラジカル重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光線に対して感光性を有する光ラジカル重合開始剤が好ましい。また、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよい。 [Polymerization initiator]
The resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat. In particular, it preferably contains a photopolymerization initiator.
The photopolymerization initiator is preferably a photoradical polymerization initiator. The radical photopolymerization initiator is not particularly limited and can be appropriately selected from known radical photopolymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. It may also be an activator that produces an active radical by producing some action with a photoexcited sensitizer.
　光ラジカル重合開始剤は、波長約２４０～８００ｎｍ（好ましくは３３０～５００ｎｍ）の範囲内で少なくとも約５０Ｌ・ｍｏｌ－１・ｃｍ－１のモル吸光係数を有する化合物を、少なくとも１種含有していることが好ましい。化合物のモル吸光係数は、公知の方法を用いて測定することができる。例えば、紫外可視分光光度計（Ｖａｒｉａｎ社製Ｃａｒｙ－５　ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）にて、酢酸エチル溶剤を用い、０．０１ｇ／Ｌの濃度で測定することが好ましい。 The radical photopolymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L·mol −1 ·cm −1 within the wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). is preferred. The molar extinction coefficient of a compound can be measured using known methods. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.
　光ラジカル重合開始剤としては、公知の化合物を任意に使用できる。例えば、ハロゲン化炭化水素誘導体（例えば、トリアジン骨格を有する化合物、オキサジアゾール骨格を有する化合物、トリハロメチル基を有する化合物など）、アシルホスフィンオキサイド等のアシルホスフィン化合物、ヘキサアリールビイミダゾール、オキシム誘導体等のオキシム化合物、有機過酸化物、チオ化合物、ケトン化合物、芳香族オニウム塩、ケトオキシムエーテル、アミノアセトフェノンなどのα－アミノケトン化合物、ヒドロキシアセトフェノンなどのα－ヒドロキシケトン化合物、アゾ系化合物、アジド化合物、メタロセン化合物、有機ホウ素化合物、鉄アレーン錯体などが挙げられる。これらの詳細については、特開２０１６－０２７３５７号公報の段落０１６５～０１８２、国際公開第２０１５／１９９２１９号の段落０１３８～０１５１の記載を参酌でき、この内容は本明細書に組み込まれる。また、特開２０１４－１３０１７３号公報の段落００６５～０１１１、特許第６３０１４８９号公報に記載された化合物、ＭＡＴＥＲＩＡＬ　ＳＴＡＧＥ　３７～６０ｐ，ｖｏｌ．１９，Ｎｏ．３，２０１９に記載されたパーオキサイド系光重合開始剤、国際公開第２０１８／２２１１７７号に記載の光重合開始剤、国際公開第２０１８／１１０１７９号に記載の光重合開始剤、特開２０１９－０４３８６４号公報に記載の光重合開始剤、特開２０１９－０４４０３０号公報に記載の光重合開始剤、特開２０１９－１６７３１３号公報に記載の過酸化物系開始剤が挙げられ、これらの内容も本明細書に組み込まれる。 Any known compound can be used as the photoradical polymerization initiator. For example, halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc. oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, and the like. For details of these, paragraphs 0165 to 0182 of JP-A-2016-027357 and paragraphs 0138 to 0151 of WO 2015/199219 can be referred to, the contents of which are incorporated herein. In addition, paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37-60p, vol. 19, No. 3, the peroxide photopolymerization initiator described in 2019, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, JP 2019-043864 The photopolymerization initiator described in JP-A-2019-044030, the photopolymerization initiator described in JP-A-2019-167313, and the peroxide-based initiator described in JP-A-2019-167313. incorporated into the specification.
　ケトン化合物としては、例えば、特開２０１５－０８７６１１号公報の段落００８７に記載の化合物が例示され、この内容は本明細書に組み込まれる。市販品では、カヤキュア－ＤＥＴＸ－Ｓ（日本化薬（株）製）も好適に用いられる。 Examples of ketone compounds include compounds described in paragraph 0087 of JP-A-2015-087611, the content of which is incorporated herein. As a commercial product, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.
　本発明の一実施態様において、光ラジカル重合開始剤としては、ヒドロキシアセトフェノン化合物、アミノアセトフェノン化合物、及び、アシルホスフィン化合物を好適に用いることができる。より具体的には、例えば、特開平１０－２９１９６９号公報に記載のアミノアセトフェノン系開始剤、特許第４２２５８９８号に記載のアシルホスフィンオキシド系開始剤を用いることができ、この内容は本明細書に組み込まれる。 In one embodiment of the present invention, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be suitably used as the radical photopolymerization initiator. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used. incorporated.
　α－ヒドロキシケトン系開始剤としては、Ｏｍｎｉｒａｄ　１８４、Ｏｍｎｉｒａｄ　１１７３、Ｏｍｎｉｒａｄ　２９５９、Ｏｍｎｉｒａｄ　１２７（以上、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、ＩＲＧＡＣＵＲＥ　１８４（ＩＲＧＡＣＵＲＥは登録商標）、ＤＡＲＯＣＵＲ　１１７３、ＩＲＧＡＣＵＲＥ　５００、ＩＲＧＡＣＵＲＥ－２９５９、ＩＲＧＡＣＵＲＥ　１２７（商品名：いずれもＢＡＳＦ社製）を用いることができる。 α-hydroxyketone initiators include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE -2959 and IRGACURE 127 (trade names: both manufactured by BASF) can be used.
　α－アミノケトン系開始剤としては、Ｏｍｎｉｒａｄ　９０７、Ｏｍｎｉｒａｄ　３６９、Ｏｍｎｉｒａｄ　３６９Ｅ、Ｏｍｎｉｒａｄ　３７９ＥＧ（以上、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、ＩＲＧＡＣＵＲＥ　９０７、ＩＲＧＡＣＵＲＥ　３６９、及び、ＩＲＧＡＣＵＲＥ　３７９（商品名：いずれもＢＡＳＦ社製）を用いることができる。 Examples of α-aminoketone initiators include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all BASF company) can be used.
　アミノアセトフェノン系開始剤として、３６５ｎｍ又は４０５ｎｍ等の波長光源に極大吸収波長がマッチングされた特開２００９－１９１１７９号公報に記載の化合物も用いることができ、この内容は本明細書に組み込まれる。 As the aminoacetophenone-based initiator, the compound described in JP-A-2009-191179 whose maximum absorption wavelength is matched to a wavelength light source such as 365 nm or 405 nm can also be used, the content of which is incorporated herein.
　アシルホスフィンオキシド系開始剤としては、２，４，６－トリメチルベンゾイル－ジフェニル－ホスフィンオキサイドなどが挙げられる。また、Ｏｍｎｉｒａｄ　８１９、Ｏｍｎｉｒａｄ　ＴＰＯ（以上、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、ＩＲＧＡＣＵＲＥ－８１９やＩＲＧＡＣＵＲＥ－ＴＰＯ（商品名：いずれもＢＡＳＦ社製）を用いることができる。 Acylphosphine oxide initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), IRGACURE-819 and IRGACURE-TPO (trade names: all manufactured by BASF) can also be used.
　メタロセン化合物としては、ＩＲＧＡＣＵＲＥ－７８４、ＩＲＧＡＣＵＲＥ－７８４ＥＧ（いずれもＢＡＳＦ社製）、Ｋｅｙｃｕｒｅ ＶＩＳ ８１３（Ｋｉｎｇ Ｂｒｏｔｈｅｒ Ｃｈｅｍ社製）などが例示される。 Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF) and Keycure VIS 813 (manufactured by King Brother Chem).
　光ラジカル重合開始剤として、より好ましくはオキシム化合物が挙げられる。オキシム化合物を用いることにより、露光ラチチュードをより効果的に向上させることが可能になる。オキシム化合物は、露光ラチチュード（露光マージン）が広く、かつ、光硬化促進剤としても働くため、特に好ましい。 The photoradical polymerization initiator is more preferably an oxime compound. By using an oxime compound, the exposure latitude can be improved more effectively. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.
　オキシム化合物の具体例としては、特開２００１－２３３８４２号公報に記載の化合物、特開２０００－０８００６８号公報に記載の化合物、特開２００６－３４２１６６号公報に記載の化合物、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年、ｐｐ．１６５３－１６６０）に記載の化合物、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年、ｐｐ．１５６－１６２）に記載の化合物、Ｊｏｕｒｎａｌ　ｏｆ　Ｐｈｏｔｏｐｏｌｙｍｅｒ　Ｓｃｉｅｎｃｅ　ａｎｄ　Ｔｅｃｈｎｏｌｏｇｙ（１９９５年、ｐｐ．２０２－２３２）に記載の化合物、特開２０００－０６６３８５号公報に記載の化合物、特表２００４－５３４７９７号公報に記載の化合物、特開２０１７－０１９７６６号公報に記載の化合物、特許第６０６５５９６号公報に記載の化合物、国際公開第２０１５／１５２１５３号に記載の化合物、国際公開第２０１７／０５１６８０号に記載の化合物、特開２０１７－１９８８６５号公報に記載の化合物、国際公開第２０１７／１６４１２７号の段落番号００２５～００３８に記載の化合物、国際公開第２０１３／１６７５１５号に記載の化合物などが挙げられ、この内容は本明細書に組み込まれる。 Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp.1653-1660); C. S. Compounds described in Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2017-019766, compounds described in Patent No. 6065596, compounds described in WO 2015/152153, WO 2017 / 051680, compounds described in JP-A-2017-198865, compounds described in paragraphs 0025 to 0038 of WO 2017/164127, compounds described in WO 2013/167515, etc. , the contents of which are incorporated herein.
　好ましいオキシム化合物としては、例えば、下記の構造の化合物や、３－（ベンゾイルオキシ（イミノ））ブタン－２－オン、３－（アセトキシ（イミノ））ブタン－２－オン、３－（プロピオニルオキシ（イミノ））ブタン－２－オン、２－（アセトキシ（イミノ））ペンタン－３－オン、２－（アセトキシ（イミノ））－１－フェニルプロパン－１－オン、２－（ベンゾイルオキシ（イミノ））－１－フェニルプロパン－１－オン、３－（（４－トルエンスルホニルオキシ）イミノ）ブタン－２－オン、及び２－（エトキシカルボニルオキシ（イミノ））－１－フェニルプロパン－１－オンなどが挙げられる。本発明の樹脂組成物においては、特に光ラジカル重合開始剤としてオキシム化合物（オキシム系の光ラジカル重合開始剤）を用いることが好ましい。オキシム系の光ラジカル重合開始剤は、分子内に　＞Ｃ＝Ｎ－Ｏ－Ｃ（＝Ｏ）－　の連結基を有する。 Preferred oxime compounds include, for example, compounds having the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy( imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino)) -1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one, etc. mentioned. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (an oxime-based radical photopolymerization initiator) as the radical photopolymerization initiator. The oxime-based radical photopolymerization initiator has a >C=N-O-C(=O)- linking group in the molecule.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　市販品ではＩＲＧＡＣＵＲＥ　ＯＸＥ　０１、ＩＲＧＡＣＵＲＥ　ＯＸＥ　０２、ＩＲＧＡＣＵＲＥ　ＯＸＥ　０３、ＩＲＧＡＣＵＲＥ　ＯＸＥ　０４（以上、ＢＡＳＦ社製）、アデカオプトマーＮ－１９１９（（株）ＡＤＥＫＡ製、特開２０１２－０１４０５２号公報に記載の光ラジカル重合開始剤２）も好適に用いられる。また、ＴＲ－ＰＢＧ－３０４、ＴＲ－ＰＢＧ－３０５（常州強力電子新材料有限公司製）、アデカアークルズＮＣＩ－７３０、ＮＣＩ－８３１及びアデカアークルズＮＣＩ－９３０（（株）ＡＤＥＫＡ製）も用いることができる。また、ＤＦＩ－０９１（ダイトーケミックス（株）製）、ＳｐｅｅｄＣｕｒｅ　ＰＤＯ（ＳＡＲＴＯＭＥＲ　ＡＲＫＥＭＡ製）を用いることができる。また、下記の構造のオキシム化合物を用いることもできる。 
Figure JPOXMLDOC01-appb-C000020
 Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., the light described in JP 2012-014052 A radical polymerization initiator 2) is also preferably used. In addition, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Tenryu Electric New Materials Co., Ltd.), Adeka Arkles NCI-730, NCI-831 and Adeka Arkles NCI-930 (manufactured by ADEKA Co., Ltd.) are also used. be able to. Also, DFI-091 (manufactured by Daito Chemix Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Also, an oxime compound having the following structure can be used.
Figure JPOXMLDOC01-appb-C000020
　光ラジカル重合開始剤としては、フルオレン環を有するオキシム化合物を用いることもできる。フルオレン環を有するオキシム化合物の具体例としては、特開２０１４－１３７４６６号公報に記載の化合物、特許０６６３６０８１号に記載の化合物が挙げられ、この内容は本明細書に組み込まれる。 An oxime compound having a fluorene ring can also be used as the photoradical polymerization initiator. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466 and compounds described in Japanese Patent No. 06636081, the contents of which are incorporated herein.
　光ラジカル重合開始剤としては、カルバゾール環の少なくとも１つのベンゼン環がナフタレン環となった骨格を有するオキシム化合物を用いることもできる。そのようなオキシム化合物の具体例としては、国際公開第２０１３／０８３５０５号に記載の化合物が挙げられ、この内容は本明細書に組み込まれる。 As the radical photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in WO2013/083505, the contents of which are incorporated herein.
　また、フッ素原子を有するオキシム化合物を用いることも可能である。そのようなオキシム化合物の具体例としては、特開２０１０－２６２０２８号公報に記載されている化合物、特表２０１４－５００８５２号公報の段落０３４５に記載されている化合物２４、３６～４０、特開２０１３－１６４４７１号公報の段落０１０１に記載されている化合物（Ｃ－３）などが挙げられ、この内容は本明細書に組み込まれる。 It is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. and compound (C-3) described in paragraph 0101 of JP-A-164471, the contents of which are incorporated herein.
　光重合開始剤としては、ニトロ基を有するオキシム化合物を用いることができる。ニトロ基を有するオキシム化合物は、二量体とすることも好ましい。ニトロ基を有するオキシム化合物の具体例としては、特開２０１３－１１４２４９号公報の段落番号００３１～００４７、特開２０１４－１３７４６６号公報の段落番号０００８～００１２、００７０～００７９に記載されている化合物、特許４２２３０７１号公報の段落番号０００７～００２５に記載されている化合物が挙げられ、この内容は本明細書に組み込まれる。また、ニトロ基を有するオキシム化合物としては、アデカアークルズＮＣＩ－８３１（（株）ＡＤＥＫＡ製）も挙げられる。 An oxime compound having a nitro group can be used as the photopolymerization initiator. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249 and paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466; Included are compounds described in paragraphs 0007-0025 of Japanese Patent No. 4223071, the contents of which are incorporated herein. Further, the oxime compound having a nitro group also includes ADEKA Arkles NCI-831 (manufactured by ADEKA Co., Ltd.).
　光ラジカル重合開始剤としては、ベンゾフラン骨格を有するオキシム化合物を用いることもできる。具体例としては、国際公開第２０１５／０３６９１０号に記載されているＯＥ－０１～ＯＥ－７５が挙げられる。 An oxime compound having a benzofuran skeleton can also be used as the photoradical polymerization initiator. Specific examples include OE-01 to OE-75 described in WO 2015/036910.
　光ラジカル重合開始剤としては、カルバゾール骨格にヒドロキシ基を有する置換基が結合したオキシム化合物を用いることもできる。このような光重合開始剤としては国際公開第２０１９／０８８０５５号に記載された化合物などが挙げられ、この内容は本明細書に組み込まれる。 As the photoradical polymerization initiator, an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used. Such photoinitiators include compounds such as those described in WO2019/088055, the contents of which are incorporated herein.
　光重合開始剤としては、芳香族環に電子求引性基が導入された芳香族環基ＡｒＯＸ１を有するオキシム化合物（以下、オキシム化合物ＯＸともいう）を用いることもできる。上記芳香族環基ＡｒＯＸ１が有する電子求引性基としては、アシル基、ニトロ基、トリフルオロメチル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、シアノ基が挙げられ、アシル基およびニトロ基が好ましく、耐光性に優れた膜を形成しやすいという理由からアシル基であることがより好ましく、ベンゾイル基であることが更に好ましい。ベンゾイル基は、置換基を有していてもよい。置換基としては、ハロゲン原子、シアノ基、ニトロ基、ヒドロキシ基、アルキル基、アルコキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルケニル基、アルキルスルファニル基、アリールスルファニル基、アシル基またはアミノ基であることが好ましく、アルキル基、アルコキシ基、アリール基、アリールオキシ基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基またはアミノ基であることがより好ましく、アルコキシ基、アルキルスルファニル基またはアミノ基であることが更に好ましい。 As the photopolymerization initiator, an oxime compound having an aromatic ring group Ar 2 OX1 in which an electron-withdrawing group is introduced into the aromatic ring (hereinafter also referred to as oxime compound OX) can be used. Examples of the electron-withdrawing group of the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. An acyl group and a nitro group are preferred, an acyl group is more preferred, and a benzoyl group is even more preferred because a film having excellent light resistance can be easily formed. A benzoyl group may have a substituent. Examples of substituents include halogen atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, It is preferably an acyl group or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group. A sulfanyl group or an amino group is more preferred.
　オキシム化合物ＯＸは、式（ＯＸ１）で表される化合物および式（ＯＸ２）で表される化合物から選ばれる少なくとも１種であることが好ましく、式（ＯＸ２）で表される化合物であることがより好ましい。
Figure JPOXMLDOC01-appb-C000021
　式中、ＲＸ１は、アルキル基、アルケニル基、アルコキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アシルオキシ基、アミノ基、ホスフィノイル基、カルバモイル基またはスルファモイル基を表し、
　ＲＸ２は、アルキル基、アルケニル基、アルコキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシルオキシ基またはアミノ基を表し、
　ＲＸ３～ＲＸ１４は、それぞれ独立して水素原子または置換基を表す；
　ただし、ＲＸ１０～ＲＸ１４のうち少なくとも一つは、電子求引性基である。 The oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), more preferably the compound represented by the formula (OX2). preferable.
Figure JPOXMLDOC01-appb-C000021
In the formula, R X1 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl a group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group,
R X2 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, aryl represents a sulfonyl group, an acyloxy group or an amino group,
R X3 to R X14 each independently represent a hydrogen atom or a substituent;
However, at least one of R X10 to R X14 is an electron-withdrawing group.
　上記式において、ＲＸ１２が電子求引性基であり、ＲＸ１０、ＲＸ１１、ＲＸ１３、ＲＸ１４は水素原子であることが好ましい。 In the above formula, R X12 is an electron-withdrawing group, and R X10 , R X11 , R X13 and R X14 are preferably hydrogen atoms.
　オキシム化合物ＯＸの具体例としては、特許第４６００６００号公報の段落番号００８３～０１０５に記載の化合物が挙げられ、この内容は本明細書に組み込まれる。 Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein.
　最も好ましいオキシム化合物としては、特開２００７－２６９７７９号公報に示される特定置換基を有するオキシム化合物や、特開２００９－１９１０６１号公報に示されるチオアリール基を有するオキシム化合物などが挙げられ、この内容は本明細書に組み込まれる。 The most preferable oxime compounds include oxime compounds having specific substituents shown in JP-A-2007-269779 and oxime compounds having a thioaryl group shown in JP-A-2009-191061. incorporated herein.
　光ラジカル重合開始剤は、露光感度の観点から、トリハロメチルトリアジン化合物、ベンジルジメチルケタール化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、アシルホスフィン化合物、ホスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリールイミダゾールダイマー、オニウム塩化合物、ベンゾチアゾール化合物、ベンゾフェノン化合物、アセトフェノン化合物及びその誘導体、シクロペンタジエン－ベンゼン－鉄錯体及びその塩、ハロメチルオキサジアゾール化合物、３－アリール置換クマリン化合物よりなる群から選択される化合物が好ましい。 From the viewpoint of exposure sensitivity, photoradical polymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds; are preferred.
　更に好ましい光ラジカル重合開始剤は、トリハロメチルトリアジン化合物、α－アミノケトン化合物、アシルホスフィン化合物、ホスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリールイミダゾールダイマー、オニウム塩化合物、ベンゾフェノン化合物、アセトフェノン化合物であり、トリハロメチルトリアジン化合物、α－アミノケトン化合物、メタロセン化合物、オキシム化合物、トリアリールイミダゾールダイマー、ベンゾフェノン化合物よりなる群から選ばれる少なくとも１種の化合物が一層好ましく、メタロセン化合物又はオキシム化合物を用いるのがより一層好ましい。 More preferred radical photopolymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds. At least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferred, and metallocene compounds or oxime compounds are even more preferred. .
　また、光ラジカル重合開始剤は、ベンゾフェノン、Ｎ，Ｎ’－テトラメチル－４，４’－ジアミノベンゾフェノン（ミヒラーケトン）等のＮ，Ｎ’－テトラアルキル－４，４’－ジアミノベンゾフェノン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタノン－１，２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノ－プロパノン－１等の芳香族ケトン、アルキルアントラキノン等の芳香環と縮環したキノン類、ベンゾインアルキルエーテル等のベンゾインエーテル化合物、ベンゾイン、アルキルベンゾイン等のベンゾイン化合物、ベンジルジメチルケタール等のベンジル誘導体などを用いることもできる。また、下記式（Ｉ）で表される化合物を用いることもできる。 Further, the photoradical polymerization initiator includes benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone such as N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), 2-benzyl -aromatic ketones such as 2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, alkylanthraquinones, etc. quinones condensed with the aromatic ring of , benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyl dimethyl ketal can also be used. A compound represented by the following formula (I) can also be used.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　式（Ｉ）中、ＲＩ００は、炭素数１～２０のアルキル基、１個以上の酸素原子によって中断された炭素数２～２０のアルキル基、炭素数１～１２のアルコキシ基、フェニル基、又は、炭素数１～２０のアルキル基、炭素数１～１２のアルコキシ基、ハロゲン原子、シクロペンチル基、シクロヘキシル基、炭素数２～１２のアルケニル基、１個以上の酸素原子によって中断された炭素数２～１８のアルキル基及び炭素数１～４のアルキル基の少なくとも１つで置換されたフェニル基、若しくは、ビフェニル基であり、ＲＩ０１は、式（ＩＩ）で表される基であるか、ＲＩ００と同じ基であり、ＲＩ０２～ＲＩ０４は各々独立に炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基又はハロゲン原子である。 In formula (I), R 100 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, Alternatively, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, a carbon number interrupted by one or more oxygen atoms a phenyl group or a biphenyl group substituted with at least one of an alkyl group having 2 to 18 carbon atoms and an alkyl group having 1 to 4 carbon atoms, and R I01 is a group represented by formula (II); R 102 to R 104 are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　式中、ＲＩ０５～ＲＩ０７は、上記式（Ｉ）のＲＩ０２～ＲＩ０４と同じである。 In the formula, R 105 to R 107 are the same as R 102 to R 104 in formula (I) above.
　また、光ラジカル重合開始剤は、国際公開第２０１５／１２５４６９号の段落００４８～００５５に記載の化合物を用いることもでき、この内容は本明細書に組み込まれる。 Also, as the photoradical polymerization initiator, compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can be used, the contents of which are incorporated herein.
　光ラジカル重合開始剤としては、２官能あるいは３官能以上の光ラジカル重合開始剤を用いてもよい。そのような光ラジカル重合開始剤を用いることにより、光ラジカル重合開始剤の１分子から２つ以上のラジカルが発生するため、良好な感度が得られる。また、非対称構造の化合物を用いた場合においては、結晶性が低下して溶剤などへの溶解性が向上して、経時で析出しにくくなり、樹脂組成物の経時安定性を向上させることができる。２官能あるいは３官能以上の光ラジカル重合開始剤の具体例としては、特表２０１０－５２７３３９号公報、特表２０１１－５２４４３６号公報、国際公開第２０１５／００４５６５号、特表２０１６－５３２６７５号公報の段落番号０４０７～０４１２、国際公開第２０１７／０３３６８０号の段落番号００３９～００５５に記載されているオキシム化合物の２量体、特表２０１３－５２２４４５号公報に記載されている化合物（Ｅ）および化合物（Ｇ）、国際公開第２０１６／０３４９６３号に記載されているＣｍｐｄ１～７、特表２０１７－５２３４６５号公報の段落番号０００７に記載されているオキシムエステル類光開始剤、特開２０１７－１６７３９９号公報の段落番号００２０～００３３に記載されている光開始剤、特開２０１７－１５１３４２号公報の段落番号００１７～００２６に記載されている光重合開始剤（Ａ）、特許第６４６９６６９号公報に記載されているオキシムエステル光開始剤などが挙げられ、この内容は本明細書に組み込まれる。 As the radical photopolymerization initiator, a difunctional or trifunctional or higher radical photopolymerization initiator may be used. By using such a radical photopolymerization initiator, two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, the crystallinity is lowered, the solubility in a solvent or the like is improved, and precipitation becomes difficult over time, and the stability over time of the resin composition can be improved. . Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Publication No. 2016-532675. Paragraph numbers 0407 to 0412, dimers of oxime compounds described in paragraph numbers 0039 to 0055 of International Publication No. 2017/033680, compound (E) and compounds described in JP-A-2013-522445 ( G), Cmpd1 to 7 described in International Publication No. 2016/034963, oxime ester photoinitiators described in paragraph number 0007 of JP 2017-523465, JP 2017-167399 Photoinitiators described in paragraph numbers 0020 to 0033, photoinitiators (A) described in paragraph numbers 0017 to 0026 of JP-A-2017-151342, described in Japanese Patent No. 6469669 and oxime ester photoinitiators, the contents of which are incorporated herein.
　光重合開始剤を含む場合、その含有量は、本発明の樹脂組成物の全固形分に対し０．１～３０質量％であることが好ましく、より好ましくは０．１～２０質量％であり、更に好ましくは０．５～１５質量％であり、一層好ましくは１．０～１０質量％である。光重合開始剤は１種のみ含有していてもよいし、２種以上含有していてもよい。光重合開始剤を２種以上含有する場合は、合計量が上記範囲であることが好ましい。
　なお、光重合開始剤は熱重合開始剤としても機能する場合があるため、オーブンやホットプレート等の加熱によって光重合開始剤による架橋を更に進行させられる場合がある。 When a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. , more preferably 0.5 to 15% by mass, and still more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range.
In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking by the photopolymerization initiator may be further advanced by heating with an oven, a hot plate, or the like.
－熱重合開始剤－
　本発明に係る樹脂組成物は、熱重合開始剤を含むことも好ましい。
　熱重合開始剤としては、重合性化合物の種類に応じて選択することができるが、熱ラジカル重合開始剤が好ましい。熱ラジカル重合開始剤は、熱のエネルギーによってラジカルを発生し、重合性を有する化合物の重合反応を開始又は促進させる化合物である。
　また、上述した光重合開始剤も熱により重合を開始する機能を有する場合があり、熱重合開始剤として添加することができる場合がある。 -Thermal polymerization initiator-
The resin composition according to the present invention preferably also contains a thermal polymerization initiator.
The thermal polymerization initiator can be selected depending on the type of polymerizable compound, but a thermal radical polymerization initiator is preferred. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes a polymerization reaction of a polymerizable compound.
Moreover, the photopolymerization initiator described above may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.
　熱重合開始剤としては、公知のアゾ系化合物、公知の過酸化物系化合物等が挙げられる。アゾ系化合物としては、アゾビス系化合物を挙げることができる。アゾ系化合物は、シアノ基を有する化合物であってもよく、シアノ基を有さない化合物であってもよい。過酸化物系化合物としては、ケトンパーオキサイド、パーオキシケタール、ハイドロパーオキサイド、ジアルキルパーオキサイド、ジアシルパーオキサイド、パーオキシジカーボネート、パーオキシエステル、等を挙げることができる。
　熱重合開始剤としては、市販品を用いることもでき、富士フイルム和光純薬（株）製のＶ－４０、Ｖ－６０１、ＶＦ－０９６、日油（株）製のパーへキシルＯ、パーへキシルＤ、パーへキシルＩ、パーヘキサ２５Ｏ、パーヘキサ２５Ｚ、パークミルＤ、パークミルＤ－４０、パークミルＤ－４０ＭＢ、パークミルＨ、パークミルＰ、パークミルＮＤ等が挙げられる。
　また、熱ラジカル重合開始剤として、具体的には、特開２００８－０６３５５４号公報の段落００７４～０１１８に記載されている化合物が挙げられ、この内容は本明細書に組み込まれる。 Examples of thermal polymerization initiators include known azo compounds and known peroxide compounds. Examples of azo-based compounds include azobis-based compounds. The azo compound may be a compound having a cyano group or a compound having no cyano group. Peroxide compounds include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters, and the like.
Commercially available products can be used as the thermal polymerization initiator, such as V-40, V-601, and VF-096 manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., perhexyl O manufactured by NOF Corporation, per Hexyl D, Perhexyl I, Perhexa 25O, Perhexa 25Z, Percmyl D, Percmyl D-40, Percmyl D-40MB, Percmyl H, Percmyl P, Percmyl ND and the like.
Further, specific examples of thermal radical polymerization initiators include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein.
　樹脂組成物における熱重合開始剤の含有量としては、組成物の全固形分に対して、０．０５質量％以上１０質量％以下が好ましく、０．１質量％以上１０質量％以下がより好ましく、０．１質量％以上５質量％以下が更に好ましく、０．５質量％以上３質量％以下が特に好ましい。
　樹脂組成物（特に、第２の樹脂組成物）は、熱重合開始剤を、１種単独で含んでいても、２種以上を含んでいてもよい。２種以上を含む場合、その合計量が上記範囲内となることが好ましい。 The content of the thermal polymerization initiator in the resin composition is preferably 0.05% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 10% by mass or less, relative to the total solid content of the composition. , more preferably 0.1% by mass or more and 5% by mass or less, and particularly preferably 0.5% by mass or more and 3% by mass or less.
The resin composition (particularly, the second resin composition) may contain one type of thermal polymerization initiator alone, or two or more types thereof. When two or more types are included, the total amount is preferably within the above range.
〔増感剤〕
　樹脂組成物は、増感剤を含んでいてもよい。増感剤は、特定の活性放射線を吸収して電子励起状態となる。電子励起状態となった増感剤は、熱ラジカル重合開始剤、光ラジカル重合開始剤などと接触して、電子移動、エネルギー移動、発熱などの作用が生じる。これにより、熱ラジカル重合開始剤、光ラジカル重合開始剤は化学変化を起こして分解し、ラジカル、酸又は塩基を生成する。
　使用可能な増感剤として、ベンゾフェノン系、ミヒラーズケトン系、クマリン系、ピラゾールアゾ系、アニリノアゾ系、トリフェニルメタン系、アントラキノン系、アントラセン系、アントラピリドン系、ベンジリデン系、オキソノール系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、シアニン系、フェノチアジン系、ピロロピラゾールアゾメチン系、キサンテン系、フタロシアニン系、べンゾピラン系、インジゴ系等の化合物を使用することができる。
　増感剤としては、例えば、ミヒラーズケトン、４，４’－ビス（ジエチルアミノ）ベンゾフェノン、２，５－ビス（４’－ジエチルアミノベンザル）シクロペンタン、２，６－ビス（４’－ジエチルアミノベンザル）シクロヘキサノン、２，６－ビス（４’－ジエチルアミノベンザル）－４－メチルシクロヘキサノン、４，４’－ビス（ジメチルアミノ）カルコン、４，４’－ビス（ジエチルアミノ）カルコン、ｐ－ジメチルアミノシンナミリデンインダノン、ｐ－ジメチルアミノベンジリデンインダノン、２－（ｐ－ジメチルアミノフェニルビフェニレン）－ベンゾチアゾール、２－（ｐ－ジメチルアミノフェニルビニレン）ベンゾチアゾール、２－（ｐ－ジメチルアミノフェニルビニレン）イソナフトチアゾール、１，３－ビス（４’－ジメチルアミノベンザル）アセトン、１，３－ビス（４’－ジエチルアミノベンザル）アセトン、３，３’－カルボニル－ビス（７－ジエチルアミノクマリン）、３－アセチル－７－ジメチルアミノクマリン、３－エトキシカルボニル－７－ジメチルアミノクマリン、３－ベンジロキシカルボニル－７－ジメチルアミノクマリン、３－メトキシカルボニル－７－ジエチルアミノクマリン、３－エトキシカルボニル－７－ジエチルアミノクマリン（７－（ジエチルアミノ）クマリン－３－カルボン酸エチル）、Ｎ－フェニル－Ｎ’－エチルエタノールアミン、Ｎ－フェニルジエタノールアミン、Ｎ－ｐ－トリルジエタノールアミン、Ｎ－フェニルエタノールアミン、４－モルホリノベンゾフェノン、ジメチルアミノ安息香酸イソアミル、ジエチルアミノ安息香酸イソアミル、２－メルカプトベンズイミダゾール、１－フェニル－５－メルカプトテトラゾール、２－メルカプトベンゾチアゾール、２－（ｐ－ジメチルアミノスチリル）ベンズオキサゾール、２－（ｐ－ジメチルアミノスチリル）ベンゾチアゾール、２－（ｐ－ジメチルアミノスチリル）ナフト（１，２－ｄ）チアゾール、２－（ｐ－ジメチルアミノベンゾイル）スチレン、ジフェニルアセトアミド、ベンズアニリド、Ｎ－メチルアセトアニリド、３‘，４’－ジメチルアセトアニリド等が挙げられる。
　また、他の増感色素を用いてもよい。
　増感色素の詳細については、特開２０１６－０２７３５７号公報の段落０１６１～０１６３の記載を参酌でき、この内容は本明細書に組み込まれる。 [Sensitizer]
The resin composition may contain a sensitizer. A sensitizer absorbs specific actinic radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and causes electron transfer, energy transfer, heat generation, or the like. As a result, the thermal radical polymerization initiator and the photoradical polymerization initiator undergo chemical changes and are decomposed to generate radicals, acids or bases.
Usable sensitizers include benzophenones, Michler's ketones, coumarins, pyrazole azos, anilinoazos, triphenylmethanes, anthraquinones, anthracenes, anthrapyridones, benzylidenes, oxonols, and pyrazolotriazole azos. , pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo compounds.
Sensitizers include, for example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal) Cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyl denindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)iso naphthothiazole, 1,3-bis(4′-dimethylaminobenzal)acetone, 1,3-bis(4′-diethylaminobenzal)acetone, 3,3′-carbonyl-bis(7-diethylaminocoumarin), 3 -acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylamino coumarin (ethyl 7-(diethylamino)coumarin-3-carboxylate), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethyl) aminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4 '-dimethylacetanilide and the like.
Other sensitizing dyes may also be used.
For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-027357 can be referred to, the contents of which are incorporated herein.
　樹脂組成物が増感剤を含む場合、増感剤の含有量は、樹脂組成物の全固形分に対し、０．０１～２０質量％であることが好ましく、０．１～１５質量％であることがより好ましく、０．５～１０質量％であることが更に好ましい。増感剤は、１種単独で用いてもよいし、２種以上を併用してもよい。 When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, preferably 0.1 to 15% by mass, based on the total solid content of the resin composition. more preferably 0.5 to 10% by mass. The sensitizers may be used singly or in combination of two or more.
〔連鎖移動剤〕
　本発明の樹脂組成物は、連鎖移動剤を含有してもよい。連鎖移動剤は、例えば高分子辞典第三版（高分子学会編、２００５年）６８３－６８４頁に定義されている。連鎖移動剤としては、例えば、分子内に－Ｓ－Ｓ－、－ＳＯ２－Ｓ－、－Ｎ－Ｏ－、ＳＨ、ＰＨ、ＳｉＨ、及びＧｅＨを有する化合物群、ＲＡＦＴ（Reversible Addition Fragmentation chain Transfer）重合に用いられるチオカルボニルチオ基を有するジチオベンゾアート、トリチオカルボナート、ジチオカルバマート、キサンタート化合物等が用いられる。これらは、低活性のラジカルに水素を供与して、ラジカルを生成するか、若しくは、酸化された後、脱プロトンすることによりラジカルを生成しうる。特に、チオール化合物を好ましく用いることができる。 [Chain transfer agent]
The resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in Kobunshi Dictionary, 3rd edition (edited by Kobunshi Gakkai, 2005), pp. 683-684. Chain transfer agents include, for example, a group of compounds having —S—S—, —SO 2 —S—, —NO—, SH, PH, SiH, and GeH in the molecule, RAFT (Reversible Addition Fragmentation Chain Transfer ) Dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds and the like having a thiocarbonylthio group used for polymerization are used. They can either donate hydrogen to less active radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds can be preferably used.
　また、連鎖移動剤は、国際公開第２０１５／１９９２１９号の段落０１５２～０１５３に記載の化合物を用いることもでき、この内容は本明細書に組み込まれる。 In addition, the chain transfer agent can also use the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219, the contents of which are incorporated herein.
　本発明の樹脂組成物が連鎖移動剤を有する場合、連鎖移動剤の含有量は、本発明の樹脂組成物の全固形分１００質量部に対し、０．０１～２０質量部が好ましく、０．１～１０質量部がより好ましく、０．５～５質量部が更に好ましい。連鎖移動剤は１種のみでもよいし、２種以上であってもよい。連鎖移動剤が２種以上の場合は、その合計が上記範囲であることが好ましい。 When the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, preferably 0.01 to 20 parts by mass, based on 100 parts by mass of the total solid content of the resin composition of the present invention. 1 to 10 parts by mass is more preferable, and 0.5 to 5 parts by mass is even more preferable. One type of chain transfer agent may be used, or two or more types may be used. When two or more chain transfer agents are used, the total is preferably within the above range.
〔光酸発生剤〕
　本発明の樹脂組成物は、光酸発生剤を含むことが好ましい。
　光酸発生剤とは、２００nm～９００nmの光照射により、ブレンステッド酸、及び、ルイス酸の少なくとも一方を発生させる化合物を表す。照射される光は、好ましくは波長３００ｎｍ～４５０nmの光であり、より好ましくは３３０nm～４２０nmの光である。光酸発生剤単独または増感剤との併用において、感光して酸を発生させることが可能な光酸発生剤であることが好ましい。
　発生する酸の例としては、ハロゲン化水素、カルボン酸、スルホン酸、スルフィン酸、チオスルフィン酸、リン酸、リン酸モノエステル、リン酸ジエステル、ホウ素誘導体、リン誘導体、アンチモン誘導体、過酸化ハロゲン、スルホンアミド等が好ましく挙げられる。  [Photoacid generator]
The resin composition of the present invention preferably contains a photoacid generator.
A photoacid generator is a compound that generates at least one of Bronsted acid and Lewis acid upon irradiation with light of 200 nm to 900 nm. The light to be irradiated is preferably light with a wavelength of 300 nm to 450 nm, more preferably light with a wavelength of 330 nm to 420 nm. When used alone or in combination with a sensitizer, the photoacid generator is preferably a photoacid generator capable of generating an acid upon exposure.
Examples of generated acids include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acid, phosphoric monoesters, phosphoric diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, Sulfonamide and the like are preferred.
　本発明の樹脂組成物に用いられる光酸発生剤としては、例えば、キノンジアジド化合物、オキシムスルホネート化合物、有機ハロゲン化化合物、有機ホウ酸塩化合物、ジスルホン化合物、オニウム塩化合物等が挙げられる。
　感度、保存安定性の観点から、有機ハロゲン化合物、オキシムスルホネート化合物、オニウム塩化合物が好ましく、形成する膜の機械特性等から、オキシムエステルが好ましい。 Examples of the photoacid generator used in the resin composition of the present invention include quinone diazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfone compounds, and onium salt compounds.
Organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred from the viewpoint of sensitivity and storage stability, and oxime esters are preferred from the viewpoint of the mechanical properties of the film to be formed.
　キノンジアジド化合物としては、１価または多価のヒドロキシ化合物にキノンジアジドのスルホン酸がエステル結合したもの、１価または多価のアミノ化合物にキノンジアジドのスルホン酸がスルホンアミド結合したもの、ポリヒドロキシポリアミノ化合物にキノンジアジドのスルホン酸がエステル結合および／またはスルホンアミド結合したものなどが挙げられる。これらポリヒドロキシ化合物、ポリアミノ化合物、ポリヒドロキシポリアミノ化合物の全ての官能基がキノンジアジドで置換されていなくてもよいが、平均して官能基全体の４０モル％以上がキノンジアジドで置換されていることが好ましい。このようなキノンジアジド化合物を含有させることで、一般的な紫外線である水銀灯のｉ線（波長３６５ｎｍ）、ｈ線（波長４０５ｎｍ）、ｇ線（波長４３６ｎｍ）に感光する樹脂組成物を得ることができる。 Examples of quinonediazide compounds include monovalent or polyvalent hydroxy compounds in which quinonediazide sulfonic acids are ester-bonded, monovalent or polyvalent amino compounds in which quinonediazide sulfonic acids are sulfonamide-bonded, and polyhydroxypolyamino compounds with quinonediazide. and/or sulfonic acid having an ester bond and/or a sulfonamide bond. Although not all the functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds may be substituted with quinonediazide, it is preferred that 40 mol % or more of all functional groups on average be substituted with quinonediazide. . By containing such a quinonediazide compound, it is possible to obtain a resin composition that is sensitive to i-line (wavelength: 365 nm), h-line (wavelength: 405 nm), and g-line (wavelength: 436 nm) of a mercury lamp, which are general UV rays. .
　ヒドロキシ化合物として具体的には、フェノール、トリヒドロキシベンゾフェノン、４メトキシフェノール、イソプロパノール、オクタノール、t-Buアルコール、シクロヘキサノール、ナフトール、Ｂｉｓ－Ｚ、ＢｉｓＰ－ＥＺ、ＴｅｋＰ－４ＨＢＰＡ、ＴｒｉｓＰ－ＨＡＰ、ＴｒｉｓＰ－ＰＡ、ＴｒｉｓＰ－ＳＡ、ＴｒｉｓＯＣＲ－ＰＡ、ＢｉｓＯＣＨＰ－Ｚ、ＢｉｓＰ－ＭＺ、ＢｉｓＰ－ＰＺ、ＢｉｓＰ－ＩＰＺ、ＢｉｓＯＣＰ－ＩＰＺ、ＢｉｓＰ－ＣＰ、ＢｉｓＲＳ－２Ｐ、ＢｉｓＲＳ－３Ｐ、ＢｉｓＰ－ＯＣＨＰ、メチレントリス－ＦＲ－ＣＲ、ＢｉｓＲＳ－２６Ｘ、ＤＭＬ－ＭＢＰＣ、ＤＭＬ－ＭＢＯＣ、ＤＭＬ－ＯＣＨＰ、ＤＭＬ－ＰＣＨＰ、ＤＭＬ－ＰＣ、ＤＭＬ－ＰＴＢＰ、ＤＭＬ－３４Ｘ、ＤＭＬ－ＥＰ、ＤＭＬ－ＰＯＰ、ジメチロール－ＢｉｓＯＣ－Ｐ、ＤＭＬ－ＰＦＰ、ＤＭＬ－ＰＳＢＰ、ＤＭＬ－ＭＴｒｉｓＰＣ、ＴｒｉＭＬ－Ｐ、ＴｒｉＭＬ－３５ＸＬ、ＴＭＬ－ＢＰ、ＴＭＬ－ＨＱ、ＴＭＬ－ｐｐ－ＢＰＦ、ＴＭＬ－ＢＰＡ、ＴＭＯＭ－ＢＰ、ＨＭＬ－ＴＰＰＨＢＡ、ＨＭＬ－ＴＰＨＡＰ（以上、商品名、本州化学工業製）、ＢＩＲ－ＯＣ、ＢＩＰ－ＰＣ、ＢＩＲ－ＰＣ、ＢＩＲ－ＰＴＢＰ、ＢＩＲ－ＰＣＨＰ、ＢＩＰ－ＢＩＯＣ－Ｆ、４ＰＣ、ＢＩＲ－ＢＩＰＣ－Ｆ、ＴＥＰ－ＢＩＰ－Ａ、４６ＤＭＯＣ、４６ＤＭＯＥＰ、ＴＭ－ＢＩＰ－Ａ（以上、商品名、旭有機材工業製）、２，６－ジメトキシメチル－４－ｔ－ブチルフェノール、２，６－ジメトキシメチル－ｐ－クレゾール、２，６－ジアセトキシメチル－ｐ－クレゾール、ナフトール、テトラヒドロキシベンゾフェノン、没食子酸メチルエステル、ビスフェノールＡ、ビスフェノールＥ、メチレンビスフェノール、ＢｉｓＰ－ＡＰ（商品名、本州化学工業製）、ノボラック樹脂などを挙げることができるが、これらに限定されない。 Specific examples of hydroxy compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, t-Bu alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP- PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris-FR -CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML -PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (above , trade name, manufactured by Honshu Chemical Industry), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade names, manufactured by Asahi Organic Chemicals Industry), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6- diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), novolak resin, and the like. , but not limited to.
　アミノ化合物として具体的には、アニリン、メチルアニリン、ジエチルアミン、ブチルアミン、１，４－フェニレンジアミン、１，３－フェニレンジアミン、４，４’－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルメタン、４，４’－ジアミノジフェニルスルホン、４，４’－ジアミノジフェニルスルフィドなどを挙げることができるが、これらに限定されない。 Specific examples of amino compounds include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, and the like, but are not limited thereto.
　また、ポリヒドロキシポリアミノ化合物として具体的には、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパン、３，３’－ジヒドロキシベンジジンなどを挙げることができるが、これらに限定されない。 Specific examples of polyhydroxypolyamino compounds include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3′-dihydroxybenzidine, but are not limited to these. .
　これらの中でも、キノンジアジド化合物として、フェノール化合物および４－ナフトキノンジアジドスルホニル基とのエステルを含むことが好ましい。これによりｉ線露光に対するより高い感度と、より高い解像度を得ることができる。 Among these, the quinonediazide compound preferably contains a phenol compound and an ester with a 4-naphthoquinonediazide sulfonyl group. This makes it possible to obtain higher sensitivity to i-line exposure and higher resolution.
　本発明の樹脂組成物に用いるキノンジアジド化合物の含有量は、樹脂１００質量部に対して、１～５０質量部が好ましく、１０～４０質量部がより好ましい。キノンジアジド化合物の含有量をこの範囲とすることにより、露光部と未露光部のコントラストが得られることでより高感度化を図ることができるため好ましい。さらに増感剤などを必要に応じて添加してもよい。 The content of the quinonediazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, based on 100 parts by mass of the resin. By setting the content of the quinonediazide compound within this range, the contrast between the exposed area and the unexposed area can be obtained, which is preferable because it is possible to achieve higher sensitivity. Furthermore, a sensitizer or the like may be added as necessary.
　光酸発生剤は、オキシムスルホネート基を含む化合物（以下、単に「オキシムスルホネート化合物」ともいう）であることが好ましい。
　オキシムスルホネート化合物は、オキシムスルホネート基を有していれば特に制限はないが、下記式（ＯＳ－１）、後述する式（ＯＳ－１０３）、式（ＯＳ－１０４）、又は、式（ＯＳ－１０５）で表されるオキシムスルホネート化合物であることが好ましい。 The photoacid generator is preferably a compound containing an oximesulfonate group (hereinafter also simply referred to as "oximesulfonate compound").
The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group. 105) is preferably an oxime sulfonate compound.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　式（ＯＳ－１）中、Ｘ３は、アルキル基、アルコキシ基、又は、ハロゲン原子を表す。Ｘ３が複数存在する場合は、それぞれ同一であってもよいし、異なっていてもよい。上記Ｘ３におけるアルキル基及びアルコキシ基は、置換基を有していてもよい。上記Ｘ３におけるアルキル基としては、炭素数１～４の、直鎖状又は分岐状アルキル基が好ましい。上記Ｘ３におけるアルコキシ基としては、炭素数１～４の直鎖状又は分岐状アルコキシ基が好ましい。上記Ｘ３におけるハロゲン原子としては、塩素原子又はフッ素原子が好ましい。
　式（ＯＳ－１）中、ｍ３は、０～３の整数を表し、０又は１が好ましい。ｍ３が２又は３であるとき、複数のＸ３は同一でも異なっていてもよい。
　式（ＯＳ－１）中、Ｒ３４は、アルキル基又はアリール基を表し、炭素数１～１０のアルキル基、炭素数１～１０のアルコキシ基、炭素数１～５のハロゲン化アルキル基、炭素数１～５のハロゲン化アルコキシ基、Ｗで置換されていてもよいフェニル基、Ｗで置換されていてもよいナフチル基又はＷで置換されていてもよいアントラニル基であることが好ましい。Ｗは、ハロゲン原子、シアノ基、ニトロ基、炭素数１～１０のアルキル基、炭素数１～１０のアルコキシ基、炭素数１～５のハロゲン化アルキル基又は炭素数１～５のハロゲン化アルコキシ基、炭素数６～２０のアリール基、炭素数６～２０のハロゲン化アリール基を表す。 In formula (OS- 1 ), X3 represents an alkyl group, an alkoxy group, or a halogen atom. When there are multiple X3's, they may be the same or different. The alkyl group and alkoxy group in X3 above may have a substituent. The alkyl group for X 3 above is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group for X 3 is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. As the halogen atom for X3 , a chlorine atom or a fluorine atom is preferable.
In formula (OS-1), m3 represents an integer of 0 to 3, preferably 0 or 1. When m3 is 2 or 3 , multiple X3's may be the same or different.
In formula (OS-1), R 34 represents an alkyl group or an aryl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a carbon It is preferably a halogenated alkoxy group of number 1 to 5, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W or an anthranyl group optionally substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms; group, an aryl group having 6 to 20 carbon atoms, and an aryl halide group having 6 to 20 carbon atoms.
　式（ＯＳ－１）中、ｍ３が３であり、Ｘ３がメチル基であり、Ｘ３の置換位置がオルト位であり、Ｒ３４が炭素数１～１０の直鎖状アルキル基、７，７－ジメチル－２－オキソノルボルニルメチル基、又は、ｐ－トリル基である化合物が特に好ましい。 In formula (OS-1), m3 is 3, X 3 is a methyl group, the substitution position of X 3 is the ortho position, R 34 is a linear alkyl group having 1 to 10 carbon atoms, 7, Compounds with a 7-dimethyl-2-oxonorbornylmethyl group or a p-tolyl group are particularly preferred.
　式（ＯＳ－１）で表されるオキシムスルホネート化合物の具体例としては、特開２０１１－２０９６９２号公報の段落番号００６４～００６８、特開２０１５－１９４６７４号公報の段落番号０１５８～０１６７に記載された以下の化合物が例示され、これらの内容は本明細書に組み込まれる。 Specific examples of the oxime sulfonate compound represented by formula (OS-1) are described in paragraph numbers 0064 to 0068 of JP-A-2011-209692 and paragraph numbers 0158-0167 of JP-A-2015-194674. The following compounds are exemplified, the contents of which are incorporated herein.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　式（ＯＳ－１０３）～式（ＯＳ－１０５）中、Ｒｓ１はアルキル基、アリール基又はヘテロアリール基を表し、複数存在する場合のあるＲｓ２はそれぞれ独立に、水素原子、アルキル基、アリール基又はハロゲン原子を表し、複数存在する場合のあるＲｓ６はそれぞれ独立に、ハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基又はアルコキシスルホニル基を表し、ＸｓはＯ又はＳを表し、ｎｓは１又は２を表し、ｍｓは０～６の整数を表す。
　式（ＯＳ－１０３）～式（ＯＳ－１０５）中、Ｒｓ１で表されるアルキル基（炭素数１～３０が好ましい）、アリール基（炭素数６～３０が好ましい）又はヘテロアリール基（炭素数４～３０が好ましい）は、本発明の効果が得られる範囲で公知の置換基を有していてもよい。 In formulas (OS-103) to (OS-105), R s1 represents an alkyl group, an aryl group or a heteroaryl group, and R s2 , which may be present in plurality, is each independently a hydrogen atom, an alkyl group, or an aryl represents a group or a halogen atom, and each R s6 which may be present in plurality independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, and Xs represents O or S. , ns represents 1 or 2, and ms represents an integer of 0-6.
In formulas (OS-103) to (OS-105), an alkyl group (preferably having 1 to 30 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms) or a heteroaryl group (preferably having 6 to 30 carbon atoms) represented by R s1 Numbers 4 to 30 are preferable) may have a known substituent as long as the effects of the present invention can be obtained.
　式（ＯＳ－１０３）～式（ＯＳ－１０５）中、Ｒｓ２は、水素原子、アルキル基（炭素数１～１２が好ましい）又はアリール基（炭素数６～３０が好ましい）であることが好ましく、水素原子又はアルキル基であることがより好ましい。化合物中に２以上存在する場合のあるＲｓ２のうち、１つ又は２つがアルキル基、アリール基又はハロゲン原子であることが好ましく、１つがアルキル基、アリール基又はハロゲン原子であることがより好ましく、１つがアルキル基であり、かつ残りが水素原子であることが特に好ましい。Ｒｓ２で表されるアルキル基又はアリール基は、本発明の効果が得られる範囲で公知の置換基を有していてもよい。
　式（ＯＳ－１０３）、式（ＯＳ－１０４）、又は、式（ＯＳ－１０５）中、ＸｓはＯ又はＳを表し、Ｏであることが好ましい。上記式（ＯＳ－１０３）～（ＯＳ－１０５）において、Ｘｓを環員として含む環は、５員環又は６員環である。 In formulas (OS-103) to (OS-105), R s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms). , a hydrogen atom or an alkyl group. Among R s2 that may be present in the compound at least two times, one or two are preferably an alkyl group, an aryl group or a halogen atom, and one is more preferably an alkyl group, an aryl group or a halogen atom. , one is an alkyl group and the rest are hydrogen atoms. The alkyl group or aryl group represented by R s2 may have a known substituent as long as the effects of the present invention can be obtained.
In formula (OS-103), formula (OS-104), or formula (OS-105), Xs represents O or S, preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5- or 6-membered ring.
　式（ＯＳ－１０３）～式（ＯＳ－１０５）中、ｎｓは１又は２を表し、ＸｓがＯである場合、ｎｓは１であることが好ましく、また、ＸｓがＳである場合、ｎｓは２であることが好ましい。
　式（ＯＳ－１０３）～式（ＯＳ－１０５）中、Ｒｓ６で表されるアルキル基（炭素数１～３０が好ましい）及びアルキルオキシ基（炭素数１～３０が好ましい）は、置換基を有していてもよい。
　式（ＯＳ－１０３）～式（ＯＳ－１０５）中、ｍｓは０～６の整数を表し、０～２の整数であることが好ましく、０又は１であることがより好ましく、０であることが特に好ましい。 In formulas (OS-103) to (OS-105), ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is 2 is preferred.
In formulas (OS-103) to (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms) and alkyloxy group (preferably having 1 to 30 carbon atoms) represented by R s6 are substituents. may have.
In formulas (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0 is particularly preferred.
　また、上記式（ＯＳ－１０３）で表される化合物は、下記式（ＯＳ－１０６）、式（ＯＳ－１１０）又は式（ＯＳ－１１１）で表される化合物であることが特に好ましく、上記式（ＯＳ－１０４）で表される化合物は、下記式（ＯＳ－１０７）で表される化合物であることが特に好ましく、上記式（ＯＳ－１０５）で表される化合物は、下記式（ＯＳ－１０８）又は式（ＯＳ－１０９）で表される化合物であることが特に好ましい。
Figure JPOXMLDOC01-appb-C000026
 Further, the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111). The compound represented by the formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is a compound represented by the following formula (OS -108) or a compound represented by the formula (OS-109).
Figure JPOXMLDOC01-appb-C000026
　式（ＯＳ－１０６）～式（ＯＳ－１１１）中、Ｒｔ１はアルキル基、アリール基又はヘテロアリール基を表し、Ｒｔ７は、水素原子又は臭素原子を表し、Ｒｔ８は水素原子、炭素数１～８のアルキル基、ハロゲン原子、クロロメチル基、ブロモメチル基、ブロモエチル基、メトキシメチル基、フェニル基又はクロロフェニル基を表し、Ｒｔ９は水素原子、ハロゲン原子、メチル基又はメトキシ基を表し、Ｒｔ２は水素原子又はメチル基を表す。
　式（ＯＳ－１０６）～式（ＯＳ－１１１）中、Ｒｔ７は、水素原子又は臭素原子を表し、水素原子であることが好ましい。 In formulas (OS-106) to (OS-111), R t1 represents an alkyl group, an aryl group or a heteroaryl group, R t7 represents a hydrogen atom or a bromine atom, R t8 represents a hydrogen atom, the number of carbon atoms 1 to 8 alkyl group, halogen atom, chloromethyl group, bromomethyl group, bromoethyl group, methoxymethyl group, phenyl group or chlorophenyl group; R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group; t2 represents a hydrogen atom or a methyl group.
In formulas (OS-106) to (OS-111), R t7 represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.
　式（ＯＳ－１０６）～式（ＯＳ－１１１）中、Ｒｔ８は、水素原子、炭素数１～８のアルキル基、ハロゲン原子、クロロメチル基、ブロモメチル基、ブロモエチル基、メトキシメチル基、フェニル基又はクロロフェニル基を表し、炭素数１～８のアルキル基、ハロゲン原子又はフェニル基であることが好ましく、炭素数１～８のアルキル基であることがより好ましく、炭素数１～６のアルキル基であることが更に好ましく、メチル基であることが特に好ましい。 In formulas (OS-106) to (OS-111), R t8 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group. or represents a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms is more preferred, and a methyl group is particularly preferred.
　式（ＯＳ－１０６）～式（ＯＳ－１１１）中、Ｒｔ９は、水素原子、ハロゲン原子、メチル基又はメトキシ基を表し、水素原子であることが好ましい。
　Ｒｔ２は、水素原子又はメチル基を表し、水素原子であることが好ましい。
　また、上記オキシムスルホネート化合物において、オキシムの立体構造（Ｅ，Ｚ）については、いずれか一方であっても、混合物であってもよい。
　上記式（ＯＳ－１０３）～式（ＯＳ－１０５）で表されるオキシムスルホネート化合物の具体例としては、特開２０１１－２０９６９２号公報の段落番号００８８～００９５、特開２０１５－１９４６７４号公報の段落番号０１６８～０１９４に記載の化合物が例示され、これらの内容は本明細書に組み込まれる。 In formulas (OS-106) to (OS-111), R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, preferably a hydrogen atom.
R t2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
In the above oxime sulfonate compound, the oximes may have either one of the three-dimensional structures (E, Z) or may be a mixture.
Specific examples of the oxime sulfonate compounds represented by the formulas (OS-103) to (OS-105) include paragraphs 0088 to 0095 of JP-A-2011-209692 and paragraphs of JP-A-2015-194674. Compounds described in numbers 0168-0194 are exemplified, the contents of which are incorporated herein.
　オキシムスルホネート基を少なくとも１つを含むオキシムスルホネート化合物の好適な他の態様としては、下記式（ＯＳ－１０１）、式（ＯＳ－１０２）で表される化合物が挙げられる。 Other preferred embodiments of the oximesulfonate compound containing at least one oximesulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　式（ＯＳ－１０１）又は式（ＯＳ－１０２）中、Ｒｕ９は、水素原子、アルキル基、アルケニル基、アルコキシ基、アルコキシカルボニル基、アシル基、カルバモイル基、スルファモイル基、スルホ基、シアノ基、アリール基又はヘテロアリール基を表す。Ｒｕ９がシアノ基又はアリール基である態様がより好ましく、Ｒｕ９がシアノ基、フェニル基又はナフチル基である態様が更に好ましい。
　式（ＯＳ－１０１）又は式（ＯＳ－１０２）中、Ｒｕ２ａは、アルキル基又はアリール基を表す。
　式（ＯＳ－１０１）又は式（ＯＳ－１０２）中、Ｘｕは、－Ｏ－、－Ｓ－、－ＮＨ－、－ＮＲｕ５－、－ＣＨ２－、－ＣＲｕ６Ｈ－又はＣＲｕ６Ｒｕ７－を表し、Ｒｕ５～Ｒｕ７はそれぞれ独立に、アルキル基又はアリール基を表す。 In formula (OS-101) or formula (OS-102), R u9 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, It represents an aryl group or a heteroaryl group. An aspect in which Ru9 is a cyano group or an aryl group is more preferred, and an aspect in which Ru9 is a cyano group, a phenyl group or a naphthyl group is even more preferred.
In formula (OS-101) or (OS-102), R u2a represents an alkyl group or an aryl group.
In formula (OS-101) or formula (OS-102), Xu is -O-, -S-, -NH-, -NR u5 -, -CH 2 -, -CR u6 H- or CR u6 R u7 —, and R u5 to R u7 each independently represent an alkyl group or an aryl group.
　式（ＯＳ－１０１）又は式（ＯＳ－１０２）中、Ｒｕ１～Ｒｕ４はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルケニル基、アルコキシ基、アミノ基、アルコキシカルボニル基、アルキルカルボニル基、アリールカルボニル基、アミド基、スルホ基、シアノ基又はアリール基を表す。Ｒｕ１～Ｒｕ４のうちの２つがそれぞれ互いに結合して環を形成してもよい。このとき、環が縮環してベンゼン環ともに縮合環を形成していてもよい。Ｒｕ１～Ｒｕ４としては、水素原子、ハロゲン原子又はアルキル基が好ましく、また、Ｒｕ１～Ｒｕ４のうちの少なくとも２つが互いに結合してアリール基を形成する態様も好ましい。中でも、Ｒｕ１～Ｒｕ４がいずれも水素原子である態様が好ましい。上記した置換基は、いずれも、更に置換基を有していてもよい。 In formula (OS-101) or (OS-102), R u1 to R u4 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group. , an arylcarbonyl group, an amido group, a sulfo group, a cyano group or an aryl group. Two of R u1 to R u4 may each combine to form a ring. At this time, the ring may be condensed to form a condensed ring together with the benzene ring. R u1 to R u4 are preferably hydrogen atoms, halogen atoms or alkyl groups, and an aspect in which at least two of R u1 to R u4 are bonded to each other to form an aryl group is also preferable. Among them, an aspect in which all of R u1 to R u4 are hydrogen atoms is preferable. Any of the substituents described above may further have a substituent.
　上記式（ＯＳ－１０１）で表される化合物は、式（ＯＳ－１０２）で表される化合物であることがより好ましい。
　また、上記オキシムスルホネート化合物において、オキシムやベンゾチアゾール環の立体構造（Ｅ，Ｚ等）についてはそれぞれ、いずれか一方であっても、混合物であってもよい。
　式（ＯＳ－１０１）で表される化合物の具体例としては、特開２０１１－２０９６９２号公報の段落番号０１０２～０１０６、特開２０１５－１９４６７４号公報の段落番号０１９５～０２０７に記載の化合物が例示され、これらの内容は本明細書に組み込まれる。
　上記化合物の中でも、下記ｂ－９、ｂ－１６、ｂ－３１、ｂ－３３が好ましい。
Figure JPOXMLDOC01-appb-C000028
　市販品としては、ＷＰＡＧ－３３６（富士フイルム和光純薬（株）製）、ＷＰＡＧ－４４３（富士フイルム和光純薬（株）製）、ＭＢＺ－１０１（みどり化学（株）製）等を挙げることができる。 The compound represented by formula (OS-101) is more preferably a compound represented by formula (OS-102).
In the above oxime sulfonate compound, the stereostructures (E, Z, etc.) of the oxime and benzothiazole rings may be either one or a mixture.
Specific examples of the compound represented by formula (OS-101) include compounds described in paragraph numbers 0102 to 0106 of JP-A-2011-209692 and paragraph numbers 0195-0207 of JP-A-2015-194674. and the contents of which are incorporated herein.
Among the above compounds, the following b-9, b-16, b-31 and b-33 are preferred.
Figure JPOXMLDOC01-appb-C000028
Examples of commercially available products include WPAG-336 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), MBZ-101 (manufactured by Midori Chemical Co., Ltd.), and the like. can be done.
　また、下記構造式で表される化合物も好ましい例として挙げられる。
Figure JPOXMLDOC01-appb-C000029
 In addition, compounds represented by the following structural formulas are also preferred examples.
Figure JPOXMLDOC01-appb-C000029
　有機ハロゲン化化合物としては、具体的には、若林等「Ｂｕｌｌ　Ｃｈｅｍ．Ｓｏｃ　Ｊａｐａｎ」４２、２９２４（１９６９）、米国特許第３，９０５，８１５号明細書、特公昭４６－４６０５号、特開昭４８－３６２８１号公報、特開昭５５－３２０７０号公報、特開昭６０－２３９７３６号公報、特開昭６１－１６９８３５号公報、特開昭６１－１６９８３７号公報、特開昭６２－５８２４１号公報、特開昭６２－２１２４０１号公報、特開昭６３－７０２４３号公報、特開昭６３－２９８３３９号公報、Ｍ．Ｐ．Ｈｕｔｔ“Ｊｕｒｎａｌ　ｏｆ　Ｈｅｔｅｒｏｃｙｃｌｉｃ　Ｃｈｅｍｉｓｔｒｙ”１（Ｎｏ３），（１９７０）などに記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。特に、トリハロメチル基が置換したオキサゾール化合物：Ｓ－トリアジン化合物が好ましい例として挙げられる。
　より好適には、すくなくとも一つのモノ、ジ、又はトリハロゲン置換メチル基がｓ－トリアジン環に結合したｓ－トリアジン誘導体、具体的には、例えば、２，４，６－トリス（モノクロロメチル）－ｓ－トリアジン、２，４，６－トリス（ジクロロメチル）－ｓ－トリアジン、２，４，６－トリス（トリクロロメチル）－ｓ－トリアジン、２－メチル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２―ｎ－プロピル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（α，α，β－トリクロロエチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－フェニル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－メトキシフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（３，４－エポキシフェニル）－４、６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－クロロフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－〔１－（ｐ－メトキシフェニル）－２，４－ブタジエニル〕－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－スチリル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－メトキシスチリル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－ｉ－プロピルオキシスチリル）－４、６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－トリル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－ナトキシナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－フェニルチオ－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－ベンジルチオ－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２，４，６－トリス（ジブロモメチル）－ｓ－トリアジン、２，４，６－トリス（トリブロモメチル）－ｓ－トリアジン、２－メチル－４，６－ビス（トリブロモメチル）－ｓ－トリアジン、２－メトキシ－４，６－ビス（トリブロモメチル）－ｓ－トリアジン等が挙げられる。 Specific examples of organic halogenated compounds include those described by Wakabayashi et al., "Bull Chem. Soc Japan" 42, 2924 (1969), US Pat. 48-36281, JP-A-55-32070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241 , JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, M.P. P. Hutt "Journal of Heterocyclic Chemistry" 1 (No 3), (1970), the contents of which are incorporated herein. Particularly preferred examples include an oxazole compound substituted with a trihalomethyl group: an S-triazine compound.
More preferably, s-triazine derivatives having at least one mono-, di-, or trihalogen-substituted methyl group attached to the s-triazine ring, specifically, for example, 2,4,6-tris(monochloromethyl)- s-triazine, 2,4,6-tris(dichloromethyl)-s-triazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)- s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine , 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4-epoxy phenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[1-(p-methoxyphenyl) -2,4-butadienyl]-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxystyryl)-4 , 6-bis(trichloromethyl)-s-triazine, 2-(pi-propyloxystyryl)-4, 6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6 -bis(trichloromethyl)-s-triazine, 2-(4-nathoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenylthio-4,6-bis(trichloromethyl)-s-triazine , 2-benzylthio-4,6-bis(trichloromethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s- triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-methoxy-4,6-bis(tribromomethyl)-s-triazine and the like.
　有機ホウ酸塩化合物としては、例えば、特開昭６２－１４３０４４号公報、特開昭６２－１５０２４２号公報、特開平９－１８８６８５号公報、特開平９－１８８６８６号公報、特開平９－１８８７１０号公報、特開２０００－１３１８３７号公報、特開２００２－１０７９１６号公報、特許第２７６４７６９号公報、特開２００２－１１６５３９号公報、等、及び、Ｋｕｎｚ，Ｍａｒｔｉｎ“Ｒａｄ　Ｔｅｃｈ'９８．Ｐｒｏｃｅｅｄｉｎｇ　Ａｐｒｉｌ　１９－２２，１９９８，Ｃｈｉｃａｇｏ”等に記載される有機ホウ酸塩、特開平６－１５７６２３号公報、特開平６－１７５５６４号公報、特開平６－１７５５６１号公報に記載の有機ホウ素スルホニウム錯体或いは有機ホウ素オキソスルホニウム錯体、特開平６－１７５５５４号公報、特開平６－１７５５５３号公報に記載の有機ホウ素ヨードニウム錯体、特開平９－１８８７１０号公報に記載の有機ホウ素ホスホニウム錯体、特開平６－３４８０１１号公報、特開平７－１２８７８５号公報、特開平７－１４０５８９号公報、特開平７－３０６５２７号公報、特開平７－２９２０１４号公報等の有機ホウ素遷移金属配位錯体等が具体例として挙げられ、これらの内容は本明細書に組み込まれる。 Examples of organic borate compounds include JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, and JP-A-9-188710. Publications, JP-A-2000-131837, JP-A-2002-107916, JP-A-2764769, JP-A-2002-116539, etc., and Kunz, Martin "Rad Tech'98. Proceeding April 19-22 , 1998, Chicago", etc., organic boron sulfonium complexes or organic boron oxosulfonium described in JP-A-6-157623, JP-A-6-175564, and JP-A-6-175561. complexes, JP-A-6-175554, organic boron-iodonium complexes described in JP-A-6-175553, organic boron-phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-H9 No. 7-128785, JP-A-7-140589, JP-A-7-306527, JP-A-7-292014 and the like organoboron transition metal coordination complexes are mentioned as specific examples. incorporated herein.
　ジスルホン化合物としては、特開昭６１－１６６５４４号公報、特願２００１－１３２３１８公報等に記載されている化合物およびジアゾジスルホン化合物が挙げられる。 Examples of the disulfone compound include compounds described in JP-A-61-166544, Japanese Patent Application No. 2001-132318, and diazodisulfone compounds.
　上記オニウム塩化合物としては、例えば、Ｓ．Ｉ．Ｓｃｈｌｅｓｉｎｇｅｒ，Ｐｈｏｔｏｇｒ．Ｓｃｉ．Ｅｎｇ．，１８，３８７（１９７４）、Ｔ．Ｓ．Ｂａｌ　ｅｔ　ａｌ，Ｐｏｌｙｍｅｒ，２１，４２３（１９８０）に記載のジアゾニウム塩、米国特許第４，０６９，０５５号明細書、特開平４－３６５０４９号公報等に記載のアンモニウム塩、米国特許第４，０６９，０５５号、同４，０６９，０５６号の各明細書に記載のホスホニウム塩、欧州特許第１０４、１４３号、米国特許第３３９，０４９号、同第４１０，２０１号の各明細書、特開平２－１５０８４８号、特開平２－２９６５１４号公報に記載のヨードニウム塩、欧州特許第３７０，６９３号、同３９０，２１４号、同２３３，５６７号、同２９７，４４３号、同２９７，４４２号、米国特許第４，９３３，３７７号、同１６１，８１１号、同４１０，２０１号、同３３９，０４９号、同４，７６０，０１３号、同４，７３４，４４４号、同２，８３３，８２７号、独国特許第２，９０４，６２６号、同３，６０４，５８０号、同３，６０４，５８１号の各明細書に記載のスルホニウム塩、Ｊ．Ｖ．Ｃｒｉｖｅｌｌｏ　ｅｔ　ａｌ，Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，１０（６），１３０７（１９７７）、Ｊ．Ｖ．Ｃｒｉｖｅｌｌｏ　ｅｔ　ａｌ，Ｊ．Ｐｏｌｙｍｅｒ　Ｓｃｉ．，Ｐｏｌｙｍｅｒ　Ｃｈｅｍ．Ｅｄ．，１７，１０４７（１９７９）に記載のセレノニウム塩、Ｃ．Ｓ．Ｗｅｎ　ｅｔ　ａｌ，Ｔｅｈ，Ｐｒｏｃ．Ｃｏｎｆ．Ｒａｄ．Ｃｕｒｉｎｇ　ＡＳＩＡ，ｐ４７８　Ｔｏｋｙｏ，Ｏｃｔ（１９８８）に記載のアルソニウム塩、ピリジニウム塩等のオニウム塩等が挙げられ、これらの内容は本明細書に組み込まれる。 As the onium salt compound, for example, S.I. I. Schlesinger, Photograph. Sci. Eng. , 18, 387 (1974); S. Bal et al, Polymer, 21,423 (1980), diazonium salts, US Pat. , 055, 4,069,056, EP 104,143, US Pat. 2-150848, iodonium salts described in JP-A-2-296514, European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, U.S. Pat. Nos. 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827 German Patent Nos. 2,904,626, 3,604,580 and 3,604,581; V. Crivello et al, Macromolecules, 10(6), 1307 (1977); V. Crivello et al, J. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979); S. Wen et al, Teh, Proc. Conf. Rad. and onium salts such as arsonium salts and pyridinium salts described in Curing ASIA, p478, Tokyo, October (1988), the contents of which are incorporated herein.
　オニウム塩としては、下記一般式（ＲＩ－Ｉ）～（ＲＩ－ＩＩＩ）で表されるオニウム塩が挙げられる。
Figure JPOXMLDOC01-appb-C000030
　式（ＲＩ－Ｉ）中、Ａｒ１１は置換基を１～６有していても良い炭素数２０以下のアリール基を表し、好ましい置換基としては炭素数１～１２のアルキル基、炭素数２～１２のアルケニル基、炭素数２～１２のアルキニル基、炭素数６～１２のアリール基、炭素数１～１２のアルコキシ基、炭素数１～１２のアリーロキシ基、ハロゲン原子、炭素数１～１２のアルキルアミノ基、炭素数２～１２のジアルキルアミノ基、アルキル基の炭素数が１～１２のアルキルアミド基又はアリール基の炭素数が６～２０のアリールアミド基、カルボニル基、カルボキシ基、シアノ基、スルホニル基、炭素数１～１２のチオアルキル基、炭素数１～１２のチオアリール基が挙げられる。Ｚ１１ －は１価の陰イオンを表し、ハロゲンイオン、過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、チオスルホン酸イオン、硫酸イオンであり、安定性の面から過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオンが好ましい。式（ＲＩ－ＩＩ）中、Ａｒ２１、Ａｒ２２は各々独立に置換基を１～６有していてもよい炭素数１～２０のアリール基を表し、好ましい置換基としては炭素数１～１２のアルキル基、炭素数２～１２のアルケニル基、炭素数２～１２のアルキニル基、炭素数１～１２のアリール基、炭素数１～１２のアルコキシ基、炭素数１～１２のアリーロキシ基、ハロゲン原子、炭素数１～１２のモノアルキルアミノ基、アルキル基の炭素数がそれぞれ独立に１～１２のジアルキルアミノ基、アルキル基の炭素数が炭素数１～１２のアルキルアミド基又はアリールアミド基、カルボニル基、カルボキシ基、シアノ基、スルホニル基、炭素数１～１２のチオアルキル基、炭素数１～１２のチオアリール基が挙げられる。Ｚ２１－は１価の陰イオンを表し、ハロゲンイオン、過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、チオスルホン酸イオン、硫酸イオンであり、安定性、反応性の面から過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、カルボン酸イオンが好ましい。式（ＲＩ－ＩＩＩ）中、Ｒ３１、Ｒ３２、Ｒ３３は各々独立に置換基を１～６有していても良い炭素数６～２０のアリール基又はアルキル基、アルケニル基、アルキニル基を表し、好ましくは反応性、安定性の面から、アリール基であることが望ましい。好ましい置換基としては炭素数１～１２のアルキル基、炭素数２～１２のアルケニル基、炭素数２～１２のアルキニル基、炭素数１～１２のアリール基、炭素数１～１２のアルコキシ基、炭素数１～１２のアリーロキシ基、ハロゲン原子、炭素数１～１２のモノアルキルアミノ基、アルキル基の炭素数がそれぞれ独立に炭素数１～１２のジアルキルアミノ基、アルキル基の炭素数が炭素数１～１２のアルキルアミド基又はアリールアミド基、カルボニル基、カルボキシ基、シアノ基、スルホニル基、炭素数１～１２のチオアルキル基、炭素数１～１２のチオアリール基が挙げられる。Ｚ３１ －は１価の陰イオンを表し、ハロゲンイオン、過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、チオスルホン酸イオン、硫酸イオンであり、安定性、反応性の面から過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、カルボン酸イオンが好ましい。 Onium salts include onium salts represented by the following general formulas (RI-I) to (RI-III).
Figure JPOXMLDOC01-appb-C000030
In formula (RI-I), Ar 11 represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents. ~12 alkenyl groups, alkynyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryloxy groups having 1 to 12 carbon atoms, halogen atoms, and 1 to 12 carbon atoms. an alkylamino group, a dialkylamino group having 2 to 12 carbon atoms, an alkylamide group having an alkyl group having 1 to 12 carbon atoms or an arylamide group having an aryl group having 6 to 20 carbon atoms, a carbonyl group, a carboxy group, a cyano groups, sulfonyl groups, thioalkyl groups having 1 to 12 carbon atoms, and thioaryl groups having 1 to 12 carbon atoms. Z 11 - represents a monovalent anion such as a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, a sulfate ion, and a stable Perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, and sulfinate ion are preferred from the aspect. In formula (RI-II), Ar 21 and Ar 22 each independently represent an aryl group having 1 to 20 carbon atoms which may have 1 to 6 substituents, and preferred substituents are 1 to 12 carbon atoms. an alkyl group having 2 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen an atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having an alkyl group having 1 to 12 carbon atoms, an alkylamido group or an arylamide group having an alkyl group having 1 to 12 carbon atoms, carbonyl group, carboxy group, cyano group, sulfonyl group, thioalkyl group having 1 to 12 carbon atoms, and thioaryl group having 1 to 12 carbon atoms. Z21 − represents a monovalent anion, and is a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, reaction Perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, and carboxylate ions are preferred from the viewpoint of their properties. In formula (RI-III), R 31 , R 32 and R 33 each independently represents an aryl group, an alkyl group, an alkenyl group or an alkynyl group having 6 to 20 carbon atoms which may have 1 to 6 substituents. In view of reactivity and stability, it is preferably an aryl group. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms in each alkyl group, and an alkyl group having 1 to 12 carbon atoms; 1 to 12 alkylamide or arylamido groups, carbonyl groups, carboxy groups, cyano groups, sulfonyl groups, C1 to C12 thioalkyl groups, and C1 to C12 thioaryl groups. Z 31 − represents a monovalent anion and is a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, From the viewpoint of reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, and carboxylate ion are preferred.
　好ましい光酸発生剤の具体例としては、以下のものが挙げられる。
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
 Specific examples of preferred photoacid generators include the following.
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
　光酸発生剤は、樹脂組成物の全固形分に対し、０．１～２０質量％使用することが好ましく、０．５～１８質量％使用することがより好ましく、０．５～１０質量％使用することが更に好ましく、０．５～３質量％使用することが一層好ましく、０．５～１．２質量％使用することがより一層好ましい。
　光酸発生剤は、１種単独で使用されても、複数種の組み合わせで使用されてもよい。複数種の組み合わせの場合には、それらの合計量が上記範囲にあることが好ましい。
　また、所望の光源に対して、感光性を付与する為、増感剤と併用することも好ましい。 The photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, and 0.5 to 10% by mass, based on the total solid content of the resin composition. It is more preferably used, more preferably 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass.
A photo-acid generator may be used individually by 1 type, or may be used in multiple types combination. In the case of a combination of multiple types, the total amount thereof is preferably within the above range.
Moreover, in order to impart photosensitivity to a desired light source, it is also preferable to use together with a sensitizer.
＜塩基発生剤＞
　本発明の樹脂組成物は、塩基発生剤を含んでもよい。ここで、塩基発生剤とは、物理的または化学的な作用によって塩基を発生することができる化合物である。本発明の樹脂組成物にとって好ましい塩基発生剤としては、熱塩基発生剤および光塩基発生剤が挙げられる。
　特に、樹脂組成物が環化樹脂の前駆体を含む場合、樹脂組成物は塩基発生剤を含むことが好ましい。樹脂組成物が熱塩基発生剤を含有することによって、例えば加熱により前駆体の環化反応を促進でき、硬化物の機械特性や耐薬品性が良好なものとなり、例えば半導体パッケージ中に含まれる再配線層用層間絶縁膜としての性能が良好となる。
　塩基発生剤としては、イオン型塩基発生剤でもよく、非イオン型塩基発生剤でもよい。塩基発生剤から発生する塩基としては、例えば、２級アミン、３級アミンが挙げられる。
　本発明に係る塩基発生剤について特に制限はなく、公知の塩基発生剤を用いることができる。公知の塩基発生剤としては、例えば、カルバモイルオキシム化合物、カルバモイルヒドロキシルアミン化合物、カルバミン酸化合物、ホルムアミド化合物、アセトアミド化合物、カルバメート化合物、ベンジルカルバメート化合物、ニトロベンジルカルバメート化合物、スルホンアミド化合物、イミダゾール誘導体化合物、アミンイミド化合物、ピリジン誘導体化合物、α－アミノアセトフェノン誘導体化合物、４級アンモニウム塩誘導体化合物、ピリジニウム塩、α－ラクトン環誘導体化合物、アミンイミド化合物、フタルイミド誘導体化合物、アシルオキシイミノ化合物、などを用いることができる。
非イオン型塩基発生剤の具体的な化合物としては、式（Ｂ１）、式（Ｂ２）、又は式（Ｂ３）で表される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000035
 <Base generator>
The resin composition of the present invention may contain a base generator. Here, the base generator is a compound capable of generating a base by physical or chemical action. Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators.
In particular, when the resin composition contains a cyclized resin precursor, the resin composition preferably contains a base generator. By containing a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted, for example, by heating, and the cured product has good mechanical properties and chemical resistance. Performance as an interlayer insulating film for wiring layers is improved.
The base generator may be an ionic base generator or a non-ionic base generator. Examples of bases generated from base generators include secondary amines and tertiary amines.
There are no particular restrictions on the base generator used in the present invention, and known base generators can be used. Examples of known base generators include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, and amine imides. compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, acyloxyimino compounds, and the like can be used.
Specific compounds of the nonionic base generator include compounds represented by Formula (B1), Formula (B2), or Formula (B3).
Figure JPOXMLDOC01-appb-C000035
　式（Ｂ１）及び式（Ｂ２）中、Ｒｂ１、Ｒｂ２及びＲｂ３はそれぞれ独立に、第三級アミン構造を有しない有機基、ハロゲン原子又は水素原子である。ただし、Ｒｂ１及びＲｂ２が同時に水素原子となることはない。また、Ｒｂ１、Ｒｂ２及びＲｂ３はいずれもカルボキシ基を有することはない。なお、本明細書で第三級アミン構造とは、３価の窒素原子の３つの結合手がいずれも炭化水素系の炭素原子と共有結合している構造を指す。したがって、結合した炭素原子がカルボニル基をなす炭素原子の場合、つまり窒素原子とともにアミド基を形成する場合はこの限りではない。 In Formula (B1) and Formula (B2), Rb 1 , Rb 2 and Rb 3 are each independently an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb 1 and Rb 2 are not hydrogen atoms at the same time. Also, none of Rb 1 , Rb 2 and Rb 3 has a carboxy group. In this specification, the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when forming an amide group together with the nitrogen atom, this is not the case.
　式（Ｂ１）、（Ｂ２）中、Ｒｂ１、Ｒｂ２及びＲｂ３は、これらのうち少なくとも１つが環状構造を含むことが好ましく、少なくとも２つが環状構造を含むことがより好ましい。環状構造としては、単環及び縮合環のいずれであってもよく、単環又は単環が２つ縮合した縮合環が好ましい。単環は、５員環又は６員環が好ましく、６員環がより好ましい。単環は、シクロヘキサン環及びベンゼン環が好ましく、シクロヘキサン環がより好ましい。 In formulas (B1) and (B2), at least one of Rb 1 , Rb 2 and Rb 3 preferably contains a cyclic structure, and more preferably at least two of them contain a cyclic structure. The cyclic structure may be either a single ring or a condensed ring, preferably a single ring or a condensed ring in which two single rings are condensed. The monocyclic ring is preferably a 5- or 6-membered ring, more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring and a benzene ring, more preferably a cyclohexane ring.
　より具体的にＲｂ１及びＲｂ２は、水素原子、アルキル基（炭素数１～２４が好ましく、２～１８がより好ましく、３～１２が更に好ましい）、アルケニル基（炭素数２～２４が好ましく、２～１８がより好ましく、３～１２が更に好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０が更に好ましい）、又はアリールアルキル基（炭素数７～２５が好ましく、７～１９がより好ましく、７～１２が更に好ましい）であることが好ましい。これらの基は、本発明の効果を奏する範囲で置換基を有していてもよい。Ｒｂ１とＲｂ２とは互いに結合して環を形成していてもよい。形成される環としては、４～７員の含窒素複素環が好ましい。Ｒｂ１及びＲｂ２は特に、置換基を有してもよい直鎖、分岐、又は環状のアルキル基（炭素数１～２４が好ましく、２～１８がより好ましく、３～１２が更に好ましい）であることが好ましく、置換基を有してもよいシクロアルキル基（炭素数３～２４が好ましく、３～１８がより好ましく、３～１２が更に好ましい）であることがより好ましく、置換基を有してもよいシクロヘキシル基が更に好ましい。 More specifically, Rb 1 and Rb 2 are a hydrogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms). , more preferably 2 to 18, more preferably 3 to 12), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 10), or an arylalkyl group (7 carbon atoms to 25 are preferred, 7 to 19 are more preferred, and 7 to 12 are even more preferred). These groups may have substituents to the extent that the effects of the present invention are exhibited. Rb 1 and Rb 2 may combine with each other to form a ring. The ring to be formed is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring. Rb 1 and Rb 2 are particularly linear, branched or cyclic alkyl groups (having preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms) which may have a substituent. is preferably a cycloalkyl group optionally having a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms), and more preferably a cycloalkyl group having a substituent A cyclohexyl group, which may be
　Ｒｂ３としては、アルキル基（炭素数１～２４が好ましく、２～１８がより好ましく、３～１２が更に好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０が更に好ましい）、アルケニル基（炭素数２～２４が好ましく、２～１２がより好ましく、２～６が更に好ましい）、アリールアルキル基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１２が更に好ましい）、アリールアルケニル基（炭素数８～２４が好ましく、８～２０がより好ましく、８～１６が更に好ましい）、アルコキシル基（炭素数１～２４が好ましく、２～１８がより好ましく、３～１２が更に好ましい）、アリールオキシ基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１２が更に好ましい）、又はアリールアルキルオキシ基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１２が更に好ましい）が挙げられる。中でも、シクロアルキル基（炭素数３～２４が好ましく、３～１８がより好ましく、３～１２が更に好ましい）、アリールアルケニル基、アリールアルキルオキシ基が好ましい。Ｒｂ３は更に本発明の効果を奏する範囲で置換基を有していてもよい。 Rb 3 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 10 are more preferred), alkenyl groups (preferably 2 to 24 carbon atoms, more preferably 2 to 12, more preferably 2 to 6), arylalkyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 19 preferably 7 to 12), arylalkenyl groups (preferably 8 to 24 carbon atoms, more preferably 8 to 20, more preferably 8 to 16), alkoxyl groups (preferably 1 to 24 carbon atoms, 2 to 18 is more preferred, and 3 to 12 are even more preferred), an aryloxy group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12), or an arylalkyloxy group (preferably 7 to 12 carbon atoms). 23 is preferred, 7 to 19 are more preferred, and 7 to 12 are even more preferred). Among them, a cycloalkyl group (having preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferred. Rb 3 may further have a substituent as long as the effects of the present invention are exhibited.
　式（Ｂ１）で表される化合物は、下記式（Ｂ１－１）又は下記式（Ｂ１－２）で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000036
 The compound represented by formula (B1) is preferably a compound represented by formula (B1-1) or formula (B1-2) below.
Figure JPOXMLDOC01-appb-C000036
　式中、Ｒｂ１１及びＲｂ１２、並びに、Ｒｂ３１及びＲｂ３２は、それぞれ、式（Ｂ１）におけるＲｂ１及びＲｂ２と同じである。
　Ｒｂ１３はアルキル基（炭素数１～２４が好ましく、２～１８がより好ましく、３～１２が更に好ましい）、アルケニル基（炭素数２～２４が好ましく、２～１８がより好ましく、３～１２が更に好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１２が更に好ましい）、アリールアルキル基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１２が更に好ましい）であり、本発明の効果を奏する範囲で置換基を有していてもよい。中でも、Ｒｂ１３はアリールアルキル基が好ましい。 In the formula, Rb 11 and Rb 12 and Rb 31 and Rb 32 are respectively the same as Rb 1 and Rb 2 in formula (B1).
Rb 13 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, 7 to 12 are more preferable), and may have a substituent within the range in which the effects of the present invention are exhibited. Among them, Rb 13 is preferably an arylalkyl group.
　Ｒｂ３３及びＲｂ３４は、それぞれ独立に、水素原子、アルキル基（炭素数１～１２が好ましく、１～８がより好ましく、１～３が更に好ましい）、アルケニル基（炭素数２～１２が好ましく、２～８がより好ましく、２～３が更に好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０が更に好ましい）、アリールアルキル基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１１が更に好ましい）であり、水素原子が好ましい。 Rb 33 and Rb 34 each independently represents a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms , more preferably 2 to 8, more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10), an arylalkyl group (7 to 23 is preferred, 7 to 19 are more preferred, and 7 to 11 are even more preferred), and a hydrogen atom is preferred.
　Ｒｂ３５は、アルキル基（炭素数１～２４が好ましく、１～１２がより好ましく、３～８が更に好ましい）、アルケニル基（炭素数２～１２が好ましく、２～１０がより好ましく、３～８が更に好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１２が更に好ましい）、アリールアルキル基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１２が更に好ましい）であり、アリール基が好ましい。 Rb 35 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 , 7 to 12 are more preferred), and aryl groups are preferred.
　式（Ｂ１－１）で表される化合物は、式（Ｂ１－１ａ）で表される化合物もまた好ましい。
Figure JPOXMLDOC01-appb-C000037
 The compound represented by formula (B1-1) is also preferably the compound represented by formula (B1-1a).
Figure JPOXMLDOC01-appb-C000037
　Ｒｂ１１及びＲｂ１２は式（Ｂ１－１）におけるＲｂ１１及びＲｂ１２と同義である。
　Ｒｂ１５及びＲｂ１６は水素原子、アルキル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３が更に好ましい）、アルケニル基（炭素数２～１２が好ましく、２～６がより好ましく、２～３が更に好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０が更に好ましい）、アリールアルキル基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１１が更に好ましい）であり、水素原子又はメチル基が好ましい。
　Ｒｂ１７はアルキル基（炭素数１～２４が好ましく、１～１２がより好ましく、３～８が更に好ましい）、アルケニル基（炭素数２～１２が好ましく、２～１０がより好ましく、３～８が更に好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１２が更に好ましい）、アリールアルキル基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１２が更に好ましい）であり、中でもアリール基が好ましい。 Rb 11 and Rb 12 have the same definitions as Rb 11 and Rb 12 in formula (B1-1).
Rb 15 and Rb 16 are hydrogen atoms, alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6, even more preferably 1 to 3), alkenyl groups (preferably 2 to 12 carbon atoms, 2 to 6 more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 10), an arylalkyl group (preferably 7 to 23 carbon atoms, 7 to 19 are more preferred, and 7 to 11 are even more preferred), and a hydrogen atom or a methyl group is preferred.
Rb 17 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, 7 to 12 are more preferable), and aryl groups are particularly preferable.
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
　式（Ｂ３）において、Ｌは、隣接する酸素原子と炭素原子を連結する連結鎖の経路上に飽和炭化水素基を有する２価の炭化水素基であって、連結鎖の経路上の原子数が３以上である炭化水素基を表す。また、ＲＮ１およびＲＮ２は、それぞれ独立に１価の有機基を表す。 In formula (B3), L is a divalent hydrocarbon group having a saturated hydrocarbon group on a connecting chain route connecting adjacent oxygen atoms and carbon atoms, wherein the number of atoms on the connecting chain route is represents a hydrocarbon group of 3 or more. R N1 and R N2 each independently represent a monovalent organic group.
　本明細書において、「連結鎖」とは、連結対象の２つの原子または原子群の間を結ぶ経路上の原子鎖のうち、これらの連結対象を最短（最小原子数）で結ぶものをいう。例えば、下記式で表される化合物において、Ｌは、フェニレンエチレン基から構成され、飽和炭化水素基としてエチレン基を有し、連結鎖は４つの炭素原子から構成されており、連結鎖の経路上の原子数（つまり、連結鎖を構成する原子の数であり、以下、「連結鎖長」あるいは「連結鎖の長さ」ともいう。）は４である。
Figure JPOXMLDOC01-appb-C000039
 As used herein, the term “connected chain” refers to the shortest (minimum number of atoms) of atomic chains on a path connecting two atoms or groups of atoms to be connected. For example, in the compound represented by the following formula, L is composed of a phenylene ethylene group, has an ethylene group as a saturated hydrocarbon group, the linking chain is composed of four carbon atoms, and on the route of the linking chain The number of atoms of (that is, the number of atoms constituting the linked chain, hereinafter also referred to as "linked chain length" or "linked chain length") is 4.
Figure JPOXMLDOC01-appb-C000039
　式（Ｂ３）におけるＬ中の炭素数（連結鎖中の炭素原子以外の炭素原子も含む）は、３～２４であることが好ましい。上限は、１２以下であることがより好ましく、１０以下であることがさらに好ましく、８以下であることが特に好ましい。下限は、４以上であることがより好ましい。上記分子内環化反応を速やかに進行させる観点から、Ｌの連結鎖長の上限は、１２以下であることが好ましく、８以下であることがより好ましく、６以下であることがさらに好ましく、５以下であることが特に好ましい。特に、Ｌの連結鎖長は、４または５であることが好ましく、４であることが最も好ましい。塩基発生剤の具体的な好ましい化合物としては、例えば、国際公開第２０２０／０６６４１６号の段落番号０１０２～０１６８に記載の化合物、国際公開第２０１８／０３８００２号の段落番号０１４３～０１７７に記載の化合物も挙げられる。 The number of carbon atoms in L (including carbon atoms other than carbon atoms in the connecting chain) in formula (B3) is preferably 3-24. The upper limit is more preferably 12 or less, still more preferably 10 or less, and particularly preferably 8 or less. More preferably, the lower limit is 4 or more. From the viewpoint of rapid progress of the intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and 5 The following are particularly preferred. In particular, the linking chain length of L is preferably 4 or 5, most preferably 4. Specific preferred compounds of the base generator include, for example, compounds described in paragraph numbers 0102 to 0168 of WO2020/066416, and compounds described in paragraph numbers 0143 to 0177 of WO2018/038002. mentioned.
また、塩基発生剤は下記式（Ｎ１）で表される化合物を含むことも好ましい。
Figure JPOXMLDOC01-appb-C000040
 Moreover, the base generator preferably contains a compound represented by the following formula (N1).
Figure JPOXMLDOC01-appb-C000040
　式（Ｎ１）中、ＲＮ１およびＲＮ２はそれぞれ独立に１価の有機基を表し、ＲC1は水素原子または保護基を表し、Ｌは２価の連結基を表す。 In formula (N1), R N1 and R N2 each independently represent a monovalent organic group, RC1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.
　Ｌは２価の連結基であり、２価の有機基であることが好ましい。連結基の連結鎖長は１以上であることが好ましく、２以上であることがより好ましい。上限としては、１２以下であることが好ましく、８以下であることがより好ましく、５以下であることがさらに好ましい。連結鎖長とは、式中の２つのカルボニル基の間において最短の道程となる原子配列に存在する原子の数である。 L is a divalent linking group, preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length is the number of atoms present in the atomic arrangement that provides the shortest path between two carbonyl groups in the formula.
　式（Ｎ１）中、ＲＮ１およびＲＮ２はそれぞれ独立に１価の有機基（炭素数１～２４が好ましく、２～１８がより好ましく、３～１２がさらに好ましい）を表し、炭化水素基（炭素数１～２４が好ましく、１～１２がより好ましく、１～１０がさらに好ましい）であることが好ましく、具体的には、脂肪族炭化水素基（炭素数１～２４が好ましく、１～１２がより好ましく、１～１０がさらに好ましい）または芳香族炭化水素基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）を挙げることができ、脂肪族炭化水素基が好ましい。ＲＮ１およびＲＮ２として、脂肪族炭化水素基を用いると、発生する塩基の塩基性が高く好ましい。なお、脂肪族炭化水素基および芳香族炭化水素基は、置換基を有していてもよく、また、脂肪族炭化水素基および芳香族炭化水素基が脂肪族炭化水素鎖中や芳香環中、置換基中に酸素原子を有していてもよい。特に、脂肪族炭化水素基が炭化水素鎖中に酸素原子を有している態様が例示される。 In formula (N1), R N1 and R N2 each independently represent a monovalent organic group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, more preferably 3 to 12 carbon atoms), and a hydrocarbon group ( preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms), specifically, an aliphatic hydrocarbon group (preferably 1 to 24 carbon atoms, 1 to 12 is more preferable, 1 to 10 are more preferable) or an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10), and an aliphatic hydrocarbon groups are preferred. It is preferable to use an aliphatic hydrocarbon group as R N1 and R N2 because the generated base has high basicity. In addition, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group are in the aliphatic hydrocarbon chain or in the aromatic ring, You may have an oxygen atom in the substituent. In particular, an aspect in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.
　ＲＮ１およびＲＮ２を構成する脂肪族炭化水素基としては、直鎖または分岐の鎖状アルキル基、環状アルキル基、鎖状アルキル基と環状アルキル基の組合せに係る基、酸素原子を鎖中に有するアルキル基が挙げられる。直鎖または分岐の鎖状アルキル基は、炭素数１～２４のものが好ましく、２～１８がより好ましく、３～１２がさらに好ましい。直鎖または分岐の鎖状アルキル基は、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、イソプロピル基、イソブチル基、セカンダリーブチル基、ターシャリーブチル基、イソペンチル基、ネオペンチル基、ターシャリーペンチル基、イソヘキシル基等が挙げられる。
　環状アルキル基は、炭素数３～１２のものが好ましく、３～６がより好ましい。環状アルキル基は、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロオクチル基等が挙げられる。
　鎖状アルキル基と環状アルキル基の組合せに係る基は、炭素数４～２４のものが好ましく、４～１８がより好ましく、４～１２がさらに好ましい。鎖状アルキル基と環状アルキル基の組合せに係る基は、例えば、シクロヘキシルメチル基、シクロヘキシルエチル基、シクロヘキシルプロピル基、メチルシクロヘキシルメチル基、エチルシクロヘキシルエチル基等が挙げられる。
　酸素原子を鎖中に有するアルキル基は、炭素数２～１２のものが好ましく、２～６がより好ましく、２～４がさらに好ましい。酸素原子を鎖中に有するアルキル基は、鎖状でも環状でもよく、直鎖でも分岐でもよい。
　なかでも、後述する分解生成塩基の沸点を高める観点で、ＲＮ１およびＲＮ２は炭素数５～１２のアルキル基が好ましい。ただし、金属（例えば銅）の層と積層する際の密着性を重視する処方においては、環状のアルキル基を有する基や炭素数１～８のアルキル基であることが好ましい。 Aliphatic hydrocarbon groups constituting R N1 and R N2 include linear or branched chain alkyl groups, cyclic alkyl groups, groups related to combinations of chain alkyl groups and cyclic alkyl groups, and oxygen atoms in the chains. Alkyl groups having The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms. Linear or branched chain alkyl groups are, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl group, isobutyl group, secondary butyl group, tertiary butyl group, isopentyl group, neopentyl group, tertiary pentyl group, isohexyl group and the like.
The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. Cyclic alkyl groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.
Groups associated with a combination of a chain alkyl group and a cyclic alkyl group preferably have 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms. Groups related to combinations of chain alkyl groups and cyclic alkyl groups include, for example, a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, and an ethylcyclohexylethyl group.
The alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms. An alkyl group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched.
Among them, from the viewpoint of raising the boiling point of the decomposition base described later, R 1 N1 and R 2 N2 are preferably alkyl groups having 5 to 12 carbon atoms. However, in a prescription that emphasizes adhesion when laminating with a metal (eg, copper) layer, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.
　ＲＮ１およびＲＮ２は互いに連結して環状構造を形成していてもよい。環状構造を形成するにあたっては、酸素原子等を鎖中に有していてもよい。また、ＲＮ１およびＲＮ２が形成する環状構造は、単環であっても、縮合環であってもよいが、単環が好ましい。形成される環状構造としては、式（Ｎ１）中の窒素原子を含有する５員環または６員環が好ましく、例えば、ピロール環、イミダゾール環、ピラゾール環、ピロリン環、ピロリジン環、イミダゾリジン環、ピラゾリジン環、ピぺリジン環、ピペラジン環、モルホリン環などが挙げられ、ピロリン環、ピロリジン環、ピペリジン環、ピペラジン環、モルホリン環が好ましく挙げられる。 RN1 and RN2 may be linked to each other to form a ring structure. In forming the cyclic structure, the chain may have an oxygen atom or the like. The cyclic structure formed by R N1 and R N2 may be a monocyclic ring or a condensed ring, but is preferably a monocyclic ring. The cyclic structure to be formed is preferably a 5- or 6-membered ring containing a nitrogen atom in formula (N1), such as pyrrole ring, imidazole ring, pyrazole ring, pyrroline ring, pyrrolidine ring, imidazolidine ring, A pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring and the like can be mentioned, and a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring and a morpholine ring are preferably mentioned.
　ＲＣ１は水素原子または保護基を表し、水素原子が好ましい。 R C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.
　保護基としては、酸または塩基の作用により分解する保護基が好ましく、酸で分解する保護基が好ましく挙げられる。 The protective group is preferably a protective group that is decomposed by the action of an acid or a base, and preferably includes a protective group that is decomposed by an acid.
　保護基の具体例としては、鎖状もしくは環状のアルキル基または鎖中に酸素原子を有する鎖状もしくは環状のアルキル基が挙げられる。鎖状もしくは環状のアルキル基としては、メチル基、エチル基、イソプロピル基、ｔｅｒｔ－ブチル基、シクロヘキシル基等が挙げられる。鎖中に酸素原子を有する鎖状のアルキル基としては、具体的にはアルキルオキシアルキル基が挙げられ、さらに具体的には、メチルオキシメチル（ＭＯＭ）基、エチルオキシエチル（ＥＥ）基等が挙げられる。鎖中に酸素原子を有する環状のアルキル基としては、エポキシ基、グリシジル基、オキセタニル基、テトラヒドロフラニル基、テトラヒドロピラニル（ＴＨＰ）基等が挙げられる。 Specific examples of protecting groups include chain or cyclic alkyl groups or chain or cyclic alkyl groups having an oxygen atom in the chain. Chain or cyclic alkyl groups include methyl group, ethyl group, isopropyl group, tert-butyl group, cyclohexyl group and the like. The chain alkyl group having an oxygen atom in the chain specifically includes an alkyloxyalkyl group, more specifically a methyloxymethyl (MOM) group, an ethyloxyethyl (EE) group, and the like. mentioned. Cyclic alkyl groups having an oxygen atom in the chain include epoxy group, glycidyl group, oxetanyl group, tetrahydrofuranyl group, tetrahydropyranyl (THP) group and the like.
　Ｌを構成する２価の連結基としては、特に定めるものではないが、炭化水素基が好ましく、脂肪族炭化水素基がより好ましい。炭化水素基は、置換基を有していてもよく、また、炭化水素鎖の中に炭素原子以外の種類の原子を有していてもよい。より具体的には、鎖中に酸素原子を有していてもよい２価の炭化水素連結基であることが好ましく、鎖中に酸素原子を有していてもよい２価の脂肪族炭化水素基、２価の芳香族炭化水素基、または鎖中に酸素原子を有していてもよい２価の脂肪族炭化水素基と２価の芳香族炭化水素基の組み合わせに係る基がより好ましく、鎖中に酸素原子を有していてもよい２価の脂肪族炭化水素基がさらに好ましい。これらの基は、酸素原子を有していないほうが好ましい。
　２価の炭化水素連結基は、炭素数１～２４のものが好ましく、２～１２がより好ましく、２～６がさらに好ましい。２価の脂肪族炭化水素基は、炭素数１～１２のものが好ましく、２～６がより好ましく、２～４がさらに好ましい。２価の芳香族炭化水素基は、炭素数６～２２のものが好ましく、６～１８がより好ましく、６～１０がさらに好ましい。２価の脂肪族炭化水素基と２価の芳香族炭化水素基の組み合わせに係る基（例えば、アリーレンアルキル基）は、炭素数７～２２のものが好ましく、７～１８がより好ましく、７～１０がさらに好ましい。 The divalent linking group constituting L is not particularly defined, but is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have substituents and may have atoms of types other than carbon atoms in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group which may have an oxygen atom in the chain, and a divalent aliphatic hydrocarbon which may have an oxygen atom in the chain group, a divalent aromatic hydrocarbon group, or a group related to a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group, A divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is more preferred. These groups preferably have no oxygen atoms.
The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. A group related to a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (eg, an arylene alkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and 7 to 10 is more preferred.
　連結基Ｌとしては、具体的に、直鎖または分岐の鎖状アルキレン基、環状アルキレン基、鎖状アルキレン基と環状アルキレン基の組み合わせに係る基、酸素原子を鎖中に有しているアルキレン基、直鎖または分岐の鎖状のアルケニレン基、環状のアルケニレン基、アリーレン基、アリーレンアルキレン基が好ましい。
　直鎖または分岐の鎖状アルキレン基は、炭素数１～１２のものが好ましく、２～６がより好ましく、２～４がさらに好ましい。
　環状アルキレン基は、炭素数３～１２のものが好ましく、３～６がより好ましい。
　鎖状アルキレン基と環状アルキレン基の組み合わせに係る基は、炭素数４～２４のものが好ましく、４～１２がより好ましく、４～６がさらに好ましい。
　酸素原子を鎖中に有するアルキレン基は、鎖状でも環状でもよく、直鎖でも分岐でもよい。酸素原子を鎖中に有するアルキレン基は、炭素数１～１２のものが好ましく、１～６がより好ましく、１～３がさらに好ましい。 Specific examples of the linking group L include a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, and an alkylene group having an oxygen atom in the chain. , a linear or branched alkenylene group, a cyclic alkenylene group, an arylene group and an arylenealkylene group are preferred.
The linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
The cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
The group associated with the combination of a chain alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms.
An alkylene group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms.
　直鎖または分岐の鎖状のアルケニレン基は、炭素数２～１２のものが好ましく、２～６がより好ましく、２～３がさらに好ましい。直鎖または分岐の鎖状のアルケニレン基は、Ｃ＝Ｃ結合の数は１～１０のものが好ましく、１～６がより好ましく、１～３がさらに好ましい。
　環状のアルケニレン基は、炭素数３～１２のものが好ましく、３～６がより好ましい。環状のアルケニレン基は、Ｃ＝Ｃ結合の数は１～６が好ましく、１～４がより好ましく、１～２がさらに好ましい。
　アリーレン基は、炭素数６～２２のものが好ましく、６～１８がより好ましく、６～１０がさらに好ましい。
　アリーレンアルキレン基は、炭素数７～２３のものが好ましく、７～１９がより好ましく、７～１１がさらに好ましい。
　中でも、鎖状アルキレン基、環状アルキレン基、酸素原子を鎖中に有するアルキレン基、鎖状のアルケニレン基、アリーレン基、アリーレンアルキレン基が好ましく、１，２－エチレン基、プロパンジイル基（特に１，３－プロパンジイル基）、シクロヘキサンジイル基（特に１，２－シクロヘキサンジイル基）、ビニレン基（特にシスビニレン基）、フェニレン基（１，２-フェニレン基）、フェニレンメチレン基（特に１，２－フェニレンメチレン基）、エチレンオキシエチレン基（特に１，２－エチレンオキシ－１，２－エチレン基）がより好ましい。 The linear or branched chain alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 3 carbon atoms. The linear or branched chain alkenylene group preferably has 1 to 10 C═C bonds, more preferably 1 to 6, even more preferably 1 to 3.
The cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. The number of C═C bonds in the cyclic alkenylene group is preferably 1-6, more preferably 1-4, even more preferably 1-2.
The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.
Among them, a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylene alkylene group are preferable, and a 1,2-ethylene group and a propanediyl group (especially 1, 3-propanediyl group), cyclohexanediyl group (especially 1,2-cyclohexanediyl group), vinylene group (especially cis-vinylene group), phenylene group (1,2-phenylene group), phenylenemethylene group (especially 1,2-phenylene methylene group) and ethyleneoxyethylene group (especially 1,2-ethyleneoxy-1,2-ethylene group) are more preferable.
　塩基発生剤としては、下記の例が挙げられるが、本発明がこれにより限定して解釈されるものではない。 Examples of base generators include the following, but the present invention should not be construed as being limited thereto.
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
　非イオン型塩基発生剤の分子量は、８００以下であることが好ましく、６００以下であることがより好ましく、５００以下であることが更に好ましい。下限としては、１００以上であることが好ましく、２００以上であることがより好ましく、３００以上であることが更に好ましい。 The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
　イオン型塩基発生剤の具体的な好ましい化合物としては、例えば、国際公開第２０１８／０３８００２号の段落番号０１４８～０１６３に記載の化合物も挙げられる。 Specific preferred compounds of the ionic base generator include, for example, compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.
　アンモニウム塩の具体例としては、以下の化合物を挙げることができるが、本発明はこれらに限定されるものではない。
Figure JPOXMLDOC01-appb-C000042
 Specific examples of ammonium salts include the following compounds, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000042
　イミニウム塩の具体例としては、以下の化合物を挙げることができるが、本発明はこれらに限定されるものではない。
Figure JPOXMLDOC01-appb-C000043
 Specific examples of iminium salts include the following compounds, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000043
　本発明の樹脂組成物が塩基発生剤を含む場合、塩基発生剤の含有量は、本発明の樹脂組成物中の樹脂１００質量部に対し、０．１～５０質量部が好ましい。下限は、０．３質量部以上がより好ましく、０．５質量部以上が更に好ましい。上限は、３０質量部以下がより好ましく、２０質量部以下が更に好ましく、１０質量部以下が一層好ましく、５質量部以下であってもよく、４質量部以下であってもよい。
　塩基発生剤は、１種又は２種以上を用いることができる。２種以上を用いる場合は、合計量が上記範囲であることが好ましい。 When the resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less.
One or two or more base generators can be used. When two or more are used, the total amount is preferably within the above range.
＜溶剤＞
　本発明の樹脂組成物は、溶剤を含むことが好ましい。
　溶剤は、公知の溶剤を任意に使用できる。溶剤は有機溶剤が好ましい。有機溶剤としては、エステル類、エーテル類、ケトン類、環状炭化水素類、スルホキシド類、アミド類、ウレア類、アルコール類などの化合物が挙げられる。 <Solvent>
The resin composition of the present invention preferably contains a solvent.
Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.
　エステル類として、例えば、酢酸エチル、酢酸－ｎ－ブチル、酢酸イソブチル、酢酸へキシル、ギ酸アミル、酢酸イソアミル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、γ－ブチロラクトン、ε－カプロラクトン、δ－バレロラクトン、アルキルオキシ酢酸アルキル（例えば、アルキルオキシ酢酸メチル、アルキルオキシ酢酸エチル、アルキルオキシ酢酸ブチル（例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等））、３－アルキルオキシプロピオン酸アルキルエステル類（例えば、３－アルキルオキシプロピオン酸メチル、３－アルキルオキシプロピオン酸エチル等（例えば、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル等））、２－アルキルオキシプロピオン酸アルキルエステル類（例えば、２－アルキルオキシプロピオン酸メチル、２－アルキルオキシプロピオン酸エチル、２－アルキルオキシプロピオン酸プロピル等（例えば、２－メトキシプロピオン酸メチル、２－メトキシプロピオン酸エチル、２－メトキシプロピオン酸プロピル、２－エトキシプロピオン酸メチル、２－エトキシプロピオン酸エチル））、２－アルキルオキシ－２－メチルプロピオン酸メチル及び２－アルキルオキシ－２－メチルプロピオン酸エチル（例えば、２－メトキシ－２－メチルプロピオン酸メチル、２－エトキシ－２－メチルプロピオン酸エチル等）、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、２－オキソブタン酸メチル、２－オキソブタン酸エチル、ヘキサン酸エチル、ヘプタン酸エチル、マロン酸ジメチル、マロン酸ジエチル等が好適なものとして挙げられる。 Esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone , ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetates (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, 3-methoxypropionic acid ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl propyl oxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvate Ethyl acetate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate and the like are preferred. .
　エーテル類として、例えば、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールブチルメチルエーテル、トリエチレングリコールジメチルエーテル、テトラエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテル、エチレングリコールモノブチルエーテルアセテート、ジエチレングリコールエチルメチルエーテル、プロピレングリコールモノプロピルエーテルアセテート、ジプロピレングリコールジメチルエーテル等が好適なものとして挙げられる。 Examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol Preferred examples include monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether, and the like.
　ケトン類として、例えば、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、２－ヘプタノン、３－ヘプタノン、３－メチルシクロヘキサノン、レボグルコセノン、ジヒドロレボグルコセノン等が好適なものとして挙げられる。 Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like.
　環状炭化水素類として、例えば、トルエン、キシレン、アニソール等の芳香族炭化水素類、リモネン等の環式テルペン類が好適なものとして挙げられる。 Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene.
　スルホキシド類として、例えば、ジメチルスルホキシドが好適なものとして挙げられる。 Suitable sulfoxides include, for example, dimethyl sulfoxide.
　アミド類として、Ｎ－メチル－２－ピロリドン、Ｎ－エチル－２－ピロリドン、Ｎ－シクロヘキシル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルイソブチルアミド、３－メトキシ－Ｎ，Ｎ－ジメチルプロピオンアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロピオンアミド、Ｎ－ホルミルモルホリン、Ｎ－アセチルモルホリン等が好適なものとして挙げられる。 As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, Suitable examples include 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine and the like.
　ウレア類として、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルウレア、１，３－ジメチル－２－イミダゾリジノン等が好適なものとして挙げられる。 Suitable ureas include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like.
アルコール類として、メタノール、エタノール、１-プロパノール、２-プロパノール、１－ブタノール、１－ペンタノール、１－ヘキサノール、ベンジルアルコール、エチレングリコールモノメチルエーテル、１－メトキシ－２－プロパノール、２－エトキシエタノール、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノヘキシルエーテル、トリエチレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、ポリエチレングリコールモノメチルエーテル、ポリプロピレングリコール、テトラエチレングリコール、エチレングリコールモノブチルエーテル、エチレングリコールモノベンジルエーテル、エチレングリコールモノフェニルエーテル、メチルフェニルカルビノール、ｎ－アミルアルコール、メチルアミルアルコール、および、ダイアセトンアルコール等が挙げられる。 Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, diacetone alcohol and the like.
　溶剤は、塗布面性状の改良などの観点から、２種以上を混合する形態も好ましい。 From the viewpoint of improving the properties of the coating surface, it is also preferable to mix two or more solvents.
　本発明では、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、３－メトキシプロピオン酸メチル、２－ヘプタノン、シクロヘキサノン、シクロペンタノン、γ－ブチロラクトン、ジメチルスルホキシド、エチルカルビトールアセテート、ブチルカルビトールアセテート、Ｎ－メチル－２－ピロリドン、プロピレングリコールメチルエーテル、及びプロピレングリコールメチルエーテルアセテート、レボグルコセノン、ジヒドロレボグルコセノンから選択される１種の溶剤、又は、２種以上で構成される混合溶剤が好ましい。ジメチルスルホキシドとγ－ブチロラクトンとの併用、又は、Ｎ－メチル－２－ピロリドンと乳酸エチルとの併用が特に好ましい。 In the present invention, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ- one solvent selected from butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, levoglucosenone, dihydrolevoglucosenone; Alternatively, a mixed solvent composed of two or more kinds is preferable. A combination of dimethyl sulfoxide and γ-butyrolactone or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.
　溶剤の含有量は、塗布性の観点から、本発明の樹脂組成物の全固形分濃度が５～８０質量％になる量とすることが好ましく、５～７５質量％となる量にすることがより好ましく、１０～７０質量％となる量にすることが更に好ましく、２０～７０質量％となるようにすることが一層好ましい。溶剤含有量は、塗膜の所望の厚さと塗布方法に応じて調節すればよい。 From the viewpoint of coating properties, the content of the solvent is preferably an amount such that the total solid concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass. More preferably, the amount is from 10 to 70% by mass, and even more preferably from 20 to 70% by mass. The solvent content may be adjusted according to the desired thickness of the coating and the method of application.
　本発明の樹脂組成物は、溶剤を１種のみ含有していてもよいし、２種以上含有していてもよい。溶剤を２種以上含有する場合は、その合計が上記範囲であることが好ましい。 The resin composition of the present invention may contain only one type of solvent, or may contain two or more types. When two or more solvents are contained, the total is preferably within the above range.
＜金属接着性改良剤＞
　本発明の樹脂組成物は、電極や配線などに用いられる金属材料との接着性を向上させるための金属接着性改良剤を含んでいることが好ましい。金属接着性改良剤としては、アルコキシシリル基を有するシランカップリング剤、アルミニウム系接着助剤、チタン系接着助剤、スルホンアミド構造を有する化合物及びチオウレア構造を有する化合物、リン酸誘導体化合物、βケトエステル化合物、アミノ化合物等が挙げられる。 <Metal adhesion improver>
The resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used for electrodes, wiring, and the like. Examples of metal adhesion improvers include alkoxysilyl group-containing silane coupling agents, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, and β-ketoesters. compounds, amino compounds, and the like.
〔シランカップリング剤〕
　シランカップリング剤としては、例えば、国際公開第２０１５／１９９２１９号の段落０１６７に記載の化合物、特開２０１４－１９１００２号公報の段落００６２～００７３に記載の化合物、国際公開第２０１１／０８０９９２号の段落００６３～００７１に記載の化合物、特開２０１４－１９１２５２号公報の段落００６０～００６１に記載の化合物、特開２０１４－０４１２６４号公報の段落００４５～００５２に記載の化合物、国際公開第２０１４／０９７５９４号の段落００５５に記載の化合物、特開２０１８－１７３５７３の段落００６７～００７８に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。また、特開２０１１－１２８３５８号公報の段落００５０～００５８に記載のように異なる２種以上のシランカップリング剤を用いることも好ましい。また、シランカップリング剤は、下記化合物を用いることも好ましい。以下の式中、Ｍｅはメチル基を、Ｅｔはエチル基を表す。 〔Silane coupling agent〕
Examples of the silane coupling agent include compounds described in paragraph 0167 of WO 2015/199219, compounds described in paragraphs 0062 to 0073 of JP 2014-191002, and paragraphs of WO 2011/080992. Compounds described in 0063-0071, compounds described in paragraphs 0060-0061 of JP-A-2014-191252, compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/097594 Compounds described in paragraph 0055, compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the following formulas, Me represents a methyl group and Et represents an ethyl group.
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
　他のシランカップリング剤としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルトリエトキシシラン、ｐ－スチリルトリメトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－アクリロキシプロピルトリメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－トリエトキシシリル－Ｎ－（１，３－ジメチル－ブチリデン）プロピルアミン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、トリス－（トリメトキシシリルプロピル）イソシアヌレート、３－ウレイドプロピルトリアルコキシシラン、３－メルカプトプロピルメチルジメトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－イソシアネートプロピルトリエトキシシラン、３－トリメトキシシリルプロピルコハク酸無水物が挙げられる。これらは１種単独または２種以上を組み合わせて使用することができる。 Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycid. xypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2 -(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used singly or in combination of two or more.
〔アルミニウム系接着助剤〕
　アルミニウム系接着助剤としては、例えば、アルミニウムトリス（エチルアセトアセテート）、アルミニウムトリス（アセチルアセトネート）、エチルアセトアセテートアルミニウムジイソプロピレート等を挙げることができる。 [Aluminum Adhesion Aid]
Examples of aluminum-based adhesion aids include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.
　また、その他の金属接着性改良剤としては、特開２０１４－１８６１８６号公報の段落００４６～００４９に記載の化合物、特開２０１３－０７２９３５号公報の段落００３２～００４３に記載のスルフィド系化合物を用いることもでき、これらの内容は本明細書に組み込まれる。 In addition, as other metal adhesion improvers, compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and sulfide compounds described in paragraphs 0032-0043 of JP-A-2013-072935 can be used. can also be used, the contents of which are incorporated herein.
　金属接着性改良剤の含有量は特定樹脂１００質量部に対して、好ましくは０．０１～３０質量部であり、より好ましくは０．１～１０質量部の範囲であり、更に好ましくは０．５～５質量部の範囲である。上記下限値以上とすることでパターンと金属層との接着性が良好となり、上記上限値以下とすることでパターンの耐熱性、機械特性が良好となる。金属接着性改良剤は１種のみでもよいし、２種以上であってもよい。２種以上用いる場合は、その合計が上記範囲であることが好ましい。 The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of the specific resin. It is in the range of 5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the pattern and the metal layer is improved, and when it is at most the above upper limit value, the heat resistance and mechanical properties of the pattern are improved. One type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, the total is preferably within the above range.
＜マイグレーション抑制剤＞
　本発明の樹脂組成物は、マイグレーション抑制剤を更に含むことが好ましい。マイグレーション抑制剤を含むことにより、金属層（金属配線）由来の金属イオンが膜内へ移動することを効果的に抑制可能となる。 <Migration inhibitor>
The resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it becomes possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the film.
　マイグレーション抑制剤としては、特に制限はないが、複素環（ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、ピラゾール環、イソオキサゾール環、イソチアゾール環、テトラゾール環、ピリジン環、ピリダジン環、ピリミジン環、ピラジン環、ピペリジン環、ピペラジン環、モルホリン環、２Ｈ－ピラン環及び６Ｈ－ピラン環、トリアジン環）を有する化合物、チオ尿素類及びスルファニル基を有する化合物、ヒンダードフェノール系化合物、サリチル酸誘導体系化合物、ヒドラジド誘導体系化合物が挙げられる。特に、１，２，４－トリアゾール、ベンゾトリアゾール、３－アミノ－１，２，４－トリアゾール、３，５－ジアミノ－１，２，４－トリアゾール等のトリアゾール系化合物、１Ｈ－テトラゾール、５－フェニルテトラゾール、５－アミノ―１Ｈ－テトラゾール等のテトラゾール系化合物が好ましく使用できる。 Migration inhibitors are not particularly limited, but heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and sulfanyl groups, hindered phenolic compounds , salicylic acid derivative-based compounds, and hydrazide derivative-based compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 1H-tetrazole, 5- Tetrazole compounds such as phenyltetrazole and 5-amino-1H-tetrazole can be preferably used.
　又はハロゲンイオンなどの陰イオンを捕捉するイオントラップ剤を使用することもできる。 Alternatively, an ion trapping agent that traps anions such as halogen ions can be used.
　その他のマイグレーション抑制剤としては、特開２０１３－０１５７０１号公報の段落００９４に記載の防錆剤、特開２００９－２８３７１１号公報の段落００７３～００７６に記載の化合物、特開２０１１－０５９６５６号公報の段落００５２に記載の化合物、特開２０１２－１９４５２０号公報の段落０１１４、０１１６及び０１１８に記載の化合物、国際公開第２０１５／１９９２１９号の段落０１６６に記載の化合物などを使用することができ、これらの内容は本明細書に組み込まれる。 Other migration inhibitors include rust inhibitors described in paragraph 0094 of JP-A-2013-015701, compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, and JP-A-2011-059656. The compound described in paragraph 0052, the compound described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, the compound described in paragraph 0166 of WO 2015/199219, etc. can be used, and these The contents are incorporated herein.
　マイグレーション抑制剤の具体例としては、下記化合物を挙げることができる。 Specific examples of migration inhibitors include the following compounds.
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
　本発明の樹脂組成物がマイグレーション抑制剤を有する場合、マイグレーション抑制剤の含有量は、本発明の樹脂組成物の全固形分に対して、０．０１～５．０質量％であることが好ましく、０．０５～２．０質量％であることがより好ましく、０．１～１．０質量％であることが更に好ましい。 When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the resin composition of the present invention. , more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass.
　マイグレーション抑制剤は１種のみでもよいし、２種以上であってもよい。マイグレーション抑制剤が２種以上の場合は、その合計が上記範囲であることが好ましい。 Only one type of migration inhibitor may be used, or two or more types may be used. When two or more migration inhibitors are used, the total is preferably within the above range.
＜重合禁止剤＞
　本発明の樹脂組成物は、重合禁止剤を含むことが好ましい。重合禁止剤としてはフェノール系化合物、キノン系化合物、アミノ系化合物、Ｎ－オキシルフリーラジカル化合物系化合物、ニトロ系化合物、ニトロソ系化合物、ヘテロ芳香環系化合物、金属化合物などが挙げられる。 <Polymerization inhibitor>
The resin composition of the present invention preferably contains a polymerization inhibitor. Polymerization inhibitors include phenol compounds, quinone compounds, amino compounds, N-oxyl free radical compound compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, metal compounds and the like.
　重合禁止剤の具体的な化合物としては、ｐ－ヒドロキノン、ｏ－ヒドロキノン、ｏ－メトキシフェノール、ｐ－メトキシフェノール、ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール、ピロガロール、ｐ－ｔｅｒｔ－ブチルカテコール、１，４－ベンゾキノン、ジフェニル－ｐ－ベンゾキノン、４，４’－チオビス（３－メチル－６－ｔｅｒｔ－ブチルフェノール）、２，２’－メチレンビス（４－メチル－６－ｔｅｒｔ－ブチルフェノール）、Ｎ－ニトロソフェニルヒドロキシアミン第一セリウム塩、Ｎ－ニトロソ－Ｎ－フェニルヒドロキシアミンアルミニウム塩、Ｎ－ニトロソジフェニルアミン、Ｎ－フェニルナフチルアミン、エチレンジアミン四酢酸、１，２－シクロヘキサンジアミン四酢酸、グリコールエーテルジアミン四酢酸、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール、５－ニトロソ－８－ヒドロキシキノリン、１－ニトロソ－２－ナフトール、２－ニトロソ－１－ナフトール、２－ニトロソ－５－（Ｎ－エチル－Ｎ－スルホプロピルアミノ）フェノール、Ｎ－ニトロソ－Ｎ－（１－ナフチル）ヒドロキシアミンアンモニウム塩、ビス（４－ヒドロキシ－３，５－ｔｅｒｔ－ブチル）フェニルメタン、１，３，５－トリス（４－ｔ－ブチル－３－ヒドロキシ－２，６－ジメチルベンジル）－１，３，５－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）－トリオン、４‐ヒドロキシ－２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカル、２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカル、フェノチアジン、フェノキサジン、１，１－ジフェニル－２－ピクリルヒドラジル、ジブチルジチオカーバネート銅（ＩＩ）、ニトロベンゼン、Ｎ－ニトロソ－Ｎ－フェニルヒドロキシルアミンアルミニウム塩、Ｎ－ニトロソ－Ｎ－フェニルヒドロキシルアミンアンモニウム塩、などが好適に用いられる。また、特開２０１５－１２７８１７号公報の段落００６０に記載の重合禁止剤、及び、国際公開第２０１５／１２５４６９号の段落００３１～００４６に記載の化合物を用いることもでき、この内容は本明細書に組み込まれる。 Specific compounds of polymerization inhibitors include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4,4′-thiobis(3-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenyl hydroxylamine cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2, 6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N -sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4- t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6, 6-tetramethylpiperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbanate Copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. are preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817, and the compounds described in paragraphs 0031 to 0046 of WO 2015/125469 can also be used, the contents of which are herein incorporated.
　本発明の樹脂組成物が重合禁止剤を有する場合、重合禁止剤の含有量は、本発明の樹脂組成物の全固形分に対して、０．０１～２０質量％であることが好ましく、０．０２～１５質量％であることがより好ましく、０．０５～１０質量％であることが更に好ましい。 When the resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass with respect to the total solid content of the resin composition of the present invention. It is more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.
　重合禁止剤は１種のみでもよいし、２種以上であってもよい。重合禁止剤が２種以上の場合は、その合計が上記範囲であることが好ましい。 Only one type of polymerization inhibitor may be used, or two or more types may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.
＜酸捕捉剤＞
　本発明の樹脂組成物は、露光から加熱までの経時による性能変化を低減するために、酸捕捉剤を含有することが好ましい。ここで酸捕捉剤とは、系中に存在することで発生酸を捕捉することができる化合物を指し、酸性度が低くｐＫａの高い化合物であることが好ましい。酸捕捉剤としては、アミノ基を有する化合物が好ましく、１級アミン、２級アミン、３級アミン、アンモニウム塩、３級アミドなどが好ましく、１級アミン、２級アミン、３級アミン、アンモニウム塩が好ましく、２級アミン、３級アミン、アンモニウム塩がより好ましい。
　酸捕捉剤としては、イミダゾール構造、ジアザビシクロ構造、オニウム構造、トリアルキルアミン構造、アニリン構造又はピリジン構造を有する化合物、水酸基及び／又はエーテル結合を有するアルキルアミン誘導体、水酸基及び／又はエーテル結合を有するアニリン誘導体等を好ましく挙げることができる。オニウム構造を有する場合、酸捕捉剤はアンモニウム、ジアゾニウム、ヨードニウム、スルホニウム、ホスホニウム、ピリジニウムなどから選択されるカチオンと、酸発生剤が発生する酸より酸性度の低い酸のアニオンとを有する塩であることが好ましい。 <Acid Scavenger>
The resin composition of the present invention preferably contains an acid scavenger in order to reduce performance changes over time from exposure to heating. Here, the acid scavenger refers to a compound that can scavenge the generated acid when present in the system, and is preferably a compound with low acidity and high pKa. The acid scavenger is preferably a compound having an amino group, preferably a primary amine, secondary amine, tertiary amine, ammonium salt, tertiary amide, etc. Primary amine, secondary amine, tertiary amine, ammonium salt are preferred, and secondary amines, tertiary amines and ammonium salts are more preferred.
Examples of acid scavengers include compounds having an imidazole structure, diazabicyclo structure, onium structure, trialkylamine structure, aniline structure or pyridine structure, alkylamine derivatives having hydroxyl groups and/or ether bonds, and anilines having hydroxyl groups and/or ether bonds. Derivatives and the like can be mentioned preferably. When having an onium structure, the acid scavenger is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, etc., and an anion of an acid less acidic than the acid generated by the acid generator. is preferred.
　イミダゾール構造を有する酸捕捉剤としてはイミダゾール、２、４、５－トリフェニルイミダゾール、ベンズイミダゾール、２－フェニルベンゾイミダゾール等が挙げられる。ジアザビシクロ構造を有する酸捕捉剤としては１、４－ジアザビシクロ［２，２，２］オクタン、１、５－ジアザビシクロ［４，３，０］ノナ－５－エン、１、８－ジアザビシクロ［５，４，０］ウンデカー７－エン等が挙げられる。オニウム構造を有する酸捕捉剤としてはテトラブチルアンモニウムヒドロキシド、トリアリールスルホニウムヒドロキシド、フェナシルスルホニウムヒドロキシド、２－オキソアルキル基を有するスルホニウムヒドロキシド、具体的にはトリフェニルスルホニウムヒドロキシド、トリス（ｔ－ブチルフェニル）スルホニウムヒドロキシド、ビス（ｔ－ブチルフェニル）ヨードニウムヒドロキシド、フェナシルチオフェニウムヒドロキシド、２－オキソプロピルチオフェニウムヒドロキシド等が挙げられる。トリアルキルアミン構造を有する酸捕捉剤としては、トリ（ｎ－ブチル）アミン、トリ（ｎ－オクチル）アミン等を挙げることができる。アニリン構造を有する酸捕捉剤としては、２，６－ジイソプロピルアニリン、Ｎ，Ｎ－ジメチルアニリン、Ｎ，Ｎ－ジブチルアニリン、Ｎ，Ｎ－ジヘキシルアニリン等を挙げることができる。ピリジン構造を有する酸捕捉剤としては、ピリジン、４－メチルピリジン等を挙げることができる。水酸基及び／又はエーテル結合を有するアルキルアミン誘導体としては、エタノールアミン、ジエタノールアミン、トリエタノールアミン、Ｎ－フェニルジエタノールアミン、トリス（メトキシエトキシエチル）アミン等を挙げることができる。水酸基及び／又はエーテル結合を有するアニリン誘導体としては、Ｎ，Ｎ－ビス（ヒドロキシエチル）アニリン等を挙げることができる。 Examples of acid scavengers having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzimidazole and the like. Acid scavengers having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, 1,8-diazabicyclo[5,4 ,0]undecar-7-ene and the like. Acid scavengers having an onium structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxides having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris ( t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide and the like. Examples of acid scavengers having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Acid scavengers having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline and N,N-dihexylaniline. Examples of acid scavengers having a pyridine structure include pyridine and 4-methylpyridine. Examples of alkylamine derivatives having hydroxyl groups and/or ether bonds include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tris(methoxyethoxyethyl)amine and the like. Examples of aniline derivatives having hydroxyl groups and/or ether bonds include N,N-bis(hydroxyethyl)aniline.
　好ましい酸捕捉剤の具体例としては、エタノールアミン、ジエタノールアミン、トリエタノールアミン、エチルアミン、ジエチルアミン、トリエチルアミン、ヘキシルアミン、ドデシルアミン、シクロヘキシルアミン、シクロヘキシルメチルアミン、シクロヘキシルジメチルアミン、アニリン、Ｎ－メチルアニリン、Ｎ，Ｎ－ジメチルアニリン、ジフェニルアミン、ピリジン、ブチルアミン、イソブチルアミン、ジブチルアミン、トリブチルアミン、ジシクロヘキシルアミン、ＤＢＵ（ジアザビシクロウンデセン）、ＤＡＢＣＯ（１，４－ジアザビシクロ［２．２．２］オクタン）、Ｎ，Ｎ－ジイソプロピルエチルアミン、テトラメチルアンモニウムヒドロキシド、エチレンジアミン、１，５－ジアミノペンタン、Ｎ－メチルヘキシルアミン、Ｎ－メチルジシクロヘキシルアミン、トリオクチルアミン、Ｎ－エチルエチレンジアミン、Ｎ，Ｎ―ジエチルエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラブチルー１，６－ヘキサンジアミン、スペルミジン、ジアミノシクロヘキサン、ビス（２－メトキシエチル）アミン、ピペリジン、メチルピペリジン、ピペラジン、トロパン、Ｎ－フェニルベンジルアミン、１，２－ジアニリノエタン、２－アミノエタノール、トルイジン、アミノフェノール、ヘキシルアニリン、フェニレンジアミン、フェニルエチルアミン、ジベンジルアミン、ピロール、Ｎ－メチルピロール、グアニジン、アミノピロリジン、ピラゾール、ピラゾリン、アミノモルホリン、アミノアルキルモルフォリン等があげられる。 Specific examples of preferred acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N , N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2 -Dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, aminomorpholine, aminoalkylmorpholine, etc. is given.
　これらの酸捕捉剤は、１種類を単独で用いてもよく、２種類以上を組み合わせて用いてもよい。
本発明に係る組成物は、酸捕捉剤を含有してもしなくてもよいが、含有する場合、酸捕捉剤の含有量は、組成物の全固形分を基準として、通常は０．００１～１０質量％であり、好ましくは０．０１～５質量％である。 These acid scavengers may be used singly or in combination of two or more.
The composition according to the present invention may or may not contain an acid scavenger, but when it does, the content of the acid scavenger is usually from 0.001 to 0.001 based on the total solid content of the composition. 10% by mass, preferably 0.01 to 5% by mass.
　酸発生剤と酸捕捉剤との使用割合は、酸発生剤／酸捕捉剤（モル比）＝２．５～３００であることが好ましい。即ち、感度、解像度の点からモル比が２．５以上であることが好ましく、露光後加熱処理までの経時でのレリーフパターンの太りによる解像度の低下抑制の点から３００以下が好ましい。酸発生剤／酸捕捉剤（モル比）は、より好ましくは５．０～２００、更に好ましくは７．０～１５０である。 The ratio of acid generator to acid scavenger used is preferably acid generator/acid scavenger (molar ratio) = 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and preferably 300 or less from the viewpoint of suppressing deterioration in resolution due to thickening of the relief pattern over time from exposure to heat treatment. The acid generator/acid scavenger (molar ratio) is more preferably 5.0-200, still more preferably 7.0-150.
　本発明の樹脂組成物は、フィラーを含んでもよい。
　フィラーは、熱伝導性であることが好ましい。フィラーは電気絶縁性であっても、半導体や導電性であってもよい。電気絶縁性および導電性の程度は、設計や目的に応じて、適宜選択される。
　例えば、電気絶縁性フィラーの場合には、そのフィラーの体積抵抗率の下限は、１．０×１０１１Ω・ｃｍ以上であることが好ましく、３．０×１０１１Ω・ｃｍ以上であることがより好ましく、１．０×１０１２Ω・ｃｍ以上であることが特に好ましい。また、体積抵抗率の上限は、特に限定されないが、例えば、１．０×１０１８以下Ω・ｃｍであることが好ましい。
　一方、半導体や、導電性フィラーの場合には、そのフィラーの体積抵抗率の下限は特に限定されないが、実用的には１．０×１０－７Ω・ｃｍ以上である。また、体積抵抗率の上限は、１．０×１０１１Ω・ｃｍ未満であることが好ましい。 The resin composition of the present invention may contain a filler.
The filler is preferably thermally conductive. The filler may be electrically insulating, semiconducting, or electrically conductive. The degree of electrical insulation and conductivity is appropriately selected according to the design and purpose.
For example, in the case of an electrically insulating filler, the lower limit of the volume resistivity of the filler is preferably 1.0×10 11 Ω·cm or more, more preferably 3.0×10 11 Ω·cm or more. is more preferable, and 1.0×10 12 Ω·cm or more is particularly preferable. Although the upper limit of the volume resistivity is not particularly limited, it is preferably 1.0×10 18 or less Ω·cm, for example.
On the other hand, in the case of a semiconductor or a conductive filler, the lower limit of the volume resistivity of the filler is not particularly limited, but practically it is 1.0×10 −7 Ω·cm or more. Moreover, the upper limit of the volume resistivity is preferably less than 1.0×10 11 Ω·cm.
　フィラーの熱拡散率は、例えば、５．０×１０－７ｍ２ｓ－１以上であることが好ましく、１．０×１０－６ｍ２ｓ－１以上であることがより好ましく２．０×１０－６ｍ２ｓ－１以上であることが更に好ましく、３．０×１０－６ｍ２ｓ－１以上であることが特に好ましい。また、フィラーの熱拡散率の上限は特に限定されないが、例えば１．０×１０－４ｍ２ｓ－１以下であることが好ましい。 The thermal diffusivity of the filler is, for example, preferably 5.0×10 −7 m 2 s −1 or more, more preferably 1.0×10 −6 m 2 s −1 or more, and more preferably 2.0. It is more preferably 3.0×10 −6 m 2 s −1 or more, particularly preferably 3.0×10 −6 m 2 s −1 or more. Although the upper limit of the thermal diffusivity of the filler is not particularly limited, it is preferably 1.0×10 −4 m 2 s −1 or less, for example.
　フィラーの密度は、例えば、４．０ｇ／ｃｍ3以下であることが好ましく、３．０ｇ／ｃｍ3以下であることがより好ましい。また、フィラーの密度の下限は特に限定されないが、例えば、１．０ｇ／ｃｍ３以上であることが好ましい。なお、フィラーが多孔質や中空粒子であるなど空隙部や空洞部を有するものである場合には、本明細書では、フィラーの密度とは、フィラーを構成する成分のうち固形分の密度を意味する。 The density of the filler is, for example, preferably 4.0 g/cm 3 or less, more preferably 3.0 g/cm 3 or less. Although the lower limit of the density of the filler is not particularly limited, it is preferably 1.0 g/cm 3 or more, for example. In addition, when the filler has voids or cavities such as porous or hollow particles, the density of the filler in this specification means the density of the solid content among the components constituting the filler. do.
　好ましくは、フィラーは電気絶縁性の材料を含む。電気絶縁性のフィラー材料は、例えば、窒素化合物、酸素化合物、ケイ素化合物、ホウ素化合物、炭素化合物およびこれらの複合的な化合物からなる電気絶縁性のセラミックである。窒素化合物としては、例えば、窒化ホウ素、窒化アルミニウム、窒化ケイ素などが挙げられる。酸素化合物としては、酸化アルミニウム（アルミナ）、酸化マグネシウム（マグネシア）、酸化亜鉛、酸化ケイ素（シリカ）、酸化ベリリウム、酸化チタン（チタニア）、酸化銅、亜酸化銅など金属酸化物が挙げられる。ケイ素化合物および炭素化合物としては、炭化ケイ素が挙げられる。ホウ素化合物としては、例えば、ホウ化チタンなど金属ホウ化物が挙げられる。その他の炭素化合物としては、例えば、ダイヤモンドなど、σ結合が支配的な炭素基質材料である。そして、上記の複合的な化合物としては、マグネサイト（炭酸マグネシウム）、ペロブスカイト（チタン酸カルシウム）、タルク、マイカ、カオリン、ベントナイト、パイロフェライトなどの鉱物系のセラミックが挙げられる。また、電気絶縁性のフィラー材料は、水酸化マグネシウム、水酸化アルミニウムなどの金属水酸化物でもよい。 Preferably, the filler contains an electrically insulating material. The electrically insulating filler material is, for example, an electrically insulating ceramic made of a nitrogen compound, an oxygen compound, a silicon compound, a boron compound, a carbon compound, or a composite compound thereof. Nitrogen compounds include, for example, boron nitride, aluminum nitride, and silicon nitride. Examples of oxygen compounds include metal oxides such as aluminum oxide (alumina), magnesium oxide (magnesia), zinc oxide, silicon oxide (silica), beryllium oxide, titanium oxide (titania), copper oxide and cuprous oxide. Silicon compounds and carbon compounds include silicon carbide. Boron compounds include, for example, metal borides such as titanium boride. Other carbon compounds are, for example, carbon matrix materials with predominantly σ bonds, such as diamond. Examples of the composite compound include mineral ceramics such as magnesite (magnesium carbonate), perovskite (calcium titanate), talc, mica, kaolin, bentonite, and pyroferrite. The electrically insulating filler material may also be a metal hydroxide such as magnesium hydroxide or aluminum hydroxide.
　これらの中でも、熱伝導性などの観点から、フィラー材料は、窒素化合物からなるセラミック、金属酸化物からなるセラミックおよび金属水酸化物のうち少なくとも一種を含むことが好ましい。そして、フィラー材料は、例えば、窒化ホウ素、窒化アルミニウム、窒化ケイ素、酸化アルミニウム、酸化マグネシウム、酸化亜鉛、及び酸化ベリリウムおよび水酸化アルミニウムよりなる群から選ばれた少なくとも１種を含むことが好ましい。特に、フィラー材料は、窒化ホウ素、窒化アルミニウム、窒化ケイ素、酸化アルミニウム、酸化マグネシウム、酸化亜鉛および酸化ベリリウムよりなる群から選ばれた少なくとも１種を含むことが特に好ましく、窒化ホウ素、窒化アルミニウム、窒化ケイ素および酸化アルミニウムのうち少なくとも１種を含むことがさらに好ましい。なお、窒化ホウ素は、ｃ－ＢＮ（立方晶構造）、ｗ－ＢＮ（ウルツ鉱構造）、ｈ－ＢＮ（六方晶構造）、ｒ－ＢＮ（菱面体晶構造）、ｔ－ＢＮ（乱層構造）などのいずれの構造であってもよい。窒化ホウ素の形状には、球状のものと鱗片状のものがあるが、いずれも用いることができる。また、日本触媒製のＩＸ－３シリーズ等も好適に使用することができる。 Among these, from the viewpoint of thermal conductivity, etc., the filler material preferably contains at least one of ceramics made of nitrogen compounds, ceramics made of metal oxides, and metal hydroxides. The filler material preferably contains, for example, boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, zinc oxide, and at least one selected from the group consisting of beryllium oxide and aluminum hydroxide. In particular, the filler material particularly preferably contains at least one selected from the group consisting of boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, zinc oxide and beryllium oxide. More preferably, it contains at least one of silicon and aluminum oxide. In addition, boron nitride has c-BN (cubic crystal structure), w-BN (wurtzite structure), h-BN (hexagonal crystal structure), r-BN (rhombohedral crystal structure), t-BN (turbulent structure ) or any other structure. Boron nitride has a spherical shape and a scaly shape, and both can be used. Also, the IX-3 series manufactured by Nippon Shokubai Co., Ltd., etc. can be suitably used.
　導電性のフィラー材料としては、例えば、黒鉛、カーボンブラック、グラファイト、炭素繊維（ピッチ系、ＰＡＮ系）、カーボンナノチューブ（ＣＮＴ）、カーボンナノファイバー（ＣＮＦ）など、π結合が支配的な炭素基質材料が挙げられる。また、このようなフィラー材料としては、銀、銅、鉄、ニッケル、アルミニウム、チタンなどの金属、および、ステンレス（ＳＵＳ）などの合金でもよい。さらに、このようなフィラー材料としては、異種元素がドープされた酸化亜鉛などの導電性金属酸化物や、フェライトなどの導電性セラミックも使用できる。 Examples of conductive filler materials include carbon substrate materials in which π bonds are dominant, such as graphite, carbon black, graphite, carbon fibers (pitch-based, PAN-based), carbon nanotubes (CNT), and carbon nanofibers (CNF). is mentioned. Such filler materials may be metals such as silver, copper, iron, nickel, aluminum and titanium, and alloys such as stainless steel (SUS). Furthermore, conductive metal oxides such as zinc oxide doped with different elements and conductive ceramics such as ferrite can also be used as such filler materials.
　フィラーは、半導体や導電性の熱伝導性粒子をシリカなどの電気絶縁性材料で被覆または表面処理をした構成でもよい。このような態様によれば、熱伝導性および電気絶縁性を個々に制御しやすくなるため、熱伝導性および電気絶縁性の調整が容易となる。例えば表面にシリカの膜を成膜する方法としては、水ガラス法とゾルゲル法が挙げられる。 The filler may have a structure in which semiconductor or conductive thermally conductive particles are coated or surface-treated with an electrically insulating material such as silica. According to such an aspect, it becomes easy to control the thermal conductivity and the electrical insulation individually, so that the adjustment of the thermal conductivity and the electrical insulation becomes easy. For example, methods for forming a silica film on the surface include a water glass method and a sol-gel method.
　これらのフィラーは、１種または２種以上を組み合わせて使用できる。また、フィラーの形状については、特に限定なく種々の形状のものを使用でき、例えば、繊維状、板状、鱗片状、棒状、球状、チューブ状、曲板状、針状などが挙げられる。 These fillers can be used singly or in combination of two or more. The shape of the filler is not particularly limited, and various shapes can be used.
　フィラーは、シランカップリング処理、チタネートカップリング処理、エポキシ処理、ウレタン処理、酸化処理などの表面処理が施されていてもよい。表面処理に用いられる表面処理剤は、例えば、ポリオール、酸化アルミニウム、水酸化アルミニウム、シリカ（酸化ケイ素）、含水シリカ、アルカノールアミン、ステアリン酸、オルガノシロキサン、酸化ジルコニウム、ハイドロゲンジメチコン、シランカップリング剤、チタネートカップリング剤などである。中でもシランカップリング剤が好ましい。 The filler may be subjected to surface treatment such as silane coupling treatment, titanate coupling treatment, epoxy treatment, urethane treatment, and oxidation treatment. Surface treatment agents used for surface treatment include, for example, polyol, aluminum oxide, aluminum hydroxide, silica (silicon oxide), hydrated silica, alkanolamine, stearic acid, organosiloxane, zirconium oxide, hydrogen dimethicone, silane coupling agent, Titanate coupling agents and the like. Among them, silane coupling agents are preferred.
　フィラーの大きさについて、フィラーの平均粒子径は、３０μｍ以下であることが好ましく、２０μｍ以下であることがより好ましく、１０μｍ以下であることが更に好ましい。
　また、フィラーの平均粒子径は、０．０１μｍ以上であることが好ましく、０．０５μｍ以上であることがより好ましく、０．１μｍ以上であることが更に好ましく、０．３μｍ以上であることが特に好ましい。
　フィラーの「平均粒子径」は、ポリイミド含有部中のフィラーを走査型電子顕微鏡（ＳＥＭ）で観察し、フィラーの粒子が凝集していない部分（一次粒子）を観測して求めることができる。
　平均粒子径は、ＳＥＭにより観察された各粒子のみかけ上の輪郭に対する最小包含円の直径の平均値として算出することができる。
　具体的には、後述する実施例に記載した方法により記載することができる。 Regarding the size of the filler, the average particle size of the filler is preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 10 μm or less.
The average particle size of the filler is preferably 0.01 µm or more, more preferably 0.05 µm or more, still more preferably 0.1 µm or more, and particularly preferably 0.3 µm or more. preferable.
The "average particle size" of the filler can be obtained by observing the filler in the polyimide-containing portion with a scanning electron microscope (SEM) and observing the portion (primary particles) where the particles of the filler are not aggregated.
The average particle size can be calculated as the average diameter of the smallest enclosing circle for the apparent outline of each particle observed by SEM.
Specifically, it can be described by the method described in Examples described later.
　フィラーは、粒子径が異なる少なくとも２種の粒子群が混合された粒状混合物を含んでいてもよい。ある粒子群の「粒子径」も、フィラーの「粒子径」の場合と同様の方法により求める。このような構成にすると、大きな粒子同士の間に小さな粒子が埋まって、単一径フィラーのみを含む場合に比べて、フィラー同士の間隔が減少し、さらには接触点が増加するため、熱伝導性が向上する。例えば、粒子径が異なる２種の粒子群が混合された場合には、これらの粒子群を含むフィラーの粒度分布において、２つのピークが観測される。したがって、フィラーの粒度分布におけるピーク数を確認することで、フィラーである粒状混合物中に、粒子径が異なる粒子群が何種類含まれているか、を確認することができる。 The filler may contain a particulate mixture in which at least two types of particle groups with different particle sizes are mixed. The "particle size" of a certain particle group is also determined by the same method as the "particle size" of the filler. With this configuration, the smaller particles are embedded between the larger particles, reducing the spacing between the fillers and thus increasing the number of contact points compared to only single-diameter fillers, thus increasing the thermal conductivity. improve sexuality. For example, when two types of particle groups with different particle sizes are mixed, two peaks are observed in the particle size distribution of the filler containing these particle groups. Therefore, by confirming the number of peaks in the particle size distribution of the filler, it is possible to confirm how many types of particle groups with different particle diameters are included in the particulate mixture that is the filler.
　フィラーの粒度分布におけるピーク数が複数ある場合には、少なくとも２つのピークの間について、ピーク粒子径比（ピーク頂点に相当する粒子径同士の比）は、１．５～５０であることが好ましい。下限は、２以上であることが好ましく、４以上であることがより好ましい。上限は、４０以下であることが好ましく、２０以下であることがより好ましい。上記ピーク比が上記範囲であれば、大径フィラーが粗大粒子となることを抑制しつつ、大径フィラーの隙間の空間を小径フィラーが占めることが容易になる。
　また、少なくとも２つのピークの間について、粒度の小さいピークに対する粒度の大きいピークのピーク強度比は、０．２～５．０であることが好ましい。下限は、０．２以上であることが好ましく、０．５以上であることがより好ましい。上限は、５．０以下であることが好ましく、３．０以下であることがより好ましい。 When there are multiple peaks in the particle size distribution of the filler, the peak particle size ratio (the ratio of particle sizes corresponding to peak apexes) between at least two peaks is preferably 1.5 to 50. . The lower limit is preferably 2 or more, more preferably 4 or more. The upper limit is preferably 40 or less, more preferably 20 or less. If the peak ratio is within the above range, it becomes easy for the small-diameter filler to occupy the space between the large-diameter fillers while preventing the large-diameter filler from becoming coarse particles.
Also, between at least two peaks, the peak intensity ratio of the peak with large particle size to the peak with small particle size is preferably 0.2 to 5.0. The lower limit is preferably 0.2 or more, more preferably 0.5 or more. The upper limit is preferably 5.0 or less, more preferably 3.0 or less.
　フィラーの含有量は、樹脂組成物の全固形分に対して、１０質量％以上が好ましく、３０質量％以上がより好ましい。
　上記含有量の上限は特に限定されないが、リソグラフィーによる加工性の観点から、９０質量％以下であることが好ましく、７５質量％以下であることがより好ましい。
　樹脂組成物がフィラーを含有する場合、フィラー以外の成分の含有量における「樹脂組成物の全固形分に対して」という主旨の記載は、「樹脂組成物の全固形分からフィラーを除いた全質量に対して」と読み替えるものとする。 The filler content is preferably 10% by mass or more, more preferably 30% by mass or more, relative to the total solid content of the resin composition.
Although the upper limit of the content is not particularly limited, it is preferably 90% by mass or less, more preferably 75% by mass or less, from the viewpoint of processability by lithography.
When the resin composition contains a filler, the description to the effect of "relative to the total solid content of the resin composition" in the content of components other than the filler is "total mass excluding the filler from the total solid content of the resin composition shall be read as "against".
　全フィラー中における、粒子径が０．５～１５μｍである粒子群の割合は、５０質量％以上が好ましく、８０質量％以上がより好ましい。この割合の上限は、１００質量％とすることもでき、９９質量％以下とすることもできる。この割合は、９９質量％以下が好ましく、９５質量％以下がさらに好ましい。 The ratio of the particle group having a particle diameter of 0.5 to 15 μm in the total filler is preferably 50% by mass or more, more preferably 80% by mass or more. The upper limit of this ratio can be 100% by mass, or can be 99% by mass or less. This ratio is preferably 99% by mass or less, more preferably 95% by mass or less.
　上記のとおり、フィラーは、１種または２種以上を組み合わせて使用でき、フィラーが２種以上含まれる場合には、それらの合計量が上記範囲にあることが好ましい。 As described above, the filler can be used singly or in combination of two or more. When two or more fillers are included, the total amount thereof is preferably within the above range.
＜その他の添加剤＞
　本発明の樹脂組成物は、本発明の効果が得られる範囲で、必要に応じて、各種の添加物、例えば、界面活性剤、高級脂肪酸誘導体、紫外線吸収剤、有機チタン化合物、酸化防止剤、凝集防止剤、フェノール系化合物、他の高分子化合物、可塑剤及びその他の助剤類（例えば、消泡剤、難燃剤など）等を配合することができる。これらの成分を適宜含有させることにより、膜物性などの性質を調整することができる。これらの成分は、例えば、特開２０１２－００３２２５号公報の段落番号０１８３以降（対応する米国特許出願公開第２０１３／００３４８１２号明細書の段落番号０２３７）の記載、特開２００８－２５００７４号公報の段落番号０１０１～０１０４、０１０７～０１０９等の記載を参酌でき、これらの内容は本明細書に組み込まれる。これらの添加剤を配合する場合、その合計配合量は本発明の樹脂組成物の固形分の３質量％以下とすることが好ましい。 <Other additives>
The resin composition of the present invention may contain various additives such as surfactants, higher fatty acid derivatives, ultraviolet absorbers, organic titanium compounds, antioxidants, Aggregation inhibitors, phenolic compounds, other polymer compounds, plasticizers and other auxiliaries (for example, antifoaming agents, flame retardants, etc.), etc., can be blended. Properties such as film physical properties can be adjusted by appropriately containing these components. These components are described, for example, from paragraph number 0183 of JP-A-2012-003225 (paragraph number 0237 of corresponding US Patent Application Publication No. 2013/0034812), paragraph of JP-A-2008-250074 The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated herein. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.
〔界面活性剤〕
　界面活性剤としては、フッ素系界面活性剤、シリコーン系界面活性剤、炭化水素系界面活性剤などの各種界面活性剤を使用できる。界面活性剤はノニオン型界面活性剤であってもよく、カチオン型界面活性剤であってもよく、アニオン型界面活性剤であってもよい。 [Surfactant]
As the surfactant, various surfactants such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
　本発明の感光性樹脂組成物に界面活性剤を含有させることで、塗布液として調製したときの液特性（特に、流動性）がより向上し、塗布厚の均一性や省液性をより改善することができる。即ち、界面活性剤を含有する組成物を適用した塗布液を用いて膜形成する場合においては、被塗布面と塗布液との界面張力が低下して、被塗布面への濡れ性が改善され、被塗布面への塗布性が向上する。このため、厚みムラの小さい均一厚の膜形成をより好適に行うことができる。 By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (especially fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and liquid saving are further improved. can do. That is, when a film is formed using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved. , the coatability to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with little unevenness in thickness.
　フッ素系界面活性剤としては、例えば、メガファックＦ１７１、同Ｆ１７２、同Ｆ１７３、同Ｆ１７６、同Ｆ１７７、同Ｆ１４１、同Ｆ１４２、同Ｆ１４３、同Ｆ１４４、同Ｒ３０、同Ｆ４３７、同Ｆ４７５、同Ｆ４７９、同Ｆ４８２、同Ｆ５５４、同Ｆ７８０、ＲＳ－７２－Ｋ（以上、ＤＩＣ（株）製）、フロラードＦＣ４３０、同ＦＣ４３１、同ＦＣ１７１、ノベックＦＣ４４３０、同ＦＣ４４３２（以上、スリーエム　ジャパン（株）製）、サーフロンＳ－３８２、同ＳＣ－１０１、同ＳＣ－１０３、同ＳＣ－１０４、同ＳＣ－１０５、同ＳＣ１０６８、同ＳＣ－３８１、同ＳＣ－３８３、同Ｓ３９３、同ＫＨ－４０（以上、旭硝子（株）製）、ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０、ＰＦ６５２０、ＰＦ７００２（ＯＭＮＯＶＡ社製）等が挙げられる。フッ素系界面活性剤は、特開２０１５－１１７３２７号公報の段落００１５～０１５８に記載の化合物、特開２０１１－１３２５０３号公報の段落０１１７～０１３２に記載の化合物を用いることもでき、これらの内容は本明細書に組み込まれる。フッ素系界面活性剤としてブロックポリマーを用いることもでき、具体例としては、例えば特開２０１１－８９０９０号公報に記載された化合物が挙げられ、これらの内容は本明細書に組み込まれる。
フッ素系界面活性剤は、フッ素原子を有する（メタ）アクリレート化合物に由来する繰り返し単位と、アルキレンオキシ基（好ましくはエチレンオキシ基、プロピレンオキシ基）を２以上（好ましくは５以上）有する（メタ）アクリレート化合物に由来する繰り返し単位と、を含む含フッ素高分子化合物も好ましく用いることができ、下記化合物も本発明で用いられるフッ素系界面活性剤として例示される。
Figure JPOXMLDOC01-appb-C000046
 Examples of fluorosurfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (manufactured by DIC Corporation), Florado FC430, FC431, FC171, Novec FC4430, FC4432 (manufactured by 3M Japan Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (Asahi Glass Co., Ltd. ), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like. Fluorinated surfactants, compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327, compounds described in paragraphs 0117-0132 of JP-A-2011-132503 can also be used, the contents of which are incorporated herein. A block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090, the contents of which are incorporated herein.
The fluorosurfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meta) A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.
Figure JPOXMLDOC01-appb-C000046
　上記の化合物の重量平均分子量は、好ましくは３，０００～５０，０００であり、５，０００～３０，０００であることがより好ましい。
　フッ素系界面活性剤は、エチレン性不飽和基を側鎖に有する含フッ素重合体をフッ素系界面活性剤として用いることもできる。具体例としては、特開２０１０－１６４９６５号公報の段落００５０～００９０および段落０２８９～０２９５に記載された化合物が挙げられ、この内容は本明細書に組み込まれる。また、市販品としては、例えばＤＩＣ（株）製のメガファックＲＳ－１０１、ＲＳ－１０２、ＲＳ－７１８Ｋ等が挙げられる。 The weight average molecular weight of the above compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
A fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used as a fluorine-based surfactant. Specific examples include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, the contents of which are incorporated herein. Commercially available products include Megafac RS-101, RS-102 and RS-718K manufactured by DIC Corporation.
　フッ素系界面活性剤中のフッ素含有率は、３～４０質量％が好適であり、より好ましくは５～３０質量％であり、特に好ましくは７～２５質量％である。フッ素含有率がこの範囲内であるフッ素系界面活性剤は、塗布膜の厚さの均一性や省液性の点で効果的であり、組成物中における溶解性も良好である。 The fluorine content in the fluorine-based surfactant is preferably 3-40% by mass, more preferably 5-30% by mass, and particularly preferably 7-25% by mass. A fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and saving liquid, and has good solubility in the composition.
　シリコーン系界面活性剤としては、例えば、トーレシリコーンＤＣ３ＰＡ、トーレシリコーンＳＨ７ＰＡ、トーレシリコーンＤＣ１１ＰＡ、トーレシリコーンＳＨ２１ＰＡ、トーレシリコーンＳＨ２８ＰＡ、トーレシリコーンＳＨ２９ＰＡ、トーレシリコーンＳＨ３０ＰＡ、トーレシリコーンＳＨ８４００（以上、東レ・ダウコーニング（株）製）、ＴＳＦ－４４４０、ＴＳＦ－４３００、ＴＳＦ－４４４５、ＴＳＦ－４４６０、ＴＳＦ－４４５２（以上、モメンティブ・パフォーマンス・マテリアルズ社製）、ＫＰ３４１、ＫＦ６００１、ＫＦ６００２（以上、信越シリコーン（株）製）、ＢＹＫ３０７、ＢＹＫ３２３、ＢＹＫ３３０（以上、ビックケミー（株）製）等が挙げられる。 Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (the above, Toray Dow Corning Co., Ltd. ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (manufactured by Shin-Etsu Silicone Co., Ltd.) ), BYK307, BYK323, and BYK330 (manufactured by BYK-Chemie Co., Ltd.).
　炭化水素系界面活性剤としては、例えば、パイオニンＡ－７６、ニューカルゲンＦＳ－３ＰＧ、パイオニンＢ－７０９、パイオニンＢ－８１１－Ｎ、パイオニンＤ－１００４、パイオニンＤ－３１０４、パイオニンＤ－３６０５、パイオニンＤ－６１１２、パイオニンＤ－２１０４－Ｄ、パイオニンＤ－２１２、パイオニンＤ－９３１、パイオニンＤ－９４１、パイオニンＤ－９５１、パイオニンＥ－５３１０、パイオニンＰ－１０５０－Ｂ、パイオニンＰ－１０２８－Ｐ、パイオニンＰ－４０５０－Ｔ等（以上、竹本油脂社製）、などが挙げられる。 Hydrocarbon surfactants include, for example, Pionin A-76, Nucalgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, Pionin D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, Pionin P-4050-T and the like (manufactured by Takemoto Oil & Fat Co., Ltd.), and the like.
　ノニオン型界面活性剤としては、グリセロール、トリメチロールプロパン、トリメチロールエタン並びにそれらのエトキシレート及びプロポキシレート（例えば、グリセロールプロポキシレート、グリセロールエトキシレート等）、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステルなどが例示される。市販品としては、プルロニック（登録商標）Ｌ１０、Ｌ３１、Ｌ６１、Ｌ６２、１０Ｒ５、１７Ｒ２、２５Ｒ２（ＢＡＳＦ社製）、テトロニック３０４、７０１、７０４、９０１、９０４、１５０Ｒ１（ＢＡＳＦ社製）、ソルスパース２００００（日本ルーブリゾール（株）製）、ＮＣＷ－１０１、ＮＣＷ－１００１、ＮＣＷ－１００２（和光純薬工業（株）製）、パイオニンＤ－６１１２、Ｄ－６１１２－Ｗ、Ｄ－６３１５（竹本油脂（株）製）、オルフィンＥ１０１０、サーフィノール１０４、４００、４４０（日信化学工業（株）製）などが挙げられる。 Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Examples include polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester. Commercially available products include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000. (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D-6315 (Takemoto oil ( Co., Ltd.), OLFINE E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.).
　カチオン型界面活性剤として具体的には、オルガノシロキサンポリマーＫＰ３４１（信越化学工業（株）製）、（メタ）アクリル酸系（共）重合体ポリフローＮｏ．７５、Ｎｏ．７７、Ｎｏ．９０、Ｎｏ．９５（共栄社化学（株）製）、Ｗ００１（裕商（株）製）等が挙げられる。 Specific examples of cationic surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 77, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.
　アニオン型界面活性剤として具体的には、Ｗ００４、Ｗ００５、Ｗ０１７（裕商（株）製）、サンデットＢＬ（三洋化成（株）製）等が挙げられる。 Specific examples of anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.), and Sandet BL (manufactured by Sanyo Kasei Co., Ltd.).
　界面活性剤は、１種のみを用いてもよいし、２種類以上を組み合わせてもよい。
界面活性剤の含有量は、組成物の全固形分に対して、０．００１～２．０質量％が好ましく、０．００５～１．０質量％がより好ましい。 Only one type of surfactant may be used, or two or more types may be used in combination.
The surfactant content is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.
〔高級脂肪酸誘導体〕
　本発明の樹脂組成物は、酸素に起因する重合阻害を防止するために、ベヘン酸やベヘン酸アミドのような高級脂肪酸誘導体を添加して、塗布後の乾燥の過程で本発明の樹脂組成物の表面に偏在させてもよい。 [Higher Fatty Acid Derivative]
In order to prevent polymerization inhibition caused by oxygen, the resin composition of the present invention is added with a higher fatty acid derivative such as behenic acid or behenic acid amide, and the resin composition of the present invention is dried in the process of drying after coating. may be unevenly distributed on the surface of the
　また、高級脂肪酸誘導体は、国際公開第２０１５／１９９２１９号の段落０１５５に記載の化合物を用いることもでき、この内容は本明細書に組み込まれる。 In addition, the compound described in paragraph 0155 of International Publication No. 2015/199219 can also be used as the higher fatty acid derivative, the content of which is incorporated herein.
　本発明の樹脂組成物が高級脂肪酸誘導体を有する場合、高級脂肪酸誘導体の含有量は、本発明の樹脂組成物の全固形分に対して、０．１～１０質量％であることが好ましい。高級脂肪酸誘導体は１種のみでもよいし、２種以上であってもよい。高級脂肪酸誘導体が２種以上の場合は、その合計が上記範囲であることが好ましい。 When the resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition of the present invention. Only one type of higher fatty acid derivative may be used, or two or more types thereof may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.
〔紫外線吸収剤〕
　本発明の組成物は、紫外線吸収剤を含んでいてもよい。紫外線吸収剤としては、サリシレート系、ベンゾフェノン系、ベンゾトリアゾール系、置換アクリロニトリル系、トリアジン系などの紫外線吸収剤を使用することができる。
　サリシレート系紫外線吸収剤の例としては、フェニルサリシレート、ｐ－オクチルフェニルサリシレート、ｐ－ｔ－ブチルフェニルサリシレートなどが挙げられ、ベンゾフェノン系紫外線吸収剤の例としては、２，２’－ジヒドロキシ－４－メトキシベンゾフェノン、２，２’－ジヒドロキシ－４，４’－ジメトキシベンゾフェノン、２，２’，４，４’－テトラヒドロキシベンゾフェノン、２－ヒドロキシ－４－メトキシベンゾフェノン、２，４－ジヒドロキシベンゾフェノン、２－ヒドロキシ－４－オクトキシベンゾフェノンなどが挙げられる。また、ベンゾトリアゾール系紫外線吸収剤の例としては、２－（２’－ヒドロキシ－３’，５’－ジ－ｔｅｒｔ－ブチルフェニル）－５－クロロベンゾトリアゾール、２－（２’－ヒドロキシ－３’－ｔｅｒｔ－ブチル－５’－メチルフェニル）－５－クロロベンゾトリアゾール、２－（２’－ヒドロキシ－３’－ｔｅｒｔ－アミル－５’－イソブチルフェニル）－５－クロロベンゾトリアゾール、２－（２’－ヒドロキシ－３’－イソブチル－５’－メチルフェニル）－５－クロロベンゾトリアゾール、２－（２’－ヒドロキシ－３’－イソブチル－５’－プロピルフェニル）－５－クロロベンゾトリアゾール、２－（２’－ヒドロキシ－３’，５’－ジ－ｔｅｒｔ－ブチルフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－５’－メチルフェニル）ベンゾトリアゾール、２－［２’－ヒドロキシ－５’－（１，１，３，３－テトラメチル）フェニル］ベンゾトリアゾールなどが挙げられる。 [Ultraviolet absorber]
The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used.
Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate, and the like. Examples of benzophenone-based UV absorbers include 2,2'-dihydroxy-4- Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- and hydroxy-4-octoxybenzophenone. Examples of benzotriazole-based UV absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3 '-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-( 2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2 -(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5' -(1,1,3,3-tetramethyl)phenyl]benzotriazole and the like.
　置換アクリロニトリル系紫外線吸収剤の例としては、２－シアノ－３，３－ジフェニルアクリル酸エチル、２－シアノ－３，３－ジフェニルアクリル酸２－エチルヘキシルなどが挙げられる。さらに、トリアジン系紫外線吸収剤の例としては、２－［４－［（２－ヒドロキシ－３－ドデシルオキシプロピル）オキシ］－２－ヒドロキシフェニル］－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン、２－［４－［（２－ヒドロキシ－３－トリデシルオキシプロピル）オキシ］－２－ヒドロキシフェニル］－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン、２－（２，４－ジヒドロキシフェニル）－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジンなどのモノ（ヒドロキシフェニル）トリアジン化合物；２，４－ビス（２－ヒドロキシ－４－プロピルオキシフェニル）－６－（２，４－ジメチルフェニル）－１，３，５－トリアジン、２，４－ビス（２－ヒドロキシ－３－メチル－４－プロピルオキシフェニル）－６－（４－メチルフェニル）－１，３，５－トリアジン、２，４－ビス（２－ヒドロキシ－３－メチル－４－ヘキシルオキシフェニル）－６－（２，４－ジメチルフェニル）－１，３，５－トリアジンなどのビス（ヒドロキシフェニル）トリアジン化合物；２，４－ビス（２－ヒドロキシ－４－ブトキシフェニル）－６－（２，４－ジブトキシフェニル）－１，３，５－トリアジン、２，４，６－トリス（２－ヒドロキシ－４－オクチルオキシフェニル）－１，３，５－トリアジン、２，４，６－トリス［２－ヒドロキシ－４－（３－ブトキシ－２－ヒドロキシプロピルオキシ）フェニル］－１，３，５－トリアジンなどのトリス（ヒドロキシフェニル）トリアジン化合物等が挙げられる。 Examples of substituted acrylonitrile UV absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Furthermore, examples of triazine-based UV absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl )-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) -mono(hydroxyphenyl)triazine compounds such as 1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl -4-propyloxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2 bis(hydroxyphenyl)triazine compounds such as ,4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl )-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4 tris(hydroxyphenyl)triazine compounds such as -(3-butoxy-2-hydroxypropyloxy)phenyl]-1,3,5-triazine;
本発明においては、上記各種の紫外線吸収剤は一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
本発明の組成物は、紫外線吸収剤を含んでも含まなくてもよいが、含む場合、紫外線吸収剤の含有量は、本発明の組成物の全固形分質量に対して、０．００１質量％以上１質量％以下であることが好ましく、０．０１質量％以上０．１質量％以下であることがより好ましい。 In the present invention, the above various ultraviolet absorbers may be used singly or in combination of two or more.
The composition of the present invention may or may not contain an ultraviolet absorber, but when it does, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid mass of the composition of the present invention. It is preferably at least 1% by mass, more preferably at least 0.01% by mass and not more than 0.1% by mass.
〔有機チタン化合物〕
　本実施形態の樹脂組成物は、有機チタン化合物を含有してもよい。樹脂組成物が有機チタン化合物を含有することにより、低温で硬化した場合であっても耐薬品性に優れる樹脂層を形成できる。 [Organic titanium compound]
The resin composition of this embodiment may contain an organic titanium compound. By including the organic titanium compound in the resin composition, it is possible to form a resin layer having excellent chemical resistance even when cured at a low temperature.
　使用可能な有機チタン化合物としては、チタン原子に有機基が共有結合又はイオン結合を介して結合しているものが挙げられる。
　有機チタン化合物の具体例を、以下のＩ）～ＶＩＩ）に示す：
　Ｉ）チタンキレート化合物：中でも、樹脂組成物の保存安定性がよく、良好な硬化パターンが得られることから、アルコキシ基を２個以上有するチタンキレート化合物がより好ましい。具体的な例は、チタニウムビス（トリエタノールアミン）ジイソプロポキサイド、チタニウムジ（ｎ－ブトキサイド）ビス（２，４－ペンタンジオネート）、チタニウムジイソプロポキサイドビス（２，４－ペンタンジオネート）、チタニウムジイソプロポキサイドビス（テトラメチルヘプタンジオネート）、チタニウムジイソプロポキサイドビス（エチルアセトアセテート）等である。
　ＩＩ）テトラアルコキシチタン化合物：例えば、チタニウムテトラ（ｎ－ブトキサイド）、チタニウムテトラエトキサイド、チタニウムテトラ（２－エチルヘキソキサイド）、チタニウムテトライソブトキサイド、チタニウムテトライソプロポキサイド、チタニウムテトラメトキサイド、チタニウムテトラメトキシプロポキサイド、チタニウムテトラメチルフェノキサイド、チタニウムテトラ（ｎ－ノニロキサイド）、チタニウムテトラ（ｎ－プロポキサイド）、チタニウムテトラステアリロキサイド、チタニウムテトラキス［ビス｛２，２－（アリロキシメチル）ブトキサイド｝］等である。
　ＩＩＩ）チタノセン化合物：例えば、ペンタメチルシクロペンタジエニルチタニウムトリメトキサイド、ビス（η５－２，４－シクロペンタジエン－１－イル）ビス（２，６－ジフルオロフェニル）チタニウム、ビス（η５－２，４－シクロペンタジエン－１－イル）ビス（２，６－ジフルオロ－３－（１Ｈ－ピロール－１－イル）フェニル）チタニウム等である。
　ＩＶ）モノアルコキシチタン化合物：例えば、チタニウムトリス（ジオクチルホスフェート）イソプロポキサイド、チタニウムトリス（ドデシルベンゼンスルホネート）イソプロポキサイド等である。
　Ｖ）チタニウムオキサイド化合物：例えば、チタニウムオキサイドビス（ペンタンジオネート）、チタニウムオキサイドビス（テトラメチルヘプタンジオネート）、フタロシアニンチタニウムオキサイド等である。
　ＶＩ）チタニウムテトラアセチルアセトネート化合物：例えば、チタニウムテトラアセチルアセトネート等である。
ＶＩＩ）チタネートカップリング剤：例えば、イソプロピルトリドデシルベンゼンスルホニルチタネート等である。 Organotitanium compounds that can be used include those in which organic groups are attached to titanium atoms through covalent or ionic bonds.
Specific examples of organotitanium compounds are shown below in I) to VII):
I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the storage stability of the resin composition is good and a good curing pattern can be obtained. Specific examples are titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate ), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like.
II) Tetraalkoxytitanium compounds: for example titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide , titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl) butoxide}] and the like.
III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2, 4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and the like.
IV) Monoalkoxy titanium compounds: for example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, and the like.
V) Titanium oxide compounds: for example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide and the like.
VI) Titanium tetraacetylacetonate compounds: such as titanium tetraacetylacetonate.
VII) Titanate coupling agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.
　中でも、有機チタン化合物としては、上記Ｉ）チタンキレート化合物、ＩＩ）テトラアルコキシチタン化合物、及びＩＩＩ）チタノセン化合物から成る群から選ばれる少なくとも１種の化合物であることが、より良好な耐薬品性を奏するという観点から好ましい。特に、チタニウムジイソプロポキサイドビス（エチルアセトアセテート）、チタニウムテトラ（ｎ－ブトキサイド）、及びビス（η５－２，４－シクロペンタジエン－１－イル）ビス（２，６－ジフルオロ－３－（１Ｈ－ピロール－１－イル）フェニル）チタニウムが好ましい。 Among them, as the organotitanium compound, at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds provides better chemical resistance. It is preferable from the viewpoint of performance. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide) and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H) -pyrrol-1-yl)phenyl)titanium is preferred.
　有機チタン化合物を配合する場合、その配合量は、特定樹脂１００質量部に対し、０．０５～１０質量部であることが好ましく、より好ましくは０．１～２質量部である。配合量が０．０５質量部以上である場合、得られる硬化パターンに良好な耐熱性及び耐薬品性がより効果的に発現し、一方１０質量部以下である場合、組成物の保存安定性により優れる。 When the organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. When the amount is 0.05 parts by mass or more, the resulting cured pattern exhibits good heat resistance and chemical resistance more effectively. Excellent.
〔酸化防止剤〕
本発明の組成物は、酸化防止剤を含んでいてもよい。添加剤として酸化防止剤を含有することで、硬化後の膜の伸度特性や、金属材料との密着性を向上させることができる。酸化防止剤としては、フェノール化合物、亜リン酸エステル化合物、チオエーテル化合物などが挙げられる。フェノール化合物としては、フェノール系酸化防止剤として知られる任意のフェノール化合物を使用することができる。好ましいフェノール化合物としては、ヒンダードフェノール化合物が挙げられる。フェノール性ヒドロキシ基に隣接する部位（オルト位）に置換基を有する化合物が好ましい。上述の置換基としては炭素数１～２２の置換又は無置換のアルキル基が好ましい。また、酸化防止剤は、同一分子内にフェノール基と亜リン酸エステル基を有する化合物も好ましい。また、酸化防止剤は、リン系酸化防止剤も好適に使用することができる。リン系酸化防止剤としてはトリス［２－［［２，４，８，１０－テトラキス（１，１－ジメチルエチル）ジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピン－６－イル］オキシ］エチル］アミン、トリス［２－［（４，６，９，１１－テトラ－ｔｅｒｔ－ブチルジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピン－２－イル）オキシ］エチル］アミン、亜リン酸エチルビス（２，４－ジ－ｔｅｒｔ－ブチル－６－メチルフェニル）などが挙げられる。酸化防止剤の市販品としては、例えば、アデカスタブ　ＡＯ－２０、アデカスタブ　ＡＯ－３０、アデカスタブ　ＡＯ－４０、アデカスタブ　ＡＯ－５０、アデカスタブ　ＡＯ－５０Ｆ、アデカスタブ　ＡＯ－６０、アデカスタブ　ＡＯ－６０Ｇ、アデカスタブ　ＡＯ－８０、アデカスタブ　ＡＯ－３３０（以上、（株）ＡＤＥＫＡ製）などが挙げられる。また、酸化防止剤は、特許第６２６８９６７号公報の段落番号００２３～００４８に記載された化合物を使用することもでき、この内容は本明細書に組み込まれる。また、本発明の組成物は、必要に応じて、潜在酸化防止剤を含有してもよい。潜在酸化防止剤としては、酸化防止剤として機能する部位が保護基で保護された化合物であって、１００～２５０℃で加熱するか、又は酸／塩基触媒存在下で８０～２００℃で加熱することにより保護基が脱離して酸化防止剤として機能する化合物が挙げられる。潜在酸化防止剤としては、国際公開第２０１４／０２１０２３号、国際公開第２０１７／０３０００５号、特開２０１７－００８２１９号公報に記載された化合物が挙げられ、この内容は本明細書に組み込まれる。潜在酸化防止剤の市販品としては、アデカアークルズＧＰＡ－５００１（（株）ＡＤＥＫＡ製）等が挙げられる。
　好ましい酸化防止剤の例としては、２，２－チオビス（４－メチル－６－ｔ－ブチルフェノール）、２，６－ジ－ｔ－ブチルフェノールおよび式（３）で表される化合物が挙げられる。 〔Antioxidant〕
The compositions of the present invention may contain antioxidants. By containing an antioxidant as an additive, it is possible to improve the elongation properties of the cured film and the adhesion to metal materials. Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. A substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable as the above substituent. The antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Phosphorus-based antioxidants can also be suitably used as antioxidants. As a phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl ) oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like. Examples of commercially available antioxidants include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Corporation) and the like. In addition, as the antioxidant, compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used, the contents of which are incorporated herein. The composition of the present invention may also contain latent antioxidants, if desired. The latent antioxidant is a compound in which the site functioning as an antioxidant is protected with a protective group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst. A compound that functions as an antioxidant by removing the protective group by the reaction is exemplified. Examples of latent antioxidants include compounds described in WO 2014/021023, WO 2017/030005, and JP 2017-008219, the contents of which are incorporated herein. Commercially available latent antioxidants include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.).
Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds of formula (3).
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
　一般式（３）中、Ｒ５は水素原子または炭素数２以上（好ましくは炭素数２～１０）のアルキル基を表し、Ｒ６は炭素数２以上（好ましくは炭素数２～１０）のアルキレン基を表す。Ｒ７は、炭素数２以上（好ましくは炭素数２～１０）のアルキレン基、酸素原子、および窒素原子のうち少なくともいずれかを含む１～４価の有機基を示す。ｋは１～４の整数を示す。 In general formula (3), R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R 6 represents alkylene having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). represents a group. R 7 represents a monovalent to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom and a nitrogen atom. k represents an integer of 1 to 4;
　式（３）で表される化合物は、樹脂が有する脂肪族基やフェノール性水酸基の酸化劣化を抑制する。また、金属材料への防錆作用により、金属酸化を抑制することができる。 The compound represented by formula (3) suppresses oxidative deterioration of the aliphatic groups and phenolic hydroxyl groups of the resin. In addition, metal oxidation can be suppressed by the antirust action on the metal material.
　樹脂と金属材料に同時に作用できるため、ｋは２～４の整数がより好ましい。Ｒ７としては、アルキル基、シクロアルキル基、アルコキシ基、アルキルエーテル基、アルキルシリル基、アルコキシシリル基、アリール基、アリールエーテル基、カルボキシル基、カルボニル基、アリル基、ビニル基、複素環基、－Ｏ－、－ＮＨ－、－ＮＨＮＨ－、それらを組み合わせたものなどが挙げられ、さらに置換基を有していてもよい。この中でも、現像液への溶解性や金属密着性の点から、アルキルエーテル基、－ＮＨ－を有することが好ましく、樹脂との相互作用と金属錯形成による金属密着性の点から－ＮＨ－がより好ましい。 More preferably, k is an integer of 2 to 4 because it can act on the resin and the metal material at the same time. R7 includes an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, combinations thereof, and the like, which may further have a substituent. Among these, it is preferable to have an alkyl ether group, -NH-, from the viewpoint of solubility in a developer and metal adhesion. more preferred.
　一般式（３）で表される化合物は、例としては以下のものが挙げられるが、下記構造に限らない。 Examples of compounds represented by general formula (3) include the following, but are not limited to the structures below.
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000051
　酸化防止剤の添加量は、特定樹脂１００質量部に対し、０．１～１０質量部が好ましく、０．５～５質量部がより好ましい。添加量を０．１質量部以上とすることにより、高温高湿環境下においても伸度特性や金属材料に対する密着性向上の効果が得られやすく、また１０質量部以下とすることにより、例えば感光剤との相互作用により、樹脂組成物の感度が向上する。酸化防止剤は１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合は、それらの合計量が上記範囲となることが好ましい。 The amount of antioxidant to be added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. By making the addition amount 0.1 parts by mass or more, the effect of improving elongation characteristics and adhesion to metal materials can be easily obtained even in a high-temperature and high-humidity environment. The interaction with the agent improves the sensitivity of the resin composition. Only one kind of antioxidant may be used, or two or more kinds thereof may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
〔凝集防止剤〕
　本実施形態の樹脂組成物は、必要に応じて凝集防止剤を含有してもよい。凝集防止剤としては、ポリアクリル酸ナトリウム等が挙げられる。 [Anti-aggregation agent]
The resin composition of the present embodiment may contain an anti-aggregation agent as necessary. Anti-aggregating agents include sodium polyacrylate and the like.
　本発明においては、凝集防止剤は一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
　本発明の組成物は、凝集防止剤を含んでも含まなくてもよいが、含む場合、凝集防止剤の含有量は、本発明の組成物の全固形分質量に対して、０．０１質量％以上１０質量％以下であることが好ましく、０．０２質量％以上５質量％以下であることがより好ましい。 In the present invention, the aggregation inhibitor may be used alone or in combination of two or more.
The composition of the present invention may or may not contain an anti-aggregating agent, but when it is included, the content of the anti-aggregating agent is 0.01% by mass relative to the total solid mass of the composition of the present invention. It is preferably at least 10% by mass, more preferably at least 0.02% by mass and not more than 5% by mass.
〔フェノール系化合物〕
　本実施形態の樹脂組成物は、必要に応じてフェノール系化合物を含有してもよい。フェノール系化合物としては、Ｂｉｓ－Ｚ、ＢｉｓＰ－ＥＺ、ＴｅｋＰ－４ＨＢＰＡ、ＴｒｉｓＰ－ＨＡＰ、ＴｒｉｓＰ－ＰＡ、ＢｉｓＯＣＨＰ－Ｚ、ＢｉｓＰ－ＭＺ、ＢｉｓＰ－ＰＺ、ＢｉｓＰ－ＩＰＺ、ＢｉｓＯＣＰ－ＩＰＺ、ＢｉｓＰ－ＣＰ、ＢｉｓＲＳ－２Ｐ、ＢｉｓＲＳ－３Ｐ、ＢｉｓＰ－ＯＣＨＰ、メチレントリス－ＦＲ－ＣＲ、ＢｉｓＲＳ－２６Ｘ（以上、商品名、本州化学工業（株）製）、ＢＩＰ－ＰＣ、ＢＩＲ－ＰＣ、ＢＩＲ－ＰＴＢＰ、ＢＩＲ－ＢＩＰＣ－Ｆ（以上、商品名、旭有機材工業（株）製）等が挙げられる。 [Phenolic compound]
The resin composition of the present embodiment may contain a phenolic compound as necessary. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X (these are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR -BIPC-F (these are trade names, manufactured by Asahi Organic Chemicals Industry Co., Ltd.) and the like.
　本発明においては、フェノール系化合物は一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
　本発明の組成物は、フェノール系化合物を含んでも含まなくてもよいが、含む場合、フェノール系化合物の含有量は、本発明の組成物の全固形分質量に対して、０．０１質量％以上３０質量％以下であることが好ましく、０．０２質量％以上２０質量％以下であることがより好ましい。 In the present invention, one type of phenolic compound may be used alone, or two or more types may be used in combination.
The composition of the present invention may or may not contain a phenolic compound, but if it does, the content of the phenolic compound is 0.01% by mass relative to the total solid mass of the composition of the present invention. It is preferably at least 30% by mass, more preferably at least 0.02% by mass and not more than 20% by mass.
〔他の高分子化合物〕
　他の高分子化合物としては、シロキサン樹脂、（メタ）アクリル酸を共重合した（メタ）アクリルポリマー、ノボラック樹脂、レゾール樹脂、ポリヒドロキシスチレン樹脂およびそれらの共重合体などが挙げられる。他の高分子化合物はメチロール基、アルコキシメチル基、エポキシ基などの架橋基が導入された変性体であってもよい。 [Other polymer compounds]
Other polymer compounds include siloxane resins, (meth)acrylic polymers obtained by copolymerizing (meth)acrylic acid, novolac resins, resole resins, polyhydroxystyrene resins, and copolymers thereof. Other polymer compounds may be modified products into which cross-linking groups such as methylol groups, alkoxymethyl groups and epoxy groups have been introduced.
　本発明においては、他の高分子化合物は一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
　本発明の組成物は、他の高分子化合物を含んでも含まなくてもよいが、含む場合、他の高分子化合物の含有量は、本発明の組成物の全固形分質量に対して、０．０１質量％以上３０質量％以下であることが好ましく、０．０２質量％以上２０質量％以下であることがより好ましい。 In the present invention, other polymer compounds may be used singly or in combination of two or more.
The composition of the present invention may or may not contain other polymer compounds, but when it does, the content of the other polymer compound is 0 relative to the total solid mass of the composition of the present invention. It is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.
＜樹脂組成物の特性＞
　本発明の樹脂組成物の粘度は、樹脂組成物の固形分濃度により調整できる。塗布膜厚の観点から、１，０００ｍｍ２／ｓ～１２，０００ｍｍ２／ｓが好ましく、２，０００ｍｍ２／ｓ～１０，０００ｍｍ２／ｓがより好ましく、２，５００ｍｍ２／ｓ～８，０００ｍｍ２／ｓが更に好ましい。上記範囲であれば、均一性の高い塗布膜を得ることが容易になる。１,０００ｍｍ２／s以上であれば、例えば再配線用絶縁膜として必要とされる膜厚で塗布することが容易であり、１２,０００ｍｍ２／s以下であれば、塗布面状に優れた塗膜が得られる。 <Characteristics of resin composition>
The viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition. From the viewpoint of coating film thickness, it is preferably 1,000 mm 2 /s to 12,000 mm 2 /s, more preferably 2,000 mm 2 /s to 10,000 mm 2 /s, and 2,500 mm 2 /s to 8,000 mm. 2 /s is more preferred. If it is the said range, it will become easy to obtain a coating film with high uniformity. If it is 1,000 mm 2 /s or more , it is easy to apply the film with a film thickness required, for example, as an insulating film for rewiring. A coating is obtained.
＜樹脂組成物の含有物質についての制限＞
　本発明の樹脂組成物の含水率は、２．０質量％未満であることが好ましく、１．５質量％未満であることがより好ましく、１．０質量％未満であることが更に好ましい。２．０％未満であれば、樹脂組成物の保存安定性が向上する。
　水分の含有量を維持する方法としては、保管条件における湿度の調整、保管時の収容容器の空隙率低減などが挙げられる。 <Restrictions on Substances Contained in Resin Composition>
The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved.
Methods for maintaining the moisture content include adjusting the humidity in the storage conditions and reducing the porosity of the storage container during storage.
　本発明の樹脂組成物の金属含有量は、絶縁性の観点から、５質量ｐｐｍ（ｐａｒｔｓ　ｐｅｒ　ｍｉｌｌｉｏｎ）未満が好ましく、１質量ｐｐｍ未満がより好ましく、０．５質量ｐｐｍ未満が更に好ましい。金属としては、ナトリウム、カリウム、マグネシウム、カルシウム、鉄、銅、クロム、ニッケルなどが挙げられるが、有機化合物と金属との錯体として含まれる金属は除く。金属を複数含む場合は、これらの金属の合計が上記範囲であることが好ましい。 From the viewpoint of insulation, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are included, the total of these metals is preferably within the above range.
　また、本発明の樹脂組成物に意図せずに含まれる金属不純物を低減する方法としては、本発明の樹脂組成物を構成する原料として金属含有量が少ない原料を選択する、本発明の樹脂組成物を構成する原料に対してフィルターろ過を行う、装置内をポリテトラフルオロエチレン等でライニングしてコンタミネーションを可能な限り抑制した条件下で蒸留を行う等の方法を挙げることができる。 In addition, as a method for reducing metal impurities unintentionally contained in the resin composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the resin composition of the present invention. For example, the raw material constituting the product is filtered through a filter, or the inside of the apparatus is lined with polytetrafluoroethylene or the like to perform distillation under conditions in which contamination is suppressed as much as possible.
　本発明の樹脂組成物は、半導体材料としての用途を考慮すると、ハロゲン原子の含有量が、配線腐食性の観点から、５００質量ｐｐｍ未満が好ましく、３００質量ｐｐｍ未満がより好ましく、２００質量ｐｐｍ未満が更に好ましい。中でも、ハロゲンイオンの状態で存在するものは、５質量ｐｐｍ未満が好ましく、１質量ｐｐｍ未満がより好ましく、０．５質量ｐｐｍ未満が更に好ましい。ハロゲン原子としては、塩素原子及び臭素原子が挙げられる。塩素原子及び臭素原子、又は塩素イオン及び臭素イオンの合計がそれぞれ上記範囲であることが好ましい。
　ハロゲン原子の含有量を調節する方法としては、イオン交換処理などが好ましく挙げられる。 Considering the use as a semiconductor material, the resin composition of the present invention preferably has a halogen atom content of less than 500 ppm by mass, more preferably less than 300 ppm by mass, and less than 200 ppm by mass from the viewpoint of wiring corrosion. is more preferred. Among them, those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Halogen atoms include chlorine and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms or chlorine ions and bromine ions is within the above ranges.
As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferably mentioned.
　本発明の樹脂組成物の収容容器としては従来公知の収容容器を用いることができる。また、収容容器としては、原材料や本発明の樹脂組成物中への不純物混入を抑制することを目的に、容器内壁を６種６層の樹脂で構成された多層ボトルや、６種の樹脂を７層構造にしたボトルを使用することも好ましい。このような容器としては例えば特開２０１５－１２３３５１号公報に記載の容器が挙げられる。 A conventionally known container can be used as the container for the resin composition of the present invention. In addition, as the storage container, for the purpose of suppressing the contamination of the raw materials and the resin composition of the present invention, the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resin are used. It is also preferred to use bottles with a seven-layer structure. Examples of such a container include the container described in JP-A-2015-123351.
＜樹脂組成物の硬化物＞
　本発明の樹脂組成物を硬化することにより、この樹脂組成物の硬化物を得ることができる。
　本発明の硬化物は、本発明の樹脂組成物を硬化してなる硬化物である。
　樹脂組成物の硬化は加熱によるものであることが好ましく、加熱温度が１２０℃～４００℃の範囲内であることがより好ましく、１４０℃～３８０℃の範囲内にあることが更に好ましく、１７０℃～３５０℃の範囲内にあることが特に好ましい。樹脂組成物の硬化物の形態は、特に限定されず、フィルム状、棒状、球状、ペレット状など、用途に合わせて選択することができる。本発明において、この硬化物は、フィルム状であることが好ましい。また、樹脂組成物のパターン加工によって、壁面への保護膜の形成、導通のためのビアホール形成、インピーダンスや静電容量あるいは内部応力の調整、放熱機能付与など、用途にあわせて、この硬化物の形状を選択することもできる。この硬化物（硬化物からなる膜）の膜厚は、０．５μｍ以上１５０μｍ以下であることが好ましい。
　本発明の樹脂組成物を硬化した際の収縮率は、５０％以下が好ましく、４５％以下がより好ましく、４０％以下が更に好ましい。ここで、収縮率は、樹脂組成物の硬化前後の体積変化の百分率を指し、下記の式より算出することができる。
　収縮率［％］＝１００－（硬化後の体積÷硬化前の体積）×１００ <Cured product of resin composition>
By curing the resin composition of the present invention, a cured product of this resin composition can be obtained.
The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.
Curing of the resin composition is preferably by heating, and the heating temperature is more preferably in the range of 120°C to 400°C, more preferably in the range of 140°C to 380°C, and 170°C. It is particularly preferred to be in the range of -350°C. The form of the cured product of the resin composition is not particularly limited, and can be selected from film-like, rod-like, spherical, pellet-like, etc. according to the application. In the present invention, this cured product is preferably in the form of a film. In addition, pattern processing of the resin composition can be used to form protective films on walls, form via holes for conduction, adjust impedance, capacitance or internal stress, and impart heat dissipation functions. You can also choose the shape. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less.
The shrinkage ratio when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage ratio refers to the percentage change in volume of the resin composition before and after curing, and can be calculated from the following formula.
Shrinkage rate [%] = 100 - (volume after curing / volume before curing) x 100
＜樹脂組成物の硬化物の特性＞
　本発明の樹脂組成物の硬化物のイミド化反応率は、７０％以上が好ましく、８０％以上がより好ましく、９０％以上が更に好ましい。７０％以上であれば、機械特性に優れた硬化物となる場合がある。
　本発明の樹脂組成物の硬化物の破断伸びは、３０％以上が好ましく、４０％以上がより好ましく、５０％以上が更に好ましい。
　本発明の樹脂組成物の硬化物のガラス転移温度（Ｔｇ）は、１８０℃以上であることが好ましく、２１０℃以上であることがより好ましく、２３０℃以上であることがさらに好ましい。 <Characteristics of Cured Product of Resin Composition>
The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or higher, more preferably 80% or higher, and even more preferably 90% or higher. If it is 70% or more, a cured product having excellent mechanical properties may be obtained.
The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180° C. or higher, more preferably 210° C. or higher, and even more preferably 230° C. or higher.
（接合体の製造方法）
　本発明の接合体の製造方法は、配線端子を備える面を有する基板Ａを準備する工程、上記基板Ａの上記配線端子を備える面上にポリイミド含有部を形成するポリイミド含有部形成工程、配線端子を備える面を有する基板Ｂを準備する工程、及び、上記基板Ａのポリイミド含有部を有する面と、上記基板Ｂにおける上記配線端子を備える面とを接合する接合工程、を含み、上記ポリイミド含有部のガラス転移温度が、上記接合工程における接合温度よりも低い温度である。
　本発明の接合体の製造方法における基板Ａ、基板Ｂ及び各工程の詳細は、上述の本発明のポリイミド含有部形成用組成物が用いられる接合体の製造方法における基板Ａ、基板Ｂ及び各工程の詳細と同様であり、好ましい態様も同様である。 (Manufacturing method of joined body)
The manufacturing method of the joined body of the present invention comprises a step of preparing a substrate A having a surface provided with a wiring terminal, a polyimide-containing portion forming step of forming a polyimide-containing portion on the surface of the substrate A provided with the wiring terminal, and a wiring terminal. and a bonding step of bonding the surface of the substrate A having the polyimide-containing portion and the surface of the substrate B having the wiring terminal, wherein the polyimide-containing portion is lower than the bonding temperature in the bonding step.
The details of the substrate A, the substrate B, and each step in the method for producing a joined body of the present invention are as follows: , and preferred embodiments are also the same.
（接合体）
　本発明の接合体は、本発明の接合体の製造方法により得られる接合体である。
　接合体の好ましい態様は、上述の本発明のポリイミド含有部形成用組成物が用いられる接合体の製造方法における接合体の好ましい態様と同様である。 (Zygotes)
The conjugate of the present invention is a conjugate obtained by the method for producing a conjugate of the present invention.
Preferred aspects of the joined body are the same as the preferred aspects of the joined body in the above-described method for producing a joined body using the composition for forming a polyimide-containing portion of the present invention.
　以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。したがって、本発明の範囲は以下に示す具体例に限定されるものではない。 The present invention will be described more specifically below with reference to examples. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
＜合成例１；ポリマーＰ－１の合成＞
　４，４’－オキシジフタル酸二無水物（ＯＤＰＡ）７．７６ｇ（２５ミリモル）および３，３’，４，４’-ビフェニルテトラカルボン酸二無水物６．２３ｇ（２５ミリモル）を反応容器に入れ、２－ヒドロキシエチルメタクリレート（ＨＥＭＡ）１３．４ｇ及びγ－ブチロラクトン１００ｍＬを加えた。室温下で撹拌しながら、ピリジン７．９１ｇを加えることにより、反応混合物を得た。反応による発熱の終了後、室温まで放冷し、更に１６時間静置した。
　次に、氷冷下において、反応混合物に、ジシクロヘキシルカルボジイミド（ＤＣＣ）２０．６ｇ（９９．９ミリモル）をγ－ブチロラクトン３０ｍＬに溶解した溶液を、撹拌しながら４０分かけて加えた。続いて、４，４’－ジアミノジフェニルエーテル（ＤＡＤＰＥ）９．３ｇ（４６ミリモル）をγ－ブチロラクトン３５０ｍＬに懸濁した懸濁液を、撹拌しながら６０分かけて加えた。
　更に室温で２時間撹拌した後、エチルアルコール３ｍＬを加えて１時間撹拌した。その後、γ－ブチロラクトン１００ｍＬを加えた。反応混合物に生じた沈殿物を、ろ過により取り除き、反応液を得た。
　得られた反応液を３リットルのエチルアルコールに加えて、粗ポリマーからなる沈殿物を生成した。生成した粗ポリマーを濾取し、テトラヒドロフラン２００ｍＬに溶解して粗ポリマー溶液を得た。得られた粗ポリマー溶液を３リットルの水に滴下してポリマーを沈殿させ、得られた沈殿物を濾取した後に真空乾燥することにより、粉末状のポリマーＰ－１を得た。
　このポリマーの重量平均分子量（Ｍｗ）を測定したところ、２３，０００であった。
　ポリマーＰ－１は下記構造の樹脂である。括弧の添字は各繰り返し単位のモル比を表す。
Figure JPOXMLDOC01-appb-C000052
 <Synthesis Example 1; Synthesis of Polymer P-1>
7.76 g (25 mmol) of 4,4'-oxydiphthalic dianhydride (ODPA) and 6.23 g (25 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride were placed in a reaction vessel. , 2-hydroxyethyl methacrylate (HEMA) 13.4 g and γ-butyrolactone 100 mL were added. A reaction mixture was obtained by adding 7.91 g of pyridine while stirring at room temperature. After the end of heat generation due to the reaction, the mixture was allowed to cool to room temperature and allowed to stand still for 16 hours.
Next, under ice-cooling, a solution of 20.6 g (99.9 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 30 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Subsequently, a suspension of 9.3 g (46 mmol) of 4,4′-diaminodiphenyl ether (DADPE) in 350 mL of γ-butyrolactone was added with stirring over 60 minutes.
After further stirring at room temperature for 2 hours, 3 mL of ethyl alcohol was added and the mixture was stirred for 1 hour. Then 100 mL of γ-butyrolactone was added. A precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
The resulting reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of crude polymer. The resulting crude polymer was collected by filtration and dissolved in 200 mL of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was dropped into 3 liters of water to precipitate the polymer, and the resulting precipitate was collected by filtration and dried in vacuo to obtain a powdery polymer P-1.
The weight average molecular weight (Mw) of this polymer was measured and found to be 23,000.
Polymer P-1 is a resin having the following structure. Subscripts in parentheses represent the molar ratio of each repeating unit.
Figure JPOXMLDOC01-appb-C000052
＜合成例２；ポリマーＰ－２の合成＞
　２０．０ｇ（６４．５ミリモル）の４，４’－オキシジフタル酸無水物（１４０℃で１２時間乾燥した）と、１６．８ｇ（１２９ミリモル）の２－ヒドロキシエチルメタクリレートと、０．０５ｇのハイドロキノンと、２０．４ｇ（２５８ミリモル）のピリジンと、１００ｇのダイグライムとを混合し、６０℃の温度で１８時間撹拌して、４，４’－オキシジフタル酸と２－ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、反応混合物を冷却し、１６．１２ｇ（１３５．５ミリモル）のＳＯＣｌ２を２時間かけて加えた。次いで、１００ｍＬのＮ－メチルピロリドンに１２．７４ｇ（６０．０ミリモル）の２，２’－ジメチルビフェニル‐４，４’－ジアミンを溶解させた溶液を、－５～０℃の温度範囲に調整しつつ、２時間かけて反応混合物に滴下した。反応混合物を０℃で１時間反応させたのち、エタノールを７０ｇ加えて、室温で１時間撹拌した。次いで、５リットルの水の中でポリイミド前駆体を沈殿させ、水－ポリイミド前駆体混合物を５，０００ｒｐｍの速度で１５分間撹拌した。ポリイミド前駆体をろ過して除き、４リットルの水の中で再度３０分間撹拌し再びろ過した。次いで、得られたポリイミド前駆体を減圧下で、２日間乾燥した。このポリイミド前駆体（ポリマーＰ－２）の重量平均分子量は、２９，０００であった。
　ポリマーＰ－２は下記構造の樹脂である。
Figure JPOXMLDOC01-appb-C000053
 <Synthesis Example 2; Synthesis of Polymer P-2>
20.0 g (64.5 mmol) of 4,4′-oxydiphthalic anhydride (dried at 140° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate and 0.05 g of hydroquinone , 20.4 g (258 mmol) of pyridine and 100 g of diglyme were mixed and stirred at a temperature of 60° C. for 18 hours to prepare a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. . The reaction mixture was then cooled and 16.12 g (135.5 mmol) of SOCl 2 was added over 2 hours. Then, a solution of 12.74 g (60.0 mmol) of 2,2'-dimethylbiphenyl-4,4'-diamine dissolved in 100 mL of N-methylpyrrolidone was adjusted to a temperature range of -5 to 0°C. was added dropwise to the reaction mixture over 2 hours. After reacting the reaction mixture at 0° C. for 1 hour, 70 g of ethanol was added and stirred at room temperature for 1 hour. The polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred at a speed of 5,000 rpm for 15 minutes. The polyimide precursor was filtered off, stirred again in 4 liters of water for 30 minutes and filtered again. The resulting polyimide precursor was then dried under reduced pressure for two days. The weight average molecular weight of this polyimide precursor (polymer P-2) was 29,000.
Polymer P-2 is a resin having the following structure.
Figure JPOXMLDOC01-appb-C000053
＜合成例３；ポリマーＰ－３の合成＞
　２０．０ｇ（６４．５ミリモル）の４，４’－オキシジフタル酸無水物（１４０℃で１２時間乾燥した）と、１６．８ｇ（１２９ミリモル）の２－ヒドロキシエチルメタクリレートと、０．０５ｇのハイドロキノンと、２０．４ｇ（２５８ミリモル）のピリジンと、１００ｇのダイグライムとを混合し、６０℃の温度で１８時間撹拌して、４，４’－オキシジフタル酸と２－ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、得られたジエステルをＳＯＣｌ２により塩素化した後、合成例２と同様にＮ－メチルピロリドンに４，４’－ジアミノジフェニルエーテルを溶解させた溶液を、反応混合物に滴下し、その後得た反応混合物を精製、乾燥した。このポリイミド前駆体（ポリマーＰ－３）の重量平均分子量は、１８，０００であった。
　ポリマーＰ－３は下記構造の樹脂である。
Figure JPOXMLDOC01-appb-C000054
 <Synthesis Example 3; Synthesis of polymer P-3>
20.0 g (64.5 mmol) of 4,4′-oxydiphthalic anhydride (dried at 140° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate and 0.05 g of hydroquinone , 20.4 g (258 mmol) of pyridine and 100 g of diglyme were mixed and stirred at a temperature of 60° C. for 18 hours to prepare a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. . Then, after chlorinating the resulting diester with SOCl 2 , a solution of 4,4'-diaminodiphenyl ether dissolved in N-methylpyrrolidone was added dropwise to the reaction mixture in the same manner as in Synthesis Example 2, and then the resulting reaction The mixture was purified and dried. The weight average molecular weight of this polyimide precursor (polymer P-3) was 18,000.
Polymer P-3 is a resin having the following structure.
Figure JPOXMLDOC01-appb-C000054
　表１に記載のとおり各成分を混合し、均一な溶液に調製した。得られた溶液を、細孔の幅が２０μｍのフィルターを通して圧力０．４ＭＰａにて、加圧ろ過し、樹脂組成物を得た。
　具体的には、表に記載の成分の含有量は、表に記載の量（質量部）とした。また、表中、「－」の記載は該当する成分を組成物が含有していないことを示している。 Each component was mixed as described in Table 1 to prepare a uniform solution. The resulting solution was pressure filtered at a pressure of 0.4 MPa through a filter with a pore width of 20 μm to obtain a resin composition.
Specifically, the contents of the components described in the table were the amounts (parts by mass) described in the table. In the table, the description of "-" indicates that the composition does not contain the corresponding component.
Figure JPOXMLDOC01-appb-T000055
Figure JPOXMLDOC01-appb-T000055
　表に記載の略語の詳細は下記の通りである。 Details of the abbreviations in the table are as follows.
〔樹脂〕
・Ｐ－１～Ｐ－３：上記で合成したＰ－１～Ｐ－３ 〔resin〕
・ P-1 to P-3: P-1 to P-3 synthesized above
〔重合性化合物〕
・Ｂ－１：テトラエチレングリコールジメタクリレート（Ａｒｋｅｍａ社製）
・Ｂ－２：ライトアクリレートＤＣＰ―Ａ（共栄社化学製）
・Ｂ－３：下記構造の化合物、括弧の添字は繰返し数を表す。
Figure JPOXMLDOC01-appb-C000056
・Ｂ－４：ＮＫエステルＡ－ＴＭＭＴ（新中村化学製） [Polymerizable compound]
· B-1: Tetraethylene glycol dimethacrylate (manufactured by Arkema)
・ B-2: Light acrylate DCP-A (manufactured by Kyoeisha Chemical)
*B-3: A compound having the following structure, the subscript in the parenthesis represents the number of repetitions.
Figure JPOXMLDOC01-appb-C000056
・ B-4: NK Ester A-TMMT (manufactured by Shin-Nakamura Chemical)
〔開始剤〕
・Ｃ－１：Ｉｒｇａｃｕｒｅ　ＯＸＥ－０１（ＢＡＳＦ社製）
・Ｃ－２：パークミルＤ（日油社製）
・Ｃ－３：下記構造の開始剤
Figure JPOXMLDOC01-appb-C000057
・Ｃ－４：Ｉｒｇａｃｕｒｅ　ＯＸＥ－０２（ＢＡＳＦ社製）
・Ｃ－５：Ｉｒｇａｃｕｒｅ　７８４（ＢＡＳＦ社製） [Initiator]
・ C-1: Irgacure OXE-01 (manufactured by BASF)
・ C-2: Parkmill D (manufactured by NOF Corporation)
· C-3: an initiator having the following structure
Figure JPOXMLDOC01-appb-C000057
・ C-4: Irgacure OXE-02 (manufactured by BASF)
・ C-5: Irgacure 784 (manufactured by BASF)
〔金属接着性改良剤〕
・Ｄ－１：Ｎ－［３－（トリエトキシシリル）プロピル］マレインアミド酸 [Metal adhesion improver]
・ D-1: N-[3-(triethoxysilyl)propyl]maleamic acid
〔マイグレーション抑制剤〕
・Ｅ－１：５－アミノテトラゾール
・Ｅ－２：１Ｈ－Ｔｅｔｒａｚｏｌｅ [Migration inhibitor]
・E-1: 5-aminotetrazole ・E-2: 1H-Tetrazole
〔重合禁止剤〕
・Ａ－１：４ＭｅＨＱ（４－メトキシフェノール）
・Ａ－２：ＴＥＭＰＯ（２，２，６，６－テトラメチルピペリジン　１－オキシル） [Polymerization inhibitor]
・ A-1: 4MeHQ (4-methoxyphenol)
・ A-2: TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl)
〔塩基発生剤〕
・Ｇ－１：１－［４－（２－ヒドロキシエチル）－１－ピペリジニル］－３－（２－ヒドロキシフェニル）－１－プロパノン
・Ｇ－２：下記化合物
Figure JPOXMLDOC01-appb-C000058
 [Base generator]
· G-1: 1-[4-(2-hydroxyethyl)-1-piperidinyl]-3-(2-hydroxyphenyl)-1-propanone · G-2: the following compound
Figure JPOXMLDOC01-appb-C000058
〔溶剤〕
・Ｈ－１：ＧＢＬ（γ－ブチロラクトン）
・Ｈ－２：EL（乳酸エチル）
・Ｈ－３：ＮＭＰ（Ｎ－メチルピロリドン）
・Ｈ－４：ＤＭＳＯ（ジメチルスルホキシド） 〔solvent〕
・ H-1: GBL (γ-butyrolactone)
・H-2: EL (ethyl lactate)
・ H-3: NMP (N-methylpyrrolidone)
· H-4: DMSO (dimethyl sulfoxide)
＜基板の作製＞
　めっきにて以下のサイズ、金属種を持つピラー基板を作製した。
ａ）ピッチ；２５μｍ、銅ピラー径;１０μｍ、銅ピラー高;１０μｍ
ｂ）ピッチ；４５μｍ、銅／錫ピラー径;２０μｍ、銅／錫ピラー高;２／８μｍｍ、シリコンウエハ、銅、錫がこの順に形成されている。
ｃ）ピッチ；４５μｍ、銅ピラー径;２０μｍ、銅ピラー高;１０μｍ
　ｄ）８インチシリコンウエハ上に厚さ５μｍのＳｉＯ２膜をＣＶＤ（chemical vapor deposition）で形成し、フォトリソグラフィおよびドライエッチングによりピッチ４５μｍ、直径２０μｍのホールパターンを正方配列で形成した。ホールパターンを形成した面に対してチタンおよび銅の薄層をＣＶＤで順に形成した後、めっきによってホールパターン内に銅を充填した。その後、パターン内に銅が充填されたＳｉＯ２膜を内部の銅とともに厚さ３μｍになるまでＣＭＰによって研磨した。 <Fabrication of substrate>
Pillar substrates having the following sizes and metal types were produced by plating.
a) Pitch: 25 μm, copper pillar diameter: 10 μm, copper pillar height: 10 μm
b) Pitch: 45 µm, copper/tin pillar diameter: 20 µm, copper/tin pillar height: 2/8 µmm, silicon wafer, copper, and tin are formed in this order.
c) Pitch: 45 µm, copper pillar diameter: 20 µm, copper pillar height: 10 µm
d) A SiO2 film with a thickness of 5 μm was formed on an 8-inch silicon wafer by CVD (chemical vapor deposition), and a hole pattern with a pitch of 45 μm and a diameter of 20 μm was formed in a square array by photolithography and dry etching. After thin layers of titanium and copper were sequentially formed by CVD on the surface where the hole pattern was formed, the hole pattern was filled with copper by plating. After that, the SiO 2 film in which the pattern was filled with copper was polished by CMP to a thickness of 3 μm together with the copper inside.
　作製したピラー基板の詳細を以下に説明する。
　図６（ａ）は上記ａ）及びｃ）の概略断面図である。
　図６（ａ）において、１０は基板を、１２は銅により形成された配線端子（ピラ－）をそれぞれ表す。
　図６（ａ）中、各ピラーにおけるピラーの直径ｄの算術平均値がピラー径であり、ａ）においては１０μｍ、ｃ）においては２０μｍである。
　図６（ａ）中、各ピラーにおけるピラーの間隔ｐの算術平均値がピッチであり、ａ）においては１０μｍ、ｃ）においては２０μｍである。
　図６（ａ）中、各ピラーにおけるピラーの高さｈの算術平均値がピラー高であり、ａ）においては１０μｍ、ｃ）においては１０μｍである。
　図６（ｂ）は上記ｂ）の概略断面図である。
　図６（ｂ）において、１０は基板を、１２は配線端子を表しており、配線端子１２は錫により形成されたピラー（導通路）１４、銅により形成されたピラ－（電極）１６から形成されている。
　図６（ｂ）中、各ピラーにおけるピラーの直径ｄの算術平均値がピラー径であり、ｂ）においては２０μｍである。
　図６（ｂ）中、各ピラーにおけるピラーの間隔ｐの算術平均値がピッチであり、ｂ）においては４５μｍである。
　図６（ｂ）中、各ピラーにおける導通路の高さｈ１の算術平均値が錫ピラー高であり、ｂ）においては８μｍである。
　図６（ｂ）中、各ピラーにおける電極の高さｈ２の算術平均値が銅ピラー高であり、ｂ）においては２μｍである。 Details of the fabricated pillar substrate will be described below.
FIG. 6(a) is a schematic sectional view of the above a) and c).
In FIG. 6A, 10 denotes a substrate, and 12 denotes wiring terminals (pillars) made of copper.
In FIG. 6(a), the arithmetic mean value of the pillar diameters d in each pillar is the pillar diameter, which is 10 μm in a) and 20 μm in c).
In FIG. 6(a), the arithmetic average value of the pillar spacing p in each pillar is the pitch, which is 10 μm in a) and 20 μm in c).
In FIG. 6(a), the arithmetic mean value of the pillar height h of each pillar is the pillar height, which is 10 μm in a) and 10 μm in c).
FIG. 6(b) is a schematic sectional view of the above b).
In FIG. 6B, 10 denotes a substrate and 12 denotes a wiring terminal. The wiring terminal 12 is formed of a pillar (conducting path) 14 made of tin and a pillar (electrode) 16 made of copper. It is
In FIG. 6(b), the arithmetic mean value of the pillar diameters d in each pillar is the pillar diameter, which is 20 μm in b).
In FIG. 6(b), the arithmetic mean value of the pillar spacing p of each pillar is the pitch, which is 45 μm in b).
In FIG. 6(b), the arithmetic mean value of the height h1 of the conduction path in each pillar is the tin pillar height, and in b) it is 8 μm.
In FIG. 6(b), the arithmetic mean value of the electrode height h2 in each pillar is the copper pillar height, which is 2 μm in b).
＜基板/基板積層体（接合体）の作製（実施例１～１４、１６、１９）＞
　後述する表に記載された各組成物をａ）、ｂ）、ｃ）の各基板に、１５μｍ膜厚となるよう塗布し、１００℃で５分間ベークした。さらに表の「成膜温度」、「成膜時間」の欄に記載の温度、時間の条件で追加ベークし、ポリイミド含有部を得た。その後ＤＩＳＣＯ製Surface planer DAS8920を用いて表面を残膜５μｍになるようカッティングすることによりポリイミド含有部の表面の平坦化を行なった。平坦化を行った基板は各２枚（表の基板Ａ、基板Ｂ）作製し、表に記載した組み合わせで、ＥＶＧ社製ボンダー５４０で基板同士の接合を実施した。表の「接合」の欄に基板・基板と表に記載された例においては、基板同士を接合させた。基板・チップと記載された例においては、基板のうち一方をダイシングして作製した１０ｍｍ四方のチップを用意して、上記チップと基板とを接着させた。接合温度は表の「接合温度」の欄に記載の温度とし、表に記載の「接合温度」、「接合時間」、「加圧力」、雰囲気圧：１×１０－３ｍｂａｒの条件で接合を実施し、基板積層体（接合体）を得た。１ｍｂａｒは１００Ｐａである。また、１Ｎは０．１０２ｋｇである。 <Fabrication of substrate/substrate laminate (bonded body) (Examples 1 to 14, 16, 19)>
Each of the compositions shown in the table below was applied to each of the substrates a), b), and c) so as to have a film thickness of 15 μm, and baked at 100° C. for 5 minutes. Furthermore, additional baking was performed under the conditions of temperature and time described in the columns of "film formation temperature" and "film formation time" in the table to obtain a polyimide-containing portion. Thereafter, the surface of the polyimide-containing portion was flattened by cutting the surface using a surface planer DAS8920 manufactured by DISCO so that the remaining film was 5 μm. Two flattened substrates (substrate A and substrate B in the table) were prepared, and the substrates were bonded together by a bonder 540 manufactured by EVG in the combination shown in the table. In the examples described in the table as "substrate/substrate" in the "bonding" column, the substrates were bonded together. In the example described as "substrate/chip", a 10 mm square chip was prepared by dicing one of the substrates, and the chip and the substrate were bonded together. The bonding temperature is the temperature described in the "bonding temperature" column of the table, and bonding is performed under the conditions of "bonding temperature", "bonding time", "pressure", and atmospheric pressure: 1 × 10 -3 mbar described in the table. A substrate laminate (bonded body) was obtained. 1 mbar is 100 Pa. 1N is 0.102 kg.
＜基板/基板積層体（接合体）の作製(実施例１５)＞
　実施例１５では、平坦化を行った基板を各２枚（表の基板Ａ及び基板Ｂ）作製した後に、基板Ｂのみを組成物塗布面にＲＡＤ３５１０Ｆ／１２　（ＬＩＮＴＥＣ社製）にて表面に保護テープを貼り付けた。その後、基板Ｂに対してＤＦＧ８５６０（ＤＩＳＣＯ社製）を用い、裏面（組成物塗布面とは反対の側の面）研磨を行い、ウェハ厚みを１５０μｍまで膜化後に、ＥＶＧ社製ボンダー５４０で基板同士の接合を実施した以外は、実施例１と同様に評価を実施した。 <Production of substrate/substrate laminate (bonded body) (Example 15)>
In Example 15, after preparing two flattened substrates (substrate A and substrate B in the table), only the substrate B was coated with the composition on the surface with RAD3510F/12 (manufactured by LINTEC). Affixed the tape. After that, using DFG8560 (manufactured by DISCO), the back surface (the surface opposite to the composition coated surface) was polished to the substrate B, and after forming the wafer to a thickness of 150 μm, the substrate was bonded with a bonder 540 manufactured by EVG. Evaluation was carried out in the same manner as in Example 1, except that they were joined together.
＜基板/基板積層体（接合体）の作製(実施例１７)＞
　実施例１７では、基板Ｂに組成物４を用い、さらに１０μｍ膜厚となるよう塗布した以外は実施例１と同様に基板作製及び評価を実施した。 <Production of substrate/substrate laminate (bonded body) (Example 17)>
In Example 17, substrate preparation and evaluation were carried out in the same manner as in Example 1, except that composition 4 was used for substrate B and was applied to a film thickness of 10 μm.
＜基板/基板積層体（接合体）の作製(実施例１８)＞
　実施例１８では、基板Ｂとして基板ｄ）を用いた以外は、実施例１と同様に基板作製及び評価を実施した。 <Production of substrate/substrate laminate (bonded body) (Example 18)>
In Example 18, substrate preparation and evaluation were carried out in the same manner as in Example 1, except that the substrate d) was used as the substrate B.
＜基板/基板積層体（接合体）の作製(実施例２０)＞
　実施例２０では、基板Ｂを７０℃で予熱してから、７０℃のまま接合を開始した以外は実施例２と同様に基板作製及び評価を実施した。 <Production of substrate/substrate laminate (bonded body) (Example 20)>
In Example 20, substrate preparation and evaluation were carried out in the same manner as in Example 2, except that the substrate B was preheated at 70°C and then bonding was started at 70°C.
＜最大剥離抗力の評価＞
　得られた各基板積層体をダイシング機を用い７ｍｍ×７ｍｍのサイズにカットし、ＸＹＺＴＥＣ社製ｃｏｎｄｏｒ　Ｓｉｇｍａダイテスターを用いて、シェアツールを用いて７ｍｍ×７ｍｍのサイズの最大剥離抗力（ｋｇ／ｃｍ２）を計測した。１水準につき５つの試験片を作製し、各５回の計測を行い、その算術平均値を採用した。最大剥離抗力は下記の３段階で評価した。評価結果は、表の「最大剥離抗力」の欄に記載した。最大剥離抗力が大きいほど、接合体は接着性に優れているといえる。
Ａ：最大剥離抗力が５０ｋｇ／ｃｍ２以上であった。
Ｂ：最大剥離抗力が５０ｋｇ／ｃｍ２未満、４０ｋｇ／ｃｍ２以上であった。
Ｃ：最大剥離抗力が４０ｋｇ／ｃｍ２未満、３０ｋｇ／ｃｍ２以上であった。
Ｄ：最大剥離抗力が３０ｋｇ／ｃｍ２未満であった。 <Evaluation of maximum peeling force>
Each obtained substrate laminate is cut into a size of 7 mm × 7 mm using a dicing machine, and a shear tool is used to measure the maximum peel resistance (kg / cm 2 ) was measured. Five test pieces were prepared for each level, five measurements were made, and the arithmetic mean value was adopted. The maximum peel resistance was evaluated in the following three stages. The evaluation results are shown in the "maximum peel resistance" column of the table. It can be said that the larger the maximum peel resistance, the more excellent the adhesiveness of the joined body.
A: Maximum peel resistance was 50 kg/cm 2 or more.
B: The maximum peel resistance was less than 50 kg/cm 2 and 40 kg/cm 2 or more.
C: The maximum peel resistance was less than 40 kg/cm 2 and 30 kg/cm 2 or more.
D: Maximum peel resistance was less than 30 kg/cm 2 .
＜ガラス転移温度の測定＞
　各基板積層体におけるポリイミド含有部を回収し、ポリイミド含有部のガラス転移温度（Ｔｇ）をＵＢＭ社製　Ｒｈｅｏｇｅｌ　Ｅ４０００を用いて測定した。測定結果は、表の「ガラス転移温度」の欄に記載した。  <Measurement of glass transition temperature>
The polyimide-containing portion in each substrate laminate was recovered, and the glass transition temperature (Tg) of the polyimide-containing portion was measured using Rheogel E4000 manufactured by UBM. The measurement results are shown in the "Glass transition temperature" column of the table.
Figure JPOXMLDOC01-appb-T000059
Figure JPOXMLDOC01-appb-T000059
　上記表の結果から明らかなとおり、本発明のポリイミド含有部形成用組成物を用いることにより、最大剥離抗力が大きい接合体が得られた。
　ポリイミド含有部のガラス転移温度が接合温度よりも高い比較例１及び比較例２においては、最大剥離抗力が小さいことがわかる。 As is clear from the results in the table above, the use of the composition for forming a polyimide-containing portion of the present invention yielded a joined body having a high maximum peel resistance.
It can be seen that the maximum peel resistance is small in Comparative Examples 1 and 2, in which the glass transition temperature of the polyimide-containing portion is higher than the bonding temperature.
　１　基板Ａ（下地基板、ドーターチップ）
　１ｘ　シリコンウエハ
　１ｙ　ポリイミド含有部配設基板
　１ｚ　積層体
　２　基板Ｂ（マザーチップ）
　２ａ　基板Ｂにおける第２のポリイミド含有部の表面
　２ｘ　シリコンウエハ
　２ｙ　スルーホール電極
　３１　電極（金属部）
　３１ａ　電極の先端
　３２　電極（金属部）
　４　樹脂組成物層
　４ａ　ポリイミド含有部の表面（平坦化前）
　４ｂ　ポリイミド含有部の表面（平坦化後）
　４１　ポリイミド含有部
　４２　第２のポリイミド含有部
　８　電子回路領域
　１０　基板
　１２　配線端子Ａ
　１４　導通路
　１６　電極
　８１　電子回路
　９０　半導体デバイス
　９１　ボンディングフィルム
　９３　はんだ電極（バンプ）
　９４　アンダーフィル
　９５　封止樹脂
　９６　ワイヤボンディング
　９７ａ　基板電極
　９７ｂ　ワイヤボンディングパッド
　９８　ベース基板
　９９　はんだボール
　１００　接合体
　１０１ａ～１０１ｄ　半導体素子
　１０１　接合体
　１０２ｂ～１０２ｄ　貫通電極
　１０３ａ～１０３ｅ　金属バンプ
　１０５　再配線層
　１１０、１１０ａ、１１０ｂ　樹脂層
　１１５　絶縁層
　１２０　配線基板
　１２０ａ　表面電極
　２００　半導体デバイス
　ｄ　ピラーの直径
　ｐ　ピラーの間隔
　ｈ　ピラーの高さ
　ｈ１　導通路の高さ
　ｈ２　電極の高さ 1 Substrate A (underlying substrate, daughter chip)
1x silicon wafer 1y substrate provided with polyimide containing portion 1z laminate 2 substrate B (mother chip)
2a surface of the second polyimide-containing portion of substrate B 2x silicon wafer 2y through-hole electrode 31 electrode (metal portion)
31a electrode tip 32 electrode (metal part)
4 Resin composition layer 4a Surface of polyimide-containing portion (before flattening)
4b Surface of polyimide-containing part (after flattening)
41 polyimide-containing portion 42 second polyimide-containing portion 8 electronic circuit region 10 substrate 12 wiring terminal A
14 conductive path 16 electrode 81 electronic circuit 90 semiconductor device 91 bonding film 93 solder electrode (bump)
94 underfill 95 sealing resin 96 wire bonding 97a substrate electrode 97b wire bonding pad 98 base substrate 99 solder ball 100 bonded body 101a to 101d semiconductor element 101 bonded body 102b to 102d through electrode 103a to 103e metal bump 105 rewiring layer 110, 110a, 110b resin layer 115 insulating layer 120 wiring substrate 120a surface electrode 200 semiconductor device d pillar diameter p pillar spacing h pillar height h1 conduction path height h2 electrode height

Claims (22)

  1. 　配線端子を備える面を有する基板Ａを準備する工程、
    　前記基板Ａの前記配線端子を備える面上にポリイミド含有部を形成するポリイミド含有部形成工程、
    　配線端子を備える面を有する基板Ｂを準備する工程、及び、
    　前記基板Ａのポリイミド含有部を有する面と、前記基板Ｂにおける前記配線端子を備える面とを接合する接合工程、を含む接合体の製造方法において使用されるポリイミド含有部形成用組成物であって、
    　前記ポリイミド含有部は前記ポリイミド含有部形成用組成物から形成される部材であり、
    前記ポリイミド含有部のガラス転移温度が、前記接合工程における接合温度より低い
    　ポリイミド含有部形成用組成物。     A step of preparing a substrate A having a surface provided with wiring terminals;
    a polyimide-containing portion forming step of forming a polyimide-containing portion on the surface of the substrate A provided with the wiring terminals;
    A step of preparing a substrate B having a surface provided with wiring terminals;
    A composition for forming a polyimide-containing portion used in a method for producing a bonded body, which includes a bonding step of bonding the surface of the substrate A having the polyimide-containing portion and the surface of the substrate B having the wiring terminal, ,
    The polyimide-containing portion is a member formed from the polyimide-containing portion-forming composition,
    A composition for forming a polyimide-containing portion, wherein the glass transition temperature of the polyimide-containing portion is lower than the bonding temperature in the bonding step.
  2. 　ポリイミド前駆体及び溶剤を含む、請求項１に記載のポリイミド含有部形成用組成物。 The composition for forming a polyimide-containing part according to claim 1, comprising a polyimide precursor and a solvent.
  3. 　マイグレーション抑制剤を更に含む、請求項１又は２に記載のポリイミド含有部形成用組成物。 The composition for forming a polyimide-containing part according to claim 1 or 2, further comprising a migration inhibitor.
  4. 前記ポリイミド含有部のガラス転移温度が３５０℃以下である、請求項１～３のいずれか１項に記載のポリイミド含有部形成用組成物。 4. The composition for forming a polyimide-containing portion according to claim 1, wherein the polyimide-containing portion has a glass transition temperature of 350° C. or lower.
  5. 前記ポリイミド含有部のガラス転移温度が、前記接合工程における接合温度より３０℃以上低い、請求項１～４のいずれか１項に記載のポリイミド含有部形成用組成物。 The composition for forming a polyimide-containing portion according to any one of claims 1 to 4, wherein the polyimide-containing portion has a glass transition temperature lower than the bonding temperature in the bonding step by 30°C or more.
  6. 　前記接合工程における接合温度が３８０℃以下である、請求項１～５のいずれか１項に記載のポリイミド含有部形成用組成物。 The composition for forming a polyimide-containing portion according to any one of claims 1 to 5, wherein the bonding temperature in the bonding step is 380°C or less.
  7. 　前記基板Ａの形態がウエハである、請求項１～６のいずれか１項に記載のポリイミド含有部形成用組成物。 The composition for forming a polyimide-containing portion according to any one of claims 1 to 6, wherein the substrate A is in the form of a wafer.
  8. 　前記基板Ｂの形態がチップである、請求項１～７のいずれか１項に記載のポリイミド含有部形成用組成物。 The composition for forming a polyimide-containing part according to any one of claims 1 to 7, wherein the form of the substrate B is a chip.
  9. 　前記基板Ｂの形態がウエハである、請求項１～７のいずれか１項に記載のポリイミド含有部形成用組成物。 The composition for forming a polyimide-containing part according to any one of claims 1 to 7, wherein the form of the substrate B is a wafer.
  10. 　接合工程において、ポリイミド含有部を備えた基板Ａの温度が７０℃以上に予熱されている、請求項１～９のいずれか１項に記載のポリイミド含有部形成用組成物。 The composition for forming a polyimide-containing portion according to any one of claims 1 to 9, wherein the temperature of the substrate A having the polyimide-containing portion is preheated to 70°C or higher in the bonding step.
  11. 　前記ポリイミド含有部形成工程と、前記接合工程との間に、基板Ａのポリイミド含有部の表面を平坦化する平坦化工程を含む、請求項１～１０のいずれか１項に記載のポリイミド含有部形成用組成物。 The polyimide-containing portion according to any one of claims 1 to 10, comprising a planarization step of planarizing the surface of the polyimide-containing portion of the substrate A between the polyimide-containing portion forming step and the bonding step. Forming composition.
  12. 　前記平坦化工程が、物理研磨によって行なわれる、請求項１１に記載のポリイミド含有部形成用組成物。 The composition for forming a polyimide-containing portion according to claim 11, wherein the planarization step is performed by physical polishing.
  13. 　前記平坦化工程が、化学研磨によって行なわれる、請求項１１に記載のポリイミド含有部形成用組成物。 The composition for forming a polyimide-containing portion according to claim 11, wherein the planarization step is performed by chemical polishing.
  14. 　前記接合工程において、前記基板Ａのポリイミド含有部を有する面に含まれる電極と、前記基板Ｂにおける前記配線端子を備える面における電極とが直接接するように接合される、請求項１～１３のいずれか１項に記載のポリイミド含有部形成用組成物。 14. Any one of claims 1 to 13, wherein in the bonding step, the electrodes included in the surface of the substrate A having the polyimide-containing portion and the electrodes on the surface of the substrate B including the wiring terminals are in direct contact with each other. 2. The composition for forming a polyimide-containing portion according to claim 1.
  15. 　前記接合工程の前に、前記基板Ｂの前記配線端子を備える面上に第２のポリイミド含有部を形成する第２のポリイミド含有部形成工程を更に含む、請求項１～１４のいずれか１項に記載のポリイミド含有部形成用組成物。 Any one of claims 1 to 14, further comprising a second polyimide-containing portion forming step of forming a second polyimide-containing portion on the surface of the substrate B provided with the wiring terminal before the bonding step. 3. The composition for forming a polyimide-containing portion according to .
  16. 　感光性化合物を更に含む、請求項１～１５のいずれか１項に記載のポリイミド含有部形成用組成物。 The composition for forming a polyimide-containing portion according to any one of claims 1 to 15, further comprising a photosensitive compound.
  17. 　前記ポリイミド含有部形成工程が、基板Ａの前記配線端子を備える面上にポリイミド含有部形成用組成物を適用し、加熱することを含む、請求項１～１６のいずれか１項に記載のポリイミド含有部形成用組成物。 The polyimide-containing part forming step comprises applying a polyimide-containing part-forming composition on the surface of the substrate A provided with the wiring terminal and heating, The polyimide according to any one of claims 1 to 16. A composition for forming a containing portion.
  18. 　前記加熱における加熱温度が、３７５℃以下である、請求項１７に記載のポリイミド含有部形成用組成物。 The composition for forming a polyimide-containing part according to claim 17, wherein the heating temperature in the heating is 375°C or less.
  19. 　配線端子を備える面を有する基板Ａを準備する工程、
    　前記基板Ａの前記配線端子を備える面上にポリイミド含有部を形成するポリイミド含有部形成工程、
    　配線端子を備える面を有する基板Ｂを準備する工程、及び、
    　前記基板Ａのポリイミド含有部を有する面と、前記基板Ｂにおける前記配線端子を備える面とを接合する接合工程、を含み、
    　前記ポリイミド含有部のガラス転移温度が、前記接合工程における接合温度よりも低い温度である接合体の製造方法。     A step of preparing a substrate A having a surface provided with wiring terminals;
    a polyimide-containing portion forming step of forming a polyimide-containing portion on the surface of the substrate A provided with the wiring terminals;
    A step of preparing a substrate B having a surface provided with wiring terminals;
    A joining step of joining the surface of the substrate A having the polyimide-containing portion and the surface of the substrate B having the wiring terminal,
    A method for producing a joined body, wherein the glass transition temperature of the polyimide-containing portion is lower than the joining temperature in the joining step.
  20. 　請求項１９に記載の製造方法によって得られる接合体。 A joined body obtained by the manufacturing method according to claim 19.
  21. 　請求項１９に記載の接合体の製造方法を含む、デバイスの製造方法。 A method for manufacturing a device, including the method for manufacturing a joined body according to claim 19.
  22. 　請求項２０に記載の接合体を含む、デバイス。 A device comprising the conjugate according to claim 20.
PCT/JP2022/020338 2021-05-17 2022-05-16 Composition for forming polyimide-containing part, joined body manufacturing method, joined body, device manufacturing method and device WO2022244717A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002299505A (en) * 2001-03-29 2002-10-11 Nippon Steel Chem Co Ltd Manufacturing method of semiconductor element
WO2012005079A1 (en) * 2010-07-09 2012-01-12 東レ株式会社 Photosensitive adhesive composition, photosensitive adhesive film, and semiconductor device using each
WO2017209176A1 (en) * 2016-06-02 2017-12-07 富士フイルム株式会社 Laminate production method, semiconductor element production method, and laminate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002299505A (en) * 2001-03-29 2002-10-11 Nippon Steel Chem Co Ltd Manufacturing method of semiconductor element
WO2012005079A1 (en) * 2010-07-09 2012-01-12 東レ株式会社 Photosensitive adhesive composition, photosensitive adhesive film, and semiconductor device using each
WO2017209176A1 (en) * 2016-06-02 2017-12-07 富士フイルム株式会社 Laminate production method, semiconductor element production method, and laminate

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