WO2023120037A1 - 接合体の製造方法、接合体、積層体の製造方法、積層体、デバイスの製造方法、及び、デバイス、並びに、ポリイミド含有前駆体部形成用組成物 - Google Patents

接合体の製造方法、接合体、積層体の製造方法、積層体、デバイスの製造方法、及び、デバイス、並びに、ポリイミド含有前駆体部形成用組成物 Download PDF

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Publication number
WO2023120037A1
WO2023120037A1 PCT/JP2022/043600 JP2022043600W WO2023120037A1 WO 2023120037 A1 WO2023120037 A1 WO 2023120037A1 JP 2022043600 W JP2022043600 W JP 2022043600W WO 2023120037 A1 WO2023120037 A1 WO 2023120037A1
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Prior art keywords
polyimide
group
containing precursor
substrate
precursor portion
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Ceased
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PCT/JP2022/043600
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English (en)
French (fr)
Japanese (ja)
Inventor
敦 中村
広祐 山下
和貴 友田
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Fujifilm Corp
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Fujifilm Corp
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Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Priority to CN202280083150.6A priority Critical patent/CN118435349A/zh
Priority to JP2023522543A priority patent/JP7354479B1/ja
Priority to EP22910755.2A priority patent/EP4456133A4/en
Priority to KR1020247020124A priority patent/KR102949337B1/ko
Publication of WO2023120037A1 publication Critical patent/WO2023120037A1/ja
Priority to JP2023152347A priority patent/JP2023178289A/ja
Priority to US18/746,015 priority patent/US20240339368A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
    • C08F283/045—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides on to unsaturated polycarbonamides, polyesteramides or polyimides
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    • C08G73/1003—Preparatory processes
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    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • H05K3/36—Assembling printed circuits with other printed circuits
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Definitions

  • the present invention relates to a method for producing a joined body, a joined body, a method for producing a laminate, a method for producing a laminate, a device, a device, and a composition for forming a polyimide-containing precursor portion.
  • Non-Patent Document 1 Electronic devices such as mobile phones and tablet terminals are getting smaller and smaller while their functions are diversifying. In order 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 multi-function, high performance and reliability. . 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. Further applying the technology of flip-chip mounting, techniques and materials for three-dimensional mounting using TSV (Through Silicon Via) are being studied (Non-Patent Document 1).
  • 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 to the mother chip 2 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 . Electrical connection between the mother chip 2 and the base substrate 98 is established through wire bonding pads 97b, wire bonding 96 and substrate electrodes 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.
  • 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 method for manufacturing a bonded body that can obtain a bonded body having a large maximum peeling force between two substrates when bonding two substrates, a bonded body that is obtained, a method for manufacturing a laminated body, and a laminated body that is obtained. It is an object of the present invention to provide a body, a method for manufacturing a device, the resulting device, and a composition for forming a polyimide-containing precursor portion.
  • the difference between the cyclization rate of polyimide in the polyimide-containing precursor portion before the bonding step and the cyclization rate of polyimide in the polyimide-containing portion formed in the bonding portion after the bonding step is 5% or more.
  • ⁇ 2> The method for producing a bonded body according to ⁇ 1>, wherein the cyclization rate of polyimide in the polyimide-containing precursor portion before the bonding step is 40 to 90%.
  • ⁇ 3> The method for producing a bonded body according to ⁇ 1> or ⁇ 2>, wherein the cyclization rate of polyimide in the polyimide-containing portion formed in the bonding portion after the bonding step is 91 to 100%.
  • ⁇ 4> The method for producing a bonded body according to any one of ⁇ 1> to ⁇ 3>, wherein the bonding temperature in the bonding step is 380° C. or less.
  • the polyimide-containing precursor part forming step includes applying a polyimide-containing precursor part-forming composition to the surface of the substrate A provided with the wiring terminal, and applying the polyimide-containing precursor part forming composition Any one of ⁇ 1> to ⁇ 5>, wherein the heating temperature in the heating is lower than the melting point of the wiring terminal, including heating the composition below the melting point of the wiring terminal of the substrate A.
  • a method for producing a conjugate of ⁇ 7> The method for producing a bonded body according to any one of ⁇ 1> to ⁇ 6>, wherein the substrate A is in the form of a wafer.
  • ⁇ 10> Further includes a planarization step of planarizing the surface of the polyimide-containing precursor portion of the substrate A, and includes the polyimide precursor portion formation step, the planarization step, and the bonding step in this order ⁇ 1 > to ⁇ 9>.
  • the bonding step the electrodes included in the surface of the substrate A having the polyimide-containing precursor portion are bonded to the electrodes on the surface of the substrate B having the wiring terminals in direct contact with each other, ⁇ 1 > to ⁇ 10>.
  • ⁇ 12> Further comprising a second polyimide-containing precursor portion forming step of forming a second polyimide-containing precursor portion on the surface of the substrate B provided with the wiring terminal, wherein the second polyimide-containing precursor portion forming step
  • ⁇ 13> Between the cyclization rate of polyimide in the second polyimide-containing precursor portion before the bonding step and the cyclization rate of polyimide contained in the polyimide-containing portion formed in the bonding portion after the bonding step The method for producing a joined body according to ⁇ 12>, wherein the difference is 5% or more.
  • ⁇ 14> The method for producing a joined body according to ⁇ 12> or ⁇ 13>, wherein the cyclization rate of polyimide in the second polyimide-containing precursor portion before the joining step is 40 to 90%.
  • ⁇ 15> The method for producing a joined body according to any one of ⁇ 1> to ⁇ 11>, wherein the substrate B includes an inorganic insulating film between the wiring terminals of the substrate B.
  • the polyimide-containing precursor part-forming step is a step of applying a polyimide-containing precursor part-forming composition onto the surface of the substrate A provided with the wiring terminal, and the polyimide-containing precursor part-forming composition
  • the polyimide-containing precursor portion-forming composition contains a migration inhibitor.
  • the polyimide-containing precursor portion-forming composition further contains a polymerizable compound having a ring structure.
  • ⁇ 19> The bonding according to any one of ⁇ 16> to ⁇ 18>, wherein the composition for forming the polyimide-containing precursor portion contains a polymerizable compound whose homopolymer has a glass transition temperature of 200° C. or higher. body manufacturing method.
  • ⁇ 20> The method for producing a joined body according to any one of ⁇ 16> to ⁇ 19>, wherein the polyimide-containing precursor portion-forming composition contains a filler.
  • ⁇ 21> A joined body obtained by the production method according to any one of ⁇ 1> to ⁇ 20>.
  • a method for manufacturing a laminate ⁇ 23> The method for producing a laminate according to ⁇ 22>, wherein the polyimide-containing precursor portion contains a filler.
  • a method of manufacturing a device including the method of manufacturing a bonded body according to any one of ⁇ 1> to ⁇ 20>, or the method of manufacturing a laminate according to ⁇ 22> or ⁇ 23>.
  • ⁇ 26> A device comprising the joined body according to ⁇ 21> or the laminate according to ⁇ 24>.
  • the polyimide-containing precursor portion is a member formed from the polyimide-containing precursor portion-forming composition
  • the difference between the cyclization rate of polyimide in the polyimide-containing precursor portion before the bonding step and the cyclization rate of polyimide in the polyimide-containing portion formed in the bonding portion after the bonding step is 5% or more Polyimide-containing precursor Part-forming composition.
  • a method for manufacturing a bonded body, a bonded body obtained, a method for manufacturing a laminated body, and a laminated body obtained by obtaining a bonded body having a large maximum peeling force between two substrates when the two substrates are bonded together A body, a method of making a device and the resulting device, and a composition for forming a polyimide-containing precursor portion are provided.
  • FIG. 1 is a cross-sectional view schematically showing the structure of a COC semiconductor device
  • FIG. FIG. 2 is a schematic cross-sectional view showing a step of joining substrates in a method for producing a joined body in which the composition for forming a polyimide-containing precursor portion of the present invention according to one embodiment of the present invention is used.
  • FIG. 1 is a schematic cross-sectional view showing a step of bonding substrates in a method for manufacturing a bonded body using the composition for forming a polyimide-containing precursor portion of the present invention according to an embodiment of the present invention. (Continued from Figure 2).
  • FIG. 2 is a schematic cross-sectional view showing a step of joining substrates in a method for producing a joined body in which the composition for forming a polyimide-containing precursor portion of the present invention according to one embodiment of the present invention is used.
  • FIG. 1 is a schematic cross-sectional view showing a step of bonding substrates in a method for manufacturing a
  • FIG. 2 is a schematic cross-sectional view showing a step of joining substrates in a method for producing a joined body in which the composition for forming a polyimide-containing precursor portion of the present invention according to one embodiment of the present invention is used.
  • 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.
  • FIG. 10 is a schematic cross-sectional view showing details of the operations performed in Examples 22 and 23;
  • FIG. 10 is a schematic cross-sectional view showing details of the operations performed in Examples 22 and 23;
  • 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).
  • Exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
  • 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 determined 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.
  • the manufacturing method of the joined body of the present invention comprises a step of preparing a substrate A having a surface provided with wiring terminals, forming a polyimide-containing precursor portion on the surface of the substrate A provided with the wiring terminals, and forming a polyimide-containing precursor portion. a step of preparing a substrate B having a surface provided with wiring terminals; and a bonding step of bonding the surface of the substrate A having the polyimide-containing precursor portion and the surface of the substrate B provided with the wiring terminals.
  • the difference between the cyclization rate of polyimide in the polyimide-containing precursor portion before the bonding step and the cyclization rate of polyimide in the polyimide-containing portion formed in the bonding portion after the bonding step is 5% or more.
  • a bonded body having a large maximum peeling force between the two substrates can be obtained. It becomes possible to manufacture. Specifically, the difference between the cyclization rate of polyimide in the polyimide-containing precursor portion before the bonding step and the cyclization rate of polyimide in the polyimide-containing portion formed in the bonding portion after the bonding step is 5% or more.
  • the manufacturing method of the joined body 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 “conducting path”) is formed to be used as solder, 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.
  • the manufacturing method of the joined body of the present invention includes a polyimide-containing precursor portion forming step of forming a polyimide-containing precursor portion on the surface of the substrate A provided with the wiring terminal (wiring terminal A).
  • the polyimide-containing precursor 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 precursor portion may be formed on at least a part of the wiring terminals A, but for example, an embodiment in which the polyimide-containing precursor portion is formed on all of the wiring terminals A is also a preferred embodiment of the present invention. is one.
  • the polyimide-containing precursor portion forming step preferably includes applying a polyimide-containing precursor portion forming composition to the surface of the substrate A provided with the wiring terminals and heating. Details of application and heating are described below.
  • the polyimide-containing precursor section is preferably a member containing a polyimide precursor, and may further contain components other than the polyimide precursor.
  • Components other than the polyimide precursor include components other than the polyimide precursor contained in the composition for forming the polyimide-containing precursor portion described below, and components modified by heating (decomposition, polymerization, structural change, etc.). are mentioned.
  • the polyimide-containing precursor portion preferably further contains a polymerizable compound having a ring structure.
  • the polyimide-containing precursor section further contains a polymerizable compound whose homopolymer has a glass transition temperature of 200° C. or higher. Details of these polymerizable compounds will be described later.
  • the thickness of the polyimide-containing precursor 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 thickness immediately before the planarization step is performed) is preferably 100 nm or more, more preferably 300 nm or more, still more preferably 500 nm or more, even more preferably 1 ⁇ m or more, and even more preferably 2 ⁇ m or more. preferable. 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 polyimide-containing precursor part forming step includes applying a composition for forming a polyimide-containing precursor part (hereinafter also simply referred to as a "resin composition") to the surface of the substrate A having the wiring terminal A (application step).
  • the polyimide-containing precursor part-forming step is a step of applying a polyimide-containing precursor part-forming composition onto the surface of the substrate A provided with the wiring terminals, and the polyimide-containing precursor part-forming composition also preferably contains a polyimide precursor and a solvent.
  • the polyimide-containing precursor portion-forming composition preferably further contains a migration inhibitor.
  • the polyimide-containing precursor portion-forming composition preferably further contains a polymerizable compound having a ring structure.
  • the polyimide-containing precursor portion-forming composition preferably further contains a polymerizable compound whose homopolymer has a glass transition temperature of 200° C. or higher.
  • a polymerizable compound whose homopolymer has a glass transition temperature of 200° C. or higher.
  • 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, ink jet method, etc.
  • slit coating and spray coating are preferable for rectangular substrates.
  • method, inkjet method, and the like are preferred.
  • spin coating 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 can be applied in which a coating film formed in advance on a temporary support by the application method described above is transferred onto a base material.
  • 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 suitably 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.
  • a pre-wetting step may also be employed in which various solvents are applied to the base material before applying the resin composition to the base material to improve the wettability of the base material, and then the resin composition is applied.
  • a step (drying step) of drying a 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 appropriately adjusted so that the thickness of the resulting polyimide-containing precursor portion is the thickness described later.
  • the polyimide-containing precursor 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. After the polyimide-containing precursor portion is formed, its 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.
  • the method for producing a joined body of the present invention may include an exposure step of selectively exposing the polyimide-containing precursor portion formed in the polyimide-containing precursor portion forming step.
  • selectively exposing is meant exposing a portion of the polyimide-containing precursor portion.
  • the polyimide-containing precursor portion is formed into exposed areas (exposed areas) and unexposed areas (non-exposed areas).
  • 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 as follows: (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.
  • the exposure method is not particularly limited as long as at least a part of the polyimide-containing precursor portion is exposed, and examples thereof include exposure using a photomask and exposure by a laser direct imaging method.
  • the polyimide-containing precursor part may be subjected to a step of heating after exposure (post-exposure heating step). That is, the method for producing a joined body of the present invention may include a post-exposure heating step of heating the polyimide-containing precursor portion 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 from 1 to 12° C./min, more preferably from 2 to 10° C./min, still more preferably from 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. It is also preferable to perform the heating in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.
  • the polyimide-containing precursor portion after exposure may be subjected to a development step of developing with a developer to form a pattern. That is, the method for manufacturing a joined body of the present invention may include a developing step of developing a film exposed in the exposing 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 polyimide-containing precursor portion is removed by the development step is called negative development
  • development in which the exposed portion of the polyimide-containing precursor portion is removed by the development step is called positive development.
  • Examples of the developer used in the development step include a developer containing an alkaline aqueous solution or 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)ammoni
  • 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 employed.
  • 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.
  • methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionate acid ethyl methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate
  • 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 employed.
  • 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 polyimide-containing precursor portion obtained by the polyimide-containing precursor portion forming step is preferably subjected to a heating step of heating the polyimide-containing precursor portion. That is, the method for producing a joined body of the present invention may include a heating step of heating the polyimide-containing precursor portion. In the heating step, a part of the resin such as the polyimide precursor is cyclized to become 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 250° C. or lower, more preferably 220° C.
  • the lower limit of the heating temperature is preferably 160° C. or higher, more preferably 170° C. or higher.
  • 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 increase 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 maximum heating temperature) is preferably 1 to 60 minutes, more preferably 2 to 30 minutes, even more preferably 5 to 20 minutes.
  • Heating may be done in stages. As an example, the temperature is raised from 25° C. to 120° C. at a rate of 3° C./min, held at 120° C. for 60 minutes, and heated from 120° C. to 200° C. at a rate of 2° C./min, and held at 200° C. for 10 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.
  • a heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, a hot air oven, an infrared oven and the like.
  • the polyimide-containing precursor portion obtained by the polyimide-containing precursor portion forming step may be subjected to a post-exposure step of exposing the polyimide-containing precursor portion instead of or in addition to the heating step.
  • the method for producing a bonded body of the present invention may include a post-exposure step of exposing the polyimide-containing precursor portion.
  • the method for manufacturing a joined body of the present invention may include a heating step and a post-exposure step, or may include only one of the heating step and the post-exposure step.
  • the post-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. be able to.
  • the post-exposure step at least a portion of the polyimide-containing precursor portion may be exposed, but the entire polyimide-containing precursor portion is preferably exposed.
  • the exposure amount in the post-exposure step is preferably 50 to 20,000 mJ/cm 2 and more preferably 100 to 15,000 mJ/cm 2 in terms of exposure energy at the wavelength to which the photosensitive compound is sensitive.
  • the post-exposure step can be performed using, for example, the light source used in the exposure step described above, and broadband light is preferably used.
  • Forming two or more layers of the polyimide-containing precursor portion in the polyimide-containing precursor portion forming step is also one of the preferred embodiments of the present invention. That is, the polyimide-containing precursor portion may have a structure in which a plurality of layers made of the resin composition are laminated. However, the interface between these layers may not be clear because part of the first layer dissolves in the solvent during the formation of the second layer.
  • the polyimide-containing precursor portion By forming the polyimide-containing precursor portion to have a structure of two or more layers, the flatness of the surface of the polyimide-containing precursor portion is improved, and there are advantages such as facilitating the flattening step described later, for example.
  • the polyimide-containing precursor section is preferably formed of 2 to 4 layers, more preferably 2 or 3 layers, and even more preferably 2 layers.
  • the application step if necessary, further drying step
  • the above-described exposure step, post-exposure heating step, and development step are required. It is also possible to adopt a mode in which the above-described heating step is performed according to the requirements.
  • the above-described heating step is performed to form the first layer, and then the above-described and, if necessary, the exposure step, the post-exposure heating step, and the development step, the above-described heating step may be performed to form the second and subsequent layers. Furthermore, when performing the application process to the heating process for the first layer, the conditions of the exposure process, the heating process, etc., which are performed as necessary, are adjusted to make it semi-cured. ⁇ A heating step may be further performed. When the polyimide-containing precursor portion is formed of two or more layers, the components contained in the resin composition used for forming each layer and the content ratio of each component may be the same or different.
  • the manufacturing method of the joined body 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. It is preferable that at least part 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.
  • the substrate B preferably has an inorganic insulating film between the wiring terminals.
  • inorganic insulating films include, but are not limited to, silicon oxide films, silicon nitride films, silicon oxynitride films (the content ratio of oxygen and nitrogen is not particularly limited), aluminum oxide films, aluminum nitride films, hafnium oxide films, and yttrium oxide films. film, zirconium oxide film, gallium oxide film, tantalum oxide film, magnesium oxide film, lanthanum oxide film, cerium oxide film, neodymium oxide film, silicon carbon nitride (SiCN) film, and the like.
  • a specific example of the case where the substrate B is provided with an inorganic insulating film includes the substrate c) in Examples described later. It is preferable that the inorganic insulating film insulates the plurality of electrodes included in the wiring terminal B.
  • FIG. Further, when the substrate B is provided with an inorganic insulating film, a second polyimide-containing precursor portion forming step, which will be described later, may be performed, but the second polyimide-containing precursor portion forming step may not be performed. .
  • the manufacturing method of the bonded body of the present invention includes, before the bonding step, a second polyimide-containing precursor portion forming step of forming a second polyimide-containing precursor portion on the surface of the substrate B provided with the wiring terminal. It is preferable to further include.
  • the second polyimide-containing precursor portion forming step can be performed, for example, by the same method as the polyimide-containing precursor portion forming step for the substrate A described above.
  • the polyimide-containing precursor part-forming composition of the present invention may be used, or another known polyimide-containing precursor part-forming composition may be used.
  • the polyimide-containing precursor portion-forming composition of the present invention it is preferable to use the polyimide-containing precursor portion-forming composition of the present invention.
  • the composition for forming the polyimide-containing precursor portion of the present invention is used in the second polyimide-containing precursor portion forming step
  • the polyimide-containing precursor portion of the present invention used in the second polyimide-containing precursor portion forming step The composition of the forming composition and the composition of the polyimide-containing precursor portion-forming composition used in the step of forming the polyimide-containing precursor portion on the substrate A may be the same or different.
  • Preferred embodiments of the second polyimide-containing precursor portion are the same as preferred embodiments of the polyimide-containing precursor portion formed in Substrate A above.
  • the second polyimide-containing precursor portion and the polyimide-containing precursor portion formed on the substrate A described above are bonded so that at least a portion thereof is in contact with each other, thereby improving the adhesiveness of the bonded body. It is thought that
  • the method for producing a bonded body of the present invention preferably includes a planarization step of planarizing the surface of the polyimide-containing precursor portion of the substrate A between the polyimide-containing precursor portion forming step and the bonding step.
  • the planarized polyimide-containing precursor portion of the substrate A and the surface of the substrate B (or the surface of the second polyimide-containing precursor portion, which may be planarized) are bonded together. Preferably, they are joined so as to make contact.
  • the wiring terminals A on the substrate A are exposed from the polyimide-containing precursor portion by the planarization. Further, in the substrate A and the polyimide-containing precursor portion after the planarization, the wiring terminal A and the polyimide-containing precursor portion may have the same height, or the wiring terminal may be the same height as the polyimide-containing precursor portion.
  • the terminal A may be recessed, and the polyimide-containing precursor portion may be recessed with respect to the wiring terminal A.
  • the difference in height between the wiring terminal A and the polyimide-containing precursor portion is preferably ⁇ 1 ⁇ m or less, more preferably ⁇ 0.5 ⁇ m or less.
  • 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).
  • the polishing rate of the polyimide-containing precursor portion during planarization is preferably 200 nm/min or more, more preferably 400 nm/min or more, further preferably 900 nm/min or more, and 1800 nm/min. It is more preferable that it is above.
  • the upper limit of the polishing rate is not particularly limited, it is preferably less than 3000 nm/min from the viewpoint of in-plane uniformity control of the object to be polished.
  • the polishing rate of the wiring terminal A on the substrate A during planarization is preferably equal to or lower than the polishing rate of the polyimide-containing precursor portion, and more preferably equal to or less than half the polishing rate of the polyimide-containing precursor portion.
  • the slurry used for the CMP is not particularly limited, silica slurry, ceria slurry, alumina slurry, and the like can be used.
  • the size of the particles of the slurry is not particularly limited, but from the viewpoint of suppressing scratches, the average particle size is preferably 1000 nm or less, more preferably 500 nm or less, and even more preferably 200 nm or less.
  • the lower limit of the particle size of the slurry is not particularly limited, it is preferably 10 nm or more from the viewpoint of the polishing rate.
  • these methods may be combined, such as performing CMP after cutting.
  • the surface of the polyimide-containing precursor portion is cut with a diamond tool to expose a new surface of the polyimide-containing precursor portion and the wiring terminal A.
  • the wiring terminal A and the polyimide-containing precursor portion on the substrate A are planarized so that the wiring terminal A is exposed. output becomes possible.
  • Flattening can be done, 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 precursor portion is preferably planarized together with the wiring terminal A in the planarization step.
  • the TTV (Total Thickness Variation) of the polyimide-containing precursor portion and the wiring terminal A is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and 3 ⁇ m or less. is more preferred.
  • TTV means that the area 1 mm or more inside from the edge portion of the polyimide-containing precursor portion is divided into 2 mm square sections (the area of the polyimide-containing precursor portion is small, etc., and cannot be divided into 2 mm square sections.
  • the entire area inside 1 mm or more from the edge of the polyimide-containing precursor portion is defined as one section), and for each section, the maximum thickness between one surface and the other surface (T1), Measure the minimum thickness (T2) between the surface and the other surface, calculate the film thickness difference (T1-T2) for each section, and rank each section in descending order of the film thickness difference (T1-T2) is provided, and the number of division groups and the lowest division (most The division groups corresponding to 10% of the total number of divisions (rounded down if there is a decimal point) are excluded in order from the smallest film thickness difference), and each film thickness difference of the remaining division groups ( The arithmetic mean value of T1-T2).
  • the TTV of a polyimide-containing precursor portion when specifically referring to the TTV of a polyimide-containing precursor portion as defined herein, it may be referred to as a "compartment-rated TTV.”
  • the film thickness becomes generally uniform and the adhesiveness to the substrate B improves.
  • the polyimide-containing precursor 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.
  • the surface of the second polyimide-containing precursor portion is planarized between the step of forming the second polyimide-containing precursor portion and the bonding step. preferably includes a second planarization step.
  • the second planarization process can be performed by the same method as the planarization process for the substrate A described above.
  • the manufacturing method of the bonded body of the present invention includes a bonding step of bonding the surface of the substrate A having the polyimide-containing precursor portion and the surface of the substrate B having the wiring terminals.
  • the bonding step includes the surface of the substrate A having the polyimide-containing precursor portion and the surface of the substrate B having the second polyimide-containing precursor portion. It is a step of joining.
  • the wiring terminal A on the substrate A and the wiring terminal B on the substrate B are electrically bonded.
  • the electrode included in the surface of the substrate A having the polyimide-containing precursor portion and the electrode included in the surface of the substrate B including the wiring terminal are bonded so as to be in direct contact. This is one of preferred embodiments. That is, it is also preferable that neither the wiring terminal A nor the wiring terminal B have a conducting path.
  • 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 while mechanically pressurizing the polyimide-containing precursor portion in a reduced pressure atmosphere.
  • 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 precursor portion is preheated to 70° C. or higher. It is also preferred that the substrate B is preheated to a temperature of 70° C. or higher when the substrate B includes the second polyimide-containing precursor portion.
  • 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.
  • the fluidity of the polyimide-containing precursor portion during bonding may be improved, and the maximum peel resistance may be improved.
  • the bonding step turns the polyimide-containing precursor portion into a polyimide-containing portion.
  • the polyimide-containing portion is formed from the polyimide-containing precursor portion and the second polyimide-containing precursor portion.
  • the polyimide-containing portion preferably has a thermal diffusivity of 2.0 ⁇ 10 ⁇ 7 m 2 s ⁇ 1 or more, more preferably 3.0 ⁇ 10 ⁇ 7 m 2 s ⁇ 1 or more. It is more preferably 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 fillers 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 composition of the present invention may contain fillers. If fillers are included, the fillers are 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 5.0 ⁇ 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 ⁇ cm, for example.
  • the lower limit of the volume resistivity of the filler is not particularly limited, but is preferably 1.0 ⁇ 10 ⁇ 7 ⁇ cm or more, for example.
  • 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, 1.0 ⁇ 10 ⁇ 6 m 2 s ⁇ 1 or more, preferably 2.0 ⁇ 10 ⁇ 6 m 2 s ⁇ 1 or more, and 5.0 ⁇ 10 ⁇ 6 m 2 s ⁇ 1 or more is particularly preferred.
  • 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.
  • the density of the filler is, for example, 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. 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.
  • 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, at least one of boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, zinc oxide, beryllium oxide and aluminum hydroxide.
  • the filler material is at least one of boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, zinc oxide and beryllium 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.
  • 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 configuration in which semiconductor or conductive thermally conductive particles are coated with an electrically insulating material such as silica or surface-treated. 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.
  • shape of the filler various shapes can be used, and examples thereof include fibrous, plate-like, scale-like, rod-like, spherical, tube-like, curved plate-like, and needle-like shapes.
  • 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 primary particle size of the filler is preferably 0.01 to 30 ⁇ m.
  • the lower limit is more preferably 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more, and particularly preferably 0.5 ⁇ m or more.
  • the upper limit is more preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, and particularly preferably 10 ⁇ m or less.
  • the "average primary particle size" of the filler can be obtained by observing the filler in the dispersion with a transmission electron microscope (TEM) and observing the portion (primary particles) where the particles of the filler are not aggregated.
  • TEM transmission electron microscope
  • the photograph is subjected to image processing with an image processing apparatus to measure the particle size distribution of the filler. Then, the number-based arithmetic mean diameter calculated from the particle size distribution is adopted as the "average primary particle diameter" of the filler.
  • an electron microscope (H-7000) manufactured by Hitachi, Ltd. is used as a transmission electron microscope
  • Luzex AP manufactured by Nireco Corporation is used as an image processing apparatus.
  • the filler may contain a particulate mixture in which at least two types of particle groups with different average primary particle sizes are mixed.
  • the "average primary particle size" of a certain particle group is also determined by the same method as the "average primary particle size” of the filler.
  • 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.
  • two types of particle groups having different average primary particle diameters 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 average primary particle sizes 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 0.3 or more, more preferably 0.5 or more.
  • the upper limit is preferably 4.0 or less, more preferably 3.0 or less.
  • the aspect ratio of the filler is preferably 2 or more, more preferably 4 or more, and particularly preferably 5 or more. Moreover, the upper limit of the aspect ratio is preferably 1000 or less, more preferably 500 or less, and particularly preferably 100 or less.
  • the "aspect ratio" of the filler is the ratio of the minimum length to the maximum length (maximum length/minimum length) among the three-dimensional lengths.
  • filler made of different materials
  • a combination of boron nitride and aluminum oxide, a combination of aluminum nitride and aluminum oxide, and the like are preferable.
  • a combination of two or more fillers made of the same material but different aspect ratios and a combination of two or more fillers made of different materials and different aspect ratios are also preferable.
  • the content of the filler in the composition is preferably 1% by volume or more, more preferably 5% by volume or more, and 10% by volume or more, relative to the volume of the total solid content of the composition. is particularly preferred, and 20% by volume or more is most preferred. Further, from the viewpoint of processability by lithography, it is more preferably 85% by volume or less, more preferably 81% by volume or less, and 75% by volume or less, relative to the volume of the total solid content of the composition. is particularly preferable, and it is most preferably 60% by volume or less.
  • the filler content in the composition is preferably 10% by mass or more, more preferably 30% by mass or more, relative to the mass of the total solid content of the composition.
  • the upper limit of this ratio is preferably 90% by mass or less, particularly preferably 70% by mass or less, from the viewpoint of processability by lithography. In this way, by considering processability in addition to thermal conductivity and electrical insulation, a heat conductive layer having high thermal conductivity and electrical insulation can be formed at desired positions and patterns.
  • the proportion of particle groups having an average primary particle diameter of 0.5 to 15 ⁇ m in the 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. From the viewpoint of processability by lithography, this proportion 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 preferably falls within the above range.
  • 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 glass transition temperature of the polyimide-containing portion is preferably 250°C or lower, more preferably 230°C or lower, and even more preferably 220°C or lower.
  • the lower limit of the glass transition temperature is not particularly limited, it is preferably 120° C. or higher.
  • the difference between the cyclization rate of polyimide in the polyimide-containing precursor portion before the bonding step and the cyclization rate of polyimide in the polyimide-containing portion formed in the bonding portion after the bonding step is 5% or more, and 6% or more. is preferably It is also one of the preferable aspects of the present invention that the difference in cyclization rate is 10% or more.
  • the cyclization rate of polyimide is measured, for example, by the following method. The infrared absorption spectrum of the polyimide is measured, and the peak intensity P1 near 1370 cm ⁇ 1 , which is the absorption peak derived from the imide structure, is obtained. Next, after heat-treating the polyimide at 350° C.
  • Cyclization rate (%) (peak intensity P1/peak intensity P2) x 100
  • the cyclization rate of polyimide in the polyimide-containing precursor portion before the bonding step is preferably 40 to 90%, more preferably 50 to 90%, and even more preferably 60 to 90%.
  • the cyclization rate of polyimide in the polyimide-containing portion formed in the bonding portion after the bonding step is preferably 91 to 100%, more preferably 94 to 100%, and 97 to 100%. is more preferred.
  • the cyclization rate of the polyimide in the second polyimide-containing precursor portion before the bonding step and the polyimide-containing portion formed in the bonding portion after the bonding step is preferably 5% or more, more preferably 6% or more. It is also one of the preferable aspects of the present invention that the difference in cyclization rate is 10% or more.
  • the cyclization rate of the polyimide in the second polyimide-containing precursor portion before the bonding step is preferably 40 to 90%, preferably 50 to 90%. more preferably 60 to 90%.
  • An annealing step is a heating step that may be incorporated after a bonding step (eg, bonding with a flip chip bonder).
  • the annealing step can increase the peel resistance of the joint.
  • the heating means is not particularly limited, for example, a heating device such as a hot plate or an oven can be used.
  • the heating temperature in the annealing step is preferably lower than the bonding temperature in the bonding step.
  • the heating temperature in the annealing step is preferably 180 to 440.degree. C., more preferably 200 to 350.degree. C., even more preferably 210 to 260.degree.
  • the heating temperature in the annealing step may be determined in consideration of the bonding temperature in the bonding step and the heating temperature in the heating step.
  • the difference between the bonding temperature in the bonding step and the heating temperature in the annealing step is preferably 10° C. or more.
  • the upper limit is not particularly limited, it is preferably 250° C. or lower, more preferably 200° C. or lower, for example.
  • the heating temperature in the annealing process is preferably higher than or equal to the heating temperature (maximum heating temperature) in the above-described heating process.
  • the difference between the heating temperature in the annealing step and the heating temperature in the heating step is preferably 10° C. or higher, more preferably 30° C. or higher.
  • the upper limit is not particularly limited, for example, it is preferably 250° C. or lower, more preferably 150° C. or lower.
  • the heating time in the annealing step is preferably longer than the bonding time in the bonding step.
  • the heating time in the annealing step (heating time at the above heating temperature) is preferably 1 hour or longer.
  • the upper limit of the heating time is not particularly limited, it is preferably 10 hours or less, more preferably 5 hours or less.
  • the difference between the heating time in the annealing step and the heating time in the bonding step is preferably 30 minutes or more.
  • the upper limit is not particularly limited, it is preferably 10 hours or less, more preferably 5 hours or less.
  • the atmosphere during heating can be appropriately selected from those that can be provided by heating equipment, such as under air, under N2 , and under vacuum.
  • the atmospheric pressure is not particularly limited, it is preferably 1 atm or less, more preferably 1 atm ⁇ 0.1 atm.
  • One atmosphere refers to 101,325 Pa.
  • the imidization rate after the annealing step is preferably 98% or more, for example.
  • the upper limit is not particularly limited, and is preferably 100%, for example.
  • the method for manufacturing a joined body of the present invention does not preclude the interposition of 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 it is assumed that a plurality of substrates B are arranged in parallel with respect to the substrate A and bonded together. good too.
  • 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 may be used.
  • 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 is prepared in which an electronic circuit region 8 is arranged on a silicon wafer 1x and electrodes 31 (wiring terminals A) are attached thereon (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, and the polyimide precursor is partially cyclized (cured) to form a polyimide-containing precursor portion 41 (FIG. 2(c)).
  • a substrate 1y provided with a polyimide-containing precursor portion is formed by disposing the polyimide-containing precursor portion 41 on the substrate A1.
  • the polyimide-containing precursor portion 41 may shrink compared to the resin composition layer 4 upon curing.
  • the amount of shrinkage is slightly exaggerated, but the shrinkage rate is not particularly limited, and the shrinkage rate may be smaller, or may not shrink upon curing.
  • 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 precursor portion may be patterned before curing, and the patterned portion may be plated to form the conductive path.
  • the heights h1 and h2 of the electrodes 31 vary.
  • the surface 4a of the polyimide-containing precursor 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 precursor portion. It is considered that the adhesion of the substrate is improved by planarizing in this way. In addition, it is considered that the bondability between the wiring terminals is improved without forming the conductive path.
  • FIGS. 3(a) to 3(c) respectively show the polyimide-containing precursor portion-mounted substrate (laminate) 1z after flattening.
  • the tip 31a of the electrode 31 is exposed on the surface 4b of the polyimide-containing precursor portion, and the entire surface 4b of the polyimide-containing precursor portion is flattened.
  • FIG. 3(a) shows an example of an embodiment in which the height of the electrode 31 and the surface 4b of the polyimide-containing precursor are the same height
  • FIG. 3(c) shows an example of an embodiment in which the surface 4b of the polyimide-containing precursor is higher than the height of the electrode 31, respectively.
  • a substrate B is separately prepared for the laminate (flattened polyimide-containing precursor portion-disposed substrate) 1z (FIG. 4(a)).
  • 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 precursor portion 42 is also formed on the surface of the substrate B having the wiring terminal B, and the surface 2a thereof is the same as the surface of the polyimide-containing precursor portion 41 of the substrate A. flattened.
  • the formation and flattening of the second polyimide-containing precursor portion 42 can be performed by the same method as the formation and flattening of the polyimide-containing precursor portion 41 .
  • the surface of the polyimide-containing precursor portion 41 and the electrode 31 of the substrate A and the surface of the second polyimide-containing precursor portion 42 and the electrode 32 of the substrate B are both flattened. Even if there is no conduction path as in the embodiment of 1, electrical connectivity is improved.
  • 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 polyimide-containing precursor portion 41 and the second polyimide-containing precursor portion 42 contains a migration inhibitor, even if a positional deviation occurs in this alignment, the polyimide-containing It is possible to suppress the migration of metal to the precursor portion 41 (the second polyimide-containing precursor portion 42), 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 precursor portion may be patterned before curing and the conducting path may be formed in the patterned portion by plating or the like.
  • the aligned substrate B2 and the laminate 1z are brought into contact with each other at the bonding surface P1 via the polyimide-containing precursor portion 41 and the second polyimide-containing precursor portion 42, and are bonded together (Fig. 4(b)).
  • 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 precursor portion 41 is softened by heating, and the polyimide-containing precursor portion surface 4b of the laminate 1z and the surface of the substrate B (flattened surface of the second polyimide-containing precursor portion 42) are formed. 2a are adhered to form a joined body 100.
  • the polyimide-containing portion 51 is formed from the polyimide-containing precursor portion 41 and the second polyimide-containing precursor portion 42 .
  • the polyimide contained in this polyimide-containing portion is further cyclized by the heating during the bonding. Therefore, the difference between the cyclization rate of polyimide in the polyimide-containing precursor portion 41 before the bonding step and the cyclization rate of polyimide in the polyimide-containing portion 51 formed in the bonding portion after the bonding step is 5% or more.
  • the substrate A and the substrate B can be electrically connected to each other, and the two can be firmly fixed by the above-described anchor effect.
  • the surface 4b of the polyimide-containing precursor portion of the laminate 1z and the surface 2a of the second polyimide-containing precursor portion have high flatness, the surface of the laminate 1z and the substrate B2 are closely and accurately aligned. contact state 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.
  • the conjugate of the present invention is a conjugate obtained by the method for producing a conjugate of the present invention.
  • the bonded body of the present invention can be suitably used for applications such as the device of the present invention, which will be described later.
  • the method for manufacturing a laminate of the present invention comprises the steps of: preparing a substrate C having two or more surfaces provided with wiring terminals; preparing a plurality of substrates D having surfaces provided with wiring terminals; A polyimide-containing precursor part forming step of forming a polyimide-containing precursor part on at least one surface of the substrate D provided with the wiring terminals, and at least two of the surfaces of the substrate C provided with the wiring terminals, Including a bonding step of bonding the surface of the substrate D provided with the wiring terminal, wherein the polyimide-containing precursor portion is present in all bonding portions in the bonding step, and at least one bonding portion is bonded at the bonding portion
  • the difference between the cyclization rate of polyimide in the polyimide-containing precursor portion before the bonding step and the cyclization rate of polyimide in the polyimide-containing portion formed in the bonding portion after the bonding step is 5% or more.
  • the manufacturing method of the joined body of the present invention includes a step of preparing a substrate C having two or more surfaces provided with wiring terminals.
  • the substrate C may be manufactured by a known method, or may be obtained by means such as purchase.
  • the same wiring terminals as the materials and wiring terminals A used for the substrate A described above can be used.
  • a preferred embodiment is also the same.
  • the substrate C may be a wafer or a chip, and the preferred aspects of these are the same as those of the substrate A.
  • the substrate D may be manufactured by a known method, or may be obtained by means such as purchase.
  • the same substrate as the above-described substrate B can be used, and the preferred embodiments are also the same.
  • the substrate D may be a wafer or a chip, and the preferred aspects of these are the same as those of the substrate B.
  • a polyimide-containing precursor portion is formed on the surface of at least one of the substrate C and the substrate D. As shown in FIG. Here, when two substrates D (substrate D1 and substrate D2) are bonded to substrate C, a polyimide-containing precursor portion is formed on the two surfaces of substrate C to which substrate D1 and substrate D2 are bonded. Alternatively, the polyimide-containing precursor portion may be formed on the surface of the substrate C to which the substrate D1 is bonded and the surface of the substrate D2 having the wiring terminals, or the wiring terminals of the substrates D1 and D2 may be formed.
  • the polyimide-containing precursor portion may be formed on the surface and the polyimide-containing precursor portion may be formed on all of the surfaces of the substrate C, the substrate D1, and the substrate D2, which are provided with the wiring terminals.
  • Preferred aspects of the method for forming the polyimide-containing precursor portion are the same as the preferred aspects of the method for forming the polyimide-containing precursor portion forming step in the above-described method for producing a joined body of the present invention.
  • the difference from the cyclization rate of the polyimide in the containing portion is 5% or more.
  • the bonding process is divided into two steps, and after bonding substrate D1 to substrate C, substrate D2 is bonded to substrate C.
  • the bonding step may be performed at once.
  • another substrate may be further bonded to the surface of the substrate D which is not bonded to the substrate C. This bonding may also be performed in separate bonding steps, or may be performed in one step.
  • the difference in cyclization rate is 5% or more, preferably 6% or more. It is also one of the preferred aspects of the present invention that the difference in cyclization rate is 10% or more. Moreover, from the viewpoint of adhesion, the difference in the cyclization rate is preferably 5% or more, more preferably 6% or more, at all joints. It is also one of the preferred aspects of the present invention that the difference in cyclization rate is 10% or more.
  • the cyclization rate of polyimide in the polyimide-containing precursor portion before the bonding step is preferably 40 to 90%, more preferably 50 to 90%, and even more preferably 60 to 90%.
  • the cyclization rate of polyimide in the polyimide-containing portion formed in the bonding portion after the bonding step is preferably 91 to 100%, more preferably 94 to 100%, and 97 to 100%. is more preferred.
  • the laminate manufacturing method of the present invention may further include an annealing step after the bonding step.
  • the details of the annealing step are the same as the details of the annealing step in the method for manufacturing a joined body of the present invention.
  • the laminate of the present invention is a laminate obtained by the method for producing a laminate of the present invention.
  • the laminate of the present invention can be suitably used for applications such as the device of the present invention, which will be described later.
  • a device according to the present invention comprises the bonded body of the present invention or the laminate of the present invention.
  • the device manufacturing method of the present invention includes the bonded body manufacturing method of the present invention or the laminate manufacturing method 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 of State-of-the-Art Semiconductor Package Technology" edited by 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.
  • the method for manufacturing a bonded body and the method for manufacturing a laminate 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. can.
  • the method for manufacturing a bonded body and the method for manufacturing a laminate 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). .
  • TSV Through silicon via
  • 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 the polyimide-containing portion in the above-described method for producing a joined body of the present invention or the method for producing a laminated body 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 board 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 bonding of the insulating layer 115 and the layered body 101 can also be performed using the bonded body manufacturing method of the present invention or the layered body manufacturing method of the present invention. 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 bonding of the insulating layer 115 and the wiring board 120 can also be performed by the method of manufacturing a bonded body of the present invention or the method of manufacturing a laminated body of the present invention. That is, for example, the resin layer 110b can be the polyimide-containing portion described above.
  • composition for forming polyimide-containing precursor portion of the present invention comprises a step of preparing a substrate A having a surface provided with wiring terminals, a polyimide-containing precursor portion forming a polyimide-containing precursor portion on the surface of the substrate A provided with the wiring terminals.
  • the difference between the cyclization rate of polyimide in the polyimide-containing precursor portion before the bonding step and the cyclization rate of polyimide in the polyimide-containing portion formed in the bonding portion after the bonding step is 5% or more.
  • the method for manufacturing a bonded body is synonymous with the method for manufacturing a bonded body according to the present invention described above, and preferred embodiments are also the same.
  • the composition for forming a polyimide-containing precursor part of the present invention is used for forming a polyimide-containing precursor part in the above-described method for producing a joined body or a laminated body of the present invention. It is synonymous with composition, and preferred embodiments are also the same.
  • the difference between the cyclization rate of polyimide in the polyimide-containing precursor portion before the bonding step in the application of the composition and the cyclization rate of polyimide in the polyimide-containing portion formed in the bonding portion after the bonding step is 5% or more. and is preferably 6% or more. It is also one of the preferred aspects of the present invention that the difference in cyclization rate is 10% or more.
  • the cyclization rate of polyimide in the polyimide-containing precursor portion before the bonding step is preferably 40 to 90%, more preferably 50 to 90%, and even more preferably 60 to 90%.
  • the cyclization rate of the polyimide in the polyimide-containing portion formed in the bonding portion after the bonding step in the application of the composition is preferably 91 to 100%, more preferably 94 to 100%, 97 It is even more preferred that it is ⁇ 100%.
  • the composition for forming a polyimide-containing precursor portion of the present invention preferably contains a polyimide precursor and a solvent. Moreover, it is preferable that the composition for forming a polyimide-containing precursor portion of the present invention further contains a photosensitive compound.
  • a photosensitive compound a photopolymerization initiator, a photoacid generator, and the like can be mentioned, 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.
  • the divalent organic group include straight-chain or branched aliphatic groups, groups containing cyclic aliphatic groups and aromatic groups, straight-chain 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 heteroatom, and in the cyclic aliphatic group and the aromatic group, the ring-membered hydrocarbon group is a heteroatom.
  • 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 and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4′- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 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., a 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 at 23° C. in an amount of 0.1 g or more in 100 g of a 2.38% by mass tetramethylammonium aqueous solution. 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.
  • R 132 in the repeating unit represented by (4) or R 131 in the repeating unit represented by formula (4) described below 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.
  • the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by formula (4) described below, and ethylene 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 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 R131 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.
  • 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.
  • the divalent organic group are the same as those of 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 the occurrence of warpage 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 preferable 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 more 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.
  • a terminal blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound.
  • monoamines 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-
  • the imidization rate (also referred to as ring closure rate) of 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.
  • the upper limit of the imidization rate is not particularly limited, and is preferably 95% or less, more preferably 90% or less.
  • the imidization rate is measured by the method described above.
  • 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 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. In order to obtain an organic film having excellent mechanical properties (e.g. elongation at break), the weight average molecular weight is particularly preferably 15,000 or more.
  • the number average molecular weight (Mn) of 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 dispersity is not particularly defined, for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
  • the resin composition contains a plurality of types of polyimide as the specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polyimide are 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-mentioned plural types 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 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.
  • a more preferable method is to obtain a diester from a tetracarboxylic dianhydride and an alcohol, then acid-halogenate the remaining dicarboxylic acid using a halogenating agent, and react it with a diamine.
  • 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 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. is 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. are 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 structure exhibiting a base-generating property can be introduced to the end of the specific resin.
  • a terminal blocker include a structure exhibiting a base-generating property, a hydroxy group, a thiol group, an amino group, a carboxy group, a carboxylic anhydride region, a carboxylic acid halide group, a sulfonic anhydride group, , a sulfonic acid halide group, or a compound having a reactive group such as a sulfonic acid carboxylic acid anhydride group can be used.
  • the terminal blocking agent for example, a compound having a structure exhibiting the property of generating one or more bases and one of the reactive groups described above can be used. Preferred embodiments of the structure exhibiting the property of generating a base are as described above.
  • a compound represented by the formula (T-1) may also be used as the terminal blocking agent. By blocking the ends with such a compound, it is possible to introduce a structure in which a base is likely to be generated at the ends, and it is thought that the elongation at break is likely to be improved even when cured at a low temperature.
  • L T represents a divalent organic group
  • Z 1 and Z 2 each independently represent an organic group
  • Z 1 and Z 2 may be bonded to form a ring structure. good.
  • L T is preferably a hydrocarbon group and may be either an aromatic hydrocarbon group or an aliphatic hydrocarbon group. It is preferably a hydrocarbon group or a cyclic aliphatic hydrocarbon group.
  • the linking chain length of L T (that is, the minimum number of atoms among the atoms connecting two carbonyl groups bonded to L T ) is preferably 2 to 4, more preferably 2.
  • Z 1 and Z 2 have the same meanings as Z 1 and Z 2 in formula (3-1), and preferred embodiments are also the same.
  • an embodiment in which at least one of Z 1 , Z 2 and LT has a polymerizable group is also one of preferred embodiments of the present invention.
  • Examples of the polymerizable group include a radically polymerizable group, an epoxy group, an oxetanyl group, a methylol group, an alkoxymethyl group and the like, and a radically polymerizable group is preferred.
  • the radically polymerizable group is preferably a group having an ethylenically unsaturated group, such as a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, a maleimide group, a styryl group, a vinyl group, a (meth)allyl group, and the like. mentioned. Among these, a (meth)acryloxy group is preferable from the viewpoint of reactivity.
  • These polymerizable groups may be directly bonded to the nitrogen atom in formula (T-1), or may be bonded via a linking group such as a hydrocarbon group (eg, an alkylene group).
  • the method for producing a polyimide precursor or the like may include a step of depositing a solid. 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 to precipitate 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.
  • 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 and the solvent resistance of the pattern (cured product) can be improved. can.
  • 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.
  • the resin composition of the present invention preferably contains a polymerizable compound having a ring structure.
  • the ring structure may be an aliphatic ring structure, an aromatic ring structure, or a ring structure combining these, but preferably includes an aliphatic ring structure.
  • the aromatic ring structure may be an aromatic hydrocarbon ring structure or an aromatic heterocyclic ring structure, preferably an aromatic hydrocarbon ring structure, more preferably a benzene ring structure.
  • the aliphatic ring structure may be either an aliphatic hydrocarbon ring structure or an aliphatic heterocyclic ring structure, but an aliphatic hydrocarbon ring structure is preferred.
  • ring structure contained in the polymerizable compound containing a ring structure examples include cyclohexane ring, norbornene ring, isonorbornene ring, dicyclopentane ring, adamantane ring, polyphenyl ring, fluorene ring, acenaphthyl ring and the like.
  • the number of ring structures in the polymerizable compound having a ring structure is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 or 2.
  • Examples of the polymerizable group in the polymerizable compound having a ring structure 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, and the like. , 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.
  • the number of polymerizable groups in the polymerizable compound having a ring structure is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 or 2, and 2 is particularly preferred.
  • the resin composition of the present invention preferably contains a polymerizable compound whose homopolymer has a glass transition temperature of 200° C. or higher.
  • the glass transition temperature (Tg) of a homopolymer is measured, for example, by a differential scanning calorimeter according to ASTM D3418-8. Although the glass transition temperature (Tg) varies depending on the molecular weight, if the weight-average molecular weight is 10,000 or more, the variation of Tg due to the molecular weight can be ignored.
  • the glass transition temperature is preferably 210° C. or higher, more preferably 220° C. or higher.
  • the upper limit of the glass transition temperature is not particularly limited, it can be, for example, 350° C. or lower.
  • the cyclization rate of the polyimide during the formation of the polyimide-containing precursor portion can be reduced, and the cyclization rate with the polyimide-containing portion obtained after the subsequent bonding step. It may be easier to adjust the difference.
  • polymerizable compounds examples include radical cross-linking agents and 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.
  • Compounds having a boiling point of 100° C. or higher under normal pressure include compounds described in paragraph 0203 of International Publication No. 2021/112189. The contents of which are incorporated herein.
  • Preferred radical cross-linking agents other than those described above include radically polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021/112189. The contents of which are incorporated herein.
  • 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 a mixture of two or more may be used. 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 or reaction products thereof in the composition. 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.
  • a photoacid generator or a photobase generator in the exposure step.
  • cross-linking agents compounds having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group and an alkoxymethyl group are preferred.
  • a compound having a structure in which at least one group selected from the group consisting of groups is directly bonded to a nitrogen atom is more preferable.
  • cross-linking agents include, for example, amino group-containing compounds such as melamine, glycoluril, urea, alkylene urea, and benzoguanamine, which are reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atoms of the amino groups are converted into acyloxymethyl groups, methylol groups,
  • a compound having a structure substituted with an ethylol group or 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.
  • the compound having at least one group selected from the group consisting of acyloxymethyl group, methylol group, ethylol group and alkoxymethyl group includes at least one group selected from the group consisting of urea bond and urethane bond.
  • compounds having A preferred embodiment of the above compound is the above-described crosslinking except that the polymerizable group is not a radically polymerizable group but at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group and an alkoxymethyl group. It is the same as the preferred embodiment of agent U.
  • Specific examples of compounds having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group and an ethylol 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 compound compound having an oxetanyl group
  • the 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 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, 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.
  • ⁇ - ⁇ Omnirad 184 ⁇ Omnirad 1173 ⁇ Omnirad 2959 ⁇ Omnirad 127( ⁇ IGM Resins B.V. ⁇ ) ⁇ IRGACURE 184(IRGACURE ⁇ ) ⁇ DAROCUR 1173 ⁇ IRGACURE 500 ⁇ IRGACURE -2959 and IRGACURE 127 (trade names: both manufactured by BASF) can be used.
  • ⁇ -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.
  • acylphosphine oxide-based initiators for example, compounds described in paragraphs 0161 to 0163 of WO2021/112189 can also be preferably used. The contents of which are incorporated herein.
  • 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.
  • photoradical polymerization initiators examples include oxime compounds having a fluorene ring described in paragraphs 0169 to 0171 of International Publication No. 2021/112189, and oximes having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring.
  • Compounds, oxime compounds having fluorine atoms can also be used. The contents of which are incorporated herein.
  • an oxime compound having a nitro group an oxime compound having a benzofuran skeleton, and a substituent having a hydroxy group on the carbazole skeleton described in paragraphs 0208 to 0210 of International Publication No. 2021/020359 are used. Bound oxime compounds can also be used. 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 possessed by 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. .
  • radical photopolymerization initiator compounds described in paragraphs 0175 to 0179 of International Publication No. 2021/020359 can be used. The contents of which are incorporated herein.
  • 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 promoted by heating with an oven, a hot plate, or the like.
  • 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, penzopyran, 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 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 precursor of the cyclized resin, the resin composition preferably contains a base generator.
  • the base generator may be an ionic base generator or a non-ionic base generator.
  • Examples of the base generated from the base generator 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 generators include compounds represented by formula (B1) or formula (B2) described in paragraphs 0275 to 0285 of International Publication No. 2021/112189, International Publication No. 2020/066416.
  • the compound represented by formula (N1) described in paragraphs 0102 to 00162 of , or the base generator is preferably a thermal base generator described in paragraphs 0013 to 0041 of WO 2020/054226. The contents of which are incorporated herein.
  • 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.
  • the aspect which does not contain a base generator substantially is also one of the preferable aspects of this invention.
  • Constant substantially no means that it is 0.1% by mass or less, more preferably 0.01% by mass or less, relative to the total solid content of the composition of the present invention.
  • One or two or more base generators can be used. When two or more kinds 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 , ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -valerolactone, alkyl alkyloxyacetates (e.g.
  • 2-alkyloxypropionic acid alkyl esters e.g., methyl 2-alkyloxypropionate, 2-alkyloxypropionic acid ethyl, propyl 2-alkyloxypropionate, 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.
  • solvent selected from methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more kinds is preferable.
  • an embodiment containing ⁇ -valerolactone as a solvent is also one of the preferred embodiments of the present invention.
  • the content of ⁇ -valerolactone with respect to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more. preferable.
  • the upper limit of the content is not particularly limited, and may be 100% by mass. The above content may be determined in consideration of the solubility of components such as the specific resin contained in the resin composition.
  • dimethylsulfoxide and ⁇ -valerolactone when dimethylsulfoxide and ⁇ -valerolactone are used in combination, it is preferable that 60 to 90% by mass of ⁇ -valerolactone and 10 to 40% by mass of dimethylsulfoxide are contained with respect to the total mass of the solvent. More preferably, 70 to 90% by mass of ⁇ -valerolactone and 10 to 30% by mass of dimethyl sulfoxide are contained, and 75 to 85% by mass of ⁇ -valerolactone and 15 to 25% by mass of dimethyl sulfoxide are contained. More preferably, it contains
  • 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 0316 of International Publication No. 2021/112189 and compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are herein described. incorporated. 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. Moreover, the following R includes a structure derived from a blocking agent in a blocked isocyanate group.
  • the blocking agent may be selected depending on the desorption temperature, and examples thereof include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, active methylene compounds, and the like.
  • examples thereof include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, active methylene compounds, and the like.
  • alcohol compounds for example, from the viewpoint of desorption temperature of 160 to 180° C., caprolactam and the like are preferable.
  • Commercially available products of such compounds include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • 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
  • an oligomer type compound having a plurality of alkoxysilyl groups can also be used as the silane coupling agent.
  • examples of such oligomer type compounds include compounds containing repeating units represented by the following formula (S-1).
  • R 1 S1 represents a monovalent organic group
  • R 2 S2 represents a hydrogen atom, a hydroxy group or an alkoxy group
  • n represents an integer of 0-2.
  • R S1 preferably has a structure containing a polymerizable group.
  • Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, an amino group, and the like.
  • 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., a vinylphenyl group), and a (meth)acrylamide group.
  • R S2 is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.
  • n represents an integer of 0 to 2, preferably 1;
  • multiple repeating units represented by formula (S-1) contained in the oligomer type compound may have the same structure.
  • n is 1 in at least two.
  • Commercially available products can be used as such oligomer type compounds, and examples of commercially available products include KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • Aluminum-based adhesion promoters 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.
  • migration inhibitors include the following compounds. Further, E-2 to E-5 in Examples described later are also included as preferred specific examples.
  • 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 compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, metal compounds and the like.
  • Specific compounds of the polymerization inhibitor include compounds described in paragraph 0310 of International Publication No. 2021/112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1- Oxyl free radical, phenoxazine, and the like. The contents of which are incorporated herein.
  • 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 from 0.02 to 15% by mass, and even more preferably from 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 optionally contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, as long as the effects of the present invention can be obtained.
  • additives such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, as long as the effects of the present invention can be obtained.
  • Organic titanium compounds, antioxidants, anti-agglomerating agents, phenolic compounds, other polymer compounds, plasticizers and other auxiliaries (for example, antifoaming agents, flame retardants, 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.
  • the total blending amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.
  • 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.
  • Fluorinated surfactants include compounds described in paragraph 0328 of WO2021/112189. 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, hydrocarbon-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants are described in paragraphs 0329 to 0334 of WO 2021/112189, respectively. compound. The contents of which are incorporated herein.
  • 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 resin composition of the present invention may contain a thermal polymerization initiator, particularly a thermal radical polymerization initiator.
  • a thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or promotes a polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be advanced, so that the solvent resistance can be further improved.
  • 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 commercially available products can also be used, 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.
  • thermal radical polymerization initiators include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein.
  • thermal polymerization initiator When a thermal polymerization 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.
  • One type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more thermal polymerization initiators are contained, the total amount is preferably within the above range.
  • the resin composition of the present invention may contain inorganic particles.
  • inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, boron nitride, boron nitride nanotubes, Boron carbon nitride, aluminum nitride, silicon nitride, and the like can be included.
  • the average particle diameter of the inorganic particles is preferably 0.01 to 2.0 ⁇ m, more preferably 0.02 to 1.5 ⁇ m, still more preferably 0.03 to 1.0 ⁇ m, and 0.04 to 0.5 ⁇ m. Especially preferred.
  • the average particle size of the inorganic particles is the primary particle size and the volume average particle size.
  • the volume average particle size can be measured by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, the centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction/scattering method can be used.
  • 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. Specific examples of UV absorbers include compounds described in paragraphs 0341 to 0342 of WO2021/112189. The contents of which are incorporated herein.
  • 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 as an additive, it is possible to improve the elongation properties of the film after curing and the adhesion to the metal material.
  • Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Specific examples of antioxidants include compounds described in paragraphs 0348 to 0357 of WO2021/112189. The contents of which are incorporated herein.
  • the amount of antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to the 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.
  • 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 with respect 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, methylene tris-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 if 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.
  • Examples include a method of performing filter filtration on the raw material constituting the product, and performing distillation under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like.
  • 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 range.
  • 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 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 added dropwise to 3 liters of water to precipitate the polymer.
  • the obtained precipitate was collected by filtration and vacuum dried 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.
  • compositions 1 to 20 Each component was mixed as described in Table 1 or Table 2 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 resin compositions (compositions 1 to 20).
  • 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.
  • F-1 Boron nitride/Platelets001 manufactured by 3M (average particle size: 500 nm)
  • F-2 Alumina / Sumitomo Chemical, Sumicorundum AA-03NF (average particle size: 250 nm)
  • F-3 Alumina / manufactured by Sumitomo Chemical, NXA-150 (average particle size: 150 nm)
  • F-4 Alumina / manufactured by Sumitomo Chemical, NXA-100 (average particle size: 100 nm)
  • Pillar substrates having the following sizes and metal types were produced by plating. a) Pitch: 45 ⁇ 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 ⁇ m, silicon wafer, copper, tin formed in this order It is c) A SiO 2 film with a thickness of 5 ⁇ m was formed on an 8-inch silicon wafer by CVD (chemical vapor deposition), and a hole pattern with a pitch of 45 ⁇ m and a diameter of 20 ⁇ m was formed in a square array by photolithography and dry etching.
  • CVD chemical vapor deposition
  • 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 until the thickness became 3 ⁇ m along with the internal copper.
  • FIG. 6(a) is a schematic sectional view of the above a).
  • 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).
  • the arithmetic mean value of the pillar spacing p in each pillar is the pitch, which is 45 ⁇ m in a).
  • the arithmetic mean value of the pillar height h of each pillar is the pillar height, which is 10 ⁇ m in a).
  • FIG. 6A is a schematic sectional view of the above a).
  • 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).
  • 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).
  • the arithmetic mean value of the pillar spacing p of each pillar is the pitch, which is 45 ⁇ m in b).
  • FIG. 6B 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).
  • a chip was created by cutting into 5 mm squares with a dicing machine, and a flip chip bonder manufactured by Toray Engineering Co., Ltd. was used. Welded under the conditions. The maximum peel force was then measured. In these examples, the chip that is the substrate A and the chip that is the substrate B are joined together, so "chip-chip” is written in the column of "joint” in the table.
  • Example 12 and 13 ⁇ Fabrication of substrate/substrate laminate (bonded body) (Examples 12 and 13)>
  • the composition 6 was applied to the substrate A so as to have a film thickness of 15 ⁇ m, and was 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 precursor portion. After that, the surface of the polyimide-containing precursor portion was flattened using CMP manufactured by Nachi-Fujikoshi Machine Industry Co., Ltd. so that the surface had a residual film thickness of 5 ⁇ m.
  • the surface on the polyimide-containing precursor portion side was attached to a dicing tape, polished with a polishing machine so that the remaining film of the silicon substrate became 50 ⁇ m, and cut into 5 mm squares with a dicing machine.
  • a flip chip bonder manufactured by Toray Engineering Co., Ltd.
  • 3 sheets were bonded in the case of Example 12, and 6 sheets were bonded in the case of Example 13.
  • the bonding conditions were those described in the columns of "bonding temperature”, “bonding time” and “pressure” in the table. The maximum peel force was then measured.
  • 3 or 6 chips, which are the substrate A are joined together, so “chip/chip x 3" or “chip/chip x 6" is described in the column of "joint" in the table. bottom.
  • Example 14 ⁇ Production of substrate/substrate laminate (bonded body) (Example 14)>
  • each composition described in the table was applied to substrate A and substrate B described in the table so as to have a film thickness of 15 ⁇ m, 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 precursor portion. Thereafter, using CMP manufactured by Nachi-Fujikoshi Machine Industry Co., Ltd., the surface of the polyimide-containing portion was flattened so that the surface had a residual film thickness of 5 ⁇ m.
  • the polyimide surfaces of the substrate B and the substrate A were bonded to each other with a bonder 540 manufactured by EVG.
  • the bonding conditions were as described in the columns of "bonding temperature”, “bonding time” and “pressure” in the table. After the joining, it was cut into 5 mm squares with a dicing machine, and the maximum peeling force was measured.
  • a wafer (substrate a) as substrate A and a wafer (substrate c) as substrate B are bonded together, so the column of "bonding" in the table is written as "wafer-wafer". .
  • Example 20 ⁇ Production of substrate/substrate laminate (bonded body) (Examples 20 to 22)>
  • each composition described in the table was applied to substrate A and substrate B described in the table so as to have a film thickness of 7.5 ⁇ m, and baked at 100° C. for 5 minutes.
  • an i-line stepper exposure apparatus FPA-3000i5+ manufactured by Canon Inc.
  • FPA-3000i5+ manufactured by Canon Inc.
  • additional baking was performed under the conditions of temperature and time described in the columns of "film formation temperature” and "film formation time” to obtain a polyimide-containing precursor portion for the first layer.
  • Example 23 and 24 ⁇ Fabrication of substrate/substrate laminate (bonded body) (Examples 23 and 24)>
  • each composition described in the table was applied to substrate A described in the table so as to have a film thickness of 15 ⁇ m, and baked at 100° C. for 5 minutes. Further, 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 precursor portion. Thereafter, using CMP manufactured by Nachi-Fujikoshi Machine Industry Co., Ltd., the surface of the polyimide-containing portion was flattened so that the surface had a residual film thickness of 5 ⁇ m.
  • TEG Transmission Element Group
  • a TEG wafer having Cu wiring under the pillars of the pillar substrate and an interposer wafer were prepared. Inside these contain a daisy chain pattern that measures the conduction resistance. Pitch of TEG wafer: 7 ⁇ m, copper/tin pillar diameter: 3.5 ⁇ m, copper/tin pillar height: 1/3 ⁇ m, silicon wafer, SiO 2 , copper and tin are formed in this order.
  • a chip size of 10 mm square was prepared because the interposer includes extraction wiring around it.
  • Interposer pitch 7 ⁇ m, copper pillar diameter: 4 ⁇ m, silicon wafer, SiO 2 , and copper are formed in this order.
  • the interposer was flattened using CMP manufactured by Nachi-Fujikoshi Machine Industry Co., Ltd. so that copper and SiO 2 were in the same plane without forming tin pillars.
  • each composition listed in the table was applied to the substrate A (TEG wafer) listed in the table so as to have a film thickness of 15 ⁇ m, and baked at 100° C. for 5 minutes. Further, 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 precursor portion.
  • FIG. 7A is a schematic cross-sectional view of the substrate A (TEG wafer) 60.
  • FIG. 7A is a schematic cross-sectional view of the substrate A (TEG wafer) 60.
  • Substrate A 60 comprises a SiO 2 layer 62 and electrodes (daisy chain pattern) 63 on a silicon wafer 61 . Further, the electrode 63 is formed of a Cu wiring 63a and a tin pillar 63b formed on a portion of the Cu wiring 63a exposed from the SiO.sub.2 layer 62. As shown in FIG. The pitch, copper/tin pillar diameter, and copper/tin pillar height in the TEG wafer are as described above.
  • FIG. 7(b) shows a state in which planarization is performed after the polyimide-containing precursor portion 64 is formed using the composition described in the table.
  • FIG. 7(c) is a schematic cross-sectional view of a chip 65 of 5 mm square obtained by cutting the substrate A60 shown in FIG. 7(b) with the dicing machine. Width W1 is 5 mm.
  • FIG. 8A is a schematic cross-sectional view of the substrate B (interposer wafer) 70.
  • FIG. Substrate B 70 comprises a SiO 2 layer 72 and electrodes (daisy chain pattern) 73 on a silicon wafer 71 .
  • the electrodes 73 are made of copper, and the pitch and copper pillar diameter in the interposer wafer are as described above.
  • FIG. 8(b) shows a chip 74 of 10 mm square obtained by cutting the substrate B70 shown in FIG. 8(a) with the dicing machine.
  • FIG. 8(c) shows the state in which the chip 65 and the chip 74 are joined by the above method.
  • the chip (TEG chip) as the substrate A and the chip (interposer chip) as the substrate B are bonded together, so the column of "bonding" in the table shows "chip/chip”. Described.
  • each composition shown in the table was applied to substrate A shown in the table so as to have a film thickness of 15 ⁇ m, and baked at 100° C. for 5 minutes. Further, 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 precursor portion. Thereafter, using CMP manufactured by Nachi-Fujikoshi Machine Industry Co., Ltd., the surface of the polyimide-containing portion was flattened so that the surface had a residual film thickness of 5 ⁇ m.
  • a chip was created by cutting into 5 mm squares with a dicing machine, and a flip chip bonder manufactured by Toray Engineering Co., Ltd. was used. Welded under the conditions. After that, each obtained substrate laminate was heat-treated using an oven under the conditions described in the columns of "annealing temperature”, "annealing time” and “annealing atmosphere” in the table. The maximum peel force was then measured.
  • a chip (substrate a)) as substrate A and a chip (substrate b) as substrate B) are bonded together, so the column of "bonding" in the table contains "chip-chip". Described.
  • the maximum peel resistance was measured by the same method as described in “Evaluation of maximum peel resistance” below, and the evaluation results are shown in the column “Maximum peel resistance after annealing” in the table.
  • the evaluation criteria were as follows. It can be said that the larger the maximum peel resistance, the more excellent the adhesiveness of the joined body.
  • the cyclization rate of polyimide in the polyimide-containing portion after the annealing step was measured by the same measurement method as for the "post-bonding cyclization rate” described later, and is listed in the "post-annealing cyclization rate” column of the table. The unit of numerical value is "%".
  • -Evaluation criteria- S The maximum peel resistance was 400 kg/cm 2 or more.
  • cyclization rate of the polyimide in the polyimide-containing precursor portion formed on the substrate A and the second polyimide-containing precursor portion formed on the substrate B was measured by the above-described measurement method, and the respective values in the table ""Pre-conjugation cyclization rate” column.
  • the cyclization rate of polyimide in the polyimide-containing portion after bonding was measured by the above-described measuring method and described in the "post-bonding cyclization rate" column of the table. The unit of each numerical value is "%".
  • Substrate A (underlying substrate, daughter chip) 1x silicon wafer 1y polyimide-containing precursor part-disposed substrate 1z laminated body 2 substrate B (mother chip) 2a surface of the second polyimide-containing precursor portion on 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 precursor portion (before flattening) 4b Surface of polyimide-containing precursor part (after flattening) 41 polyimide-containing precursor portion 42 second polyimide-containing precursor portion 51 polyimide-containing portion 8 electronic circuit region 10 substrate 12 wiring terminal A 14 conducting path 16 electrode 60 substrate A (TEG wafer) 61 silicon wafer 62 SiO 2 layer 63 electrode (daisy chain pattern) 63a Cu wiring 63b Tin pillar 64 Precursor portion containing polyimide 65 Chip 70 Substrate B (interposer wafer) 71 silicon wafer 72 SiO 2 layer 73 electrode (daisy chain pattern) 74

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