WO2022230899A1 - 接合体の製造方法、半導体デバイスの製造方法、及び、樹脂組成物。 - Google Patents

接合体の製造方法、半導体デバイスの製造方法、及び、樹脂組成物。 Download PDF

Info

Publication number
WO2022230899A1
WO2022230899A1 PCT/JP2022/018934 JP2022018934W WO2022230899A1 WO 2022230899 A1 WO2022230899 A1 WO 2022230899A1 JP 2022018934 W JP2022018934 W JP 2022018934W WO 2022230899 A1 WO2022230899 A1 WO 2022230899A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
filler
acid
compounds
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/018934
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
敦 中村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Priority to KR1020237036904A priority Critical patent/KR102906195B1/ko
Priority to JP2023517573A priority patent/JPWO2022230899A1/ja
Priority to CN202280031212.9A priority patent/CN117203746A/zh
Publication of WO2022230899A1 publication Critical patent/WO2022230899A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K7/00—Constructional details common to different types of electric apparatus
    • H05K7/20—Modifications to facilitate cooling, ventilating, or heating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P52/00—Grinding, lapping or polishing of wafers, substrates or parts of devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/071—Connecting or disconnecting
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/071—Connecting or disconnecting
    • H10W72/073—Connecting or disconnecting of die-attach connectors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/071—Connecting or disconnecting
    • H10W72/073—Connecting or disconnecting of die-attach connectors
    • H10W72/07331—Connecting techniques
    • H10W72/07337—Connecting techniques using a polymer adhesive, e.g. an adhesive based on silicone or epoxy
    • H10W72/07338—Connecting techniques using a polymer adhesive, e.g. an adhesive based on silicone or epoxy hardening the adhesive by curing, e.g. thermosetting
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/30—Die-attach connectors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/30—Die-attach connectors
    • H10W72/351—Materials of die-attach connectors
    • H10W72/353—Materials of die-attach connectors not comprising solid metals or solid metalloids, e.g. ceramics
    • H10W72/354—Materials of die-attach connectors not comprising solid metals or solid metalloids, e.g. ceramics comprising polymers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/851—Dispositions of multiple connectors or interconnections
    • H10W72/874—On different surfaces
    • H10W72/884—Die-attach connectors and bond wires
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
    • H10W74/15—Encapsulations, e.g. protective coatings characterised by their shape or disposition on active surfaces of flip-chip devices, e.g. underfills
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W90/00—Package configurations
    • H10W90/701—Package configurations characterised by the relative positions of pads or connectors relative to package parts
    • H10W90/721—Package configurations characterised by the relative positions of pads or connectors relative to package parts of bump connectors
    • H10W90/722—Package configurations characterised by the relative positions of pads or connectors relative to package parts of bump connectors between stacked chips
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W90/00—Package configurations
    • H10W90/701—Package configurations characterised by the relative positions of pads or connectors relative to package parts
    • H10W90/731—Package configurations characterised by the relative positions of pads or connectors relative to package parts of die-attach connectors
    • H10W90/732—Package configurations characterised by the relative positions of pads or connectors relative to package parts of die-attach connectors between stacked chips
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W90/00—Package configurations
    • H10W90/701—Package configurations characterised by the relative positions of pads or connectors relative to package parts
    • H10W90/731—Package configurations characterised by the relative positions of pads or connectors relative to package parts of die-attach connectors
    • H10W90/734—Package configurations characterised by the relative positions of pads or connectors relative to package parts of die-attach connectors between a chip and a stacked insulating package substrate, interposer or RDL
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W90/00—Package configurations
    • H10W90/701—Package configurations characterised by the relative positions of pads or connectors relative to package parts
    • H10W90/751—Package configurations characterised by the relative positions of pads or connectors relative to package parts of bond wires
    • H10W90/754—Package configurations characterised by the relative positions of pads or connectors relative to package parts of bond wires between a chip and a stacked insulating package substrate, interposer or RDL

Definitions

  • the present invention relates to a method for manufacturing a bonded body, a method for manufacturing a semiconductor device, and a resin composition.
  • Electronic devices such as mobile phones and tablet terminals are getting smaller and smaller, while their functions are diversifying.
  • electronic circuits incorporated in electronic devices are required to be further miniaturized, highly integrated, and mounted at high density.
  • Packaging technologies such as SIP (System in Package), MCM (Multi Chip Module), and POP (Package on Package) are attracting attention as technologies that achieve miniaturization while maintaining high performance and reliability with multiple functions. . Since these techniques can reduce the number of parts and simplify the semiconductor manufacturing process, they are also expected to reduce the cost of electronic devices.
  • FIG. 1 is a cross-sectional view showing the structure of a typical COC.
  • the COC in this example comprises a daughter chip (first substrate) 1 and a mother chip (second substrate) 2 .
  • An electronic circuit (not shown) and flip chip electrodes (not shown) are formed on the mother chip 2 , and the daughter chip 1 is supported and connected via solder electrodes (bumps) 93 .
  • the periphery of the solder electrode 93 is filled with an underfill 94 to ensure insulation.
  • the mother chip 2 is mounted on the base substrate 98 while maintaining insulation by being adhered to the base substrate 98 by the bonding film 91 .
  • the electrical connection is made through wire bonding pad 97b, wire bonding 96 and substrate electrode 97a.
  • Such a COC structure is sealed with a sealing resin 95 to form a semiconductor device 90 .
  • the semiconductor device 90 is provided with solder balls 99, through which it is incorporated into electronic equipment. Further, by further applying this flip-chip mounting technique, techniques and materials for three-dimensional mounting using TSV (Through Silicon Via) are being studied (Non-Patent Document 1).
  • the underfill 94 is filled in the gap. Therefore, a fluid resin is used as the material forming the underfill, and the resin is cured and molded after being filled between the solder bumps.
  • members such as wire bonding pads 97b around the COC, and it is not easy to fill the underfill without contaminating the surfaces of these members.
  • the pitch of solder bumps is becoming narrower as circuits become more highly integrated. It is difficult to reliably fill the underfill during this time. Further, such underfilling is only used to mitigate physical damage and improve connection reliability.
  • the present invention provides a method for manufacturing a bonded body comprising a filler-containing layer having excellent thermal conductivity, a method for manufacturing a semiconductor device including the bonded body obtained by the above manufacturing method, and a resin composition used in the above manufacturing method.
  • the purpose is to provide goods.
  • a method for producing a joined body comprising: joining a surface having a filler-containing layer of the laminate and at least part of the wiring terminals of the substrate B.
  • the step of forming the filler-containing layer includes applying a resin composition containing at least one resin selected from the group consisting of a binder and a binder precursor and a filler to the convex portion of the substrate A.
  • the method for producing a joined body according to ⁇ 1> which is a step including applying on the surface having the conjugate.
  • the method for producing a joined body according to ⁇ 2>, wherein the step of forming the filler-containing layer includes heating the composition at a temperature of 150 to 300° C. after the application.
  • the TTV of the filler-containing layer in the laminate is 10 ⁇ m or less, and the TTV is defined as dividing a region 1 mm or more inward from the edge of the filler-containing layer into 2 mm square sections, and dividing each section into one side.
  • T1-T2 Measure the maximum thickness (T1) between one surface and the other surface and the minimum thickness (T2) between one surface and the other surface, and the film thickness difference (T1-T2) for each section is calculated, and each section is ranked in descending order of the film thickness difference (T1-T2), and from the highest section to the largest section in order of the film thickness difference, the number of sections corresponding to 10% of the total number of sections and the lowest section Section groups corresponding to 10% of the total number of sections are excluded in ascending order of film thickness difference, and the arithmetic mean value of each film thickness difference (T1-T2) of the remaining section groups ⁇ 1> to ⁇ 4
  • ⁇ 6> The method for producing a joined body according to any one of ⁇ 1> to ⁇ 5>, wherein the convex portion contains a metal.
  • the metal includes at least one metal selected from the group consisting of copper, tin and nickel.
  • the convex portion includes at least a layer containing copper and a layer containing tin.
  • the binder contained in the filler-containing layer is an insulating binder.
  • ⁇ 10> Any one of ⁇ 1> to ⁇ 9>, wherein the binder contained in the filler-containing layer contains at least one group selected from the group consisting of a vinyl group, an acrylic group, and a methacrylic group. 3.
  • ⁇ 12> The method for producing a joined body according to any one of ⁇ 1> to ⁇ 11>, wherein the filler has a volume resistivity of 1.0 ⁇ 10 11 ⁇ cm or more.
  • ⁇ 13> Any one of ⁇ 1> to ⁇ 12>, wherein the average particle size of the filler is 10 ⁇ m or less, and the average particle size is the average value of the diameter of the minimum enclosing circle for the apparent contour of each particle or 1.
  • ⁇ 14> The method for producing a joined body according to any one of ⁇ 1> to ⁇ 13>, wherein the flattening in the step of obtaining the laminate is performed by cutting.
  • ⁇ 15> The method for producing a bonded body according to any one of ⁇ 1> to ⁇ 14>, wherein the bonding temperature in the bonding step is 300° C. or less.
  • ⁇ 16> The bonded body according to any one of ⁇ 1> to ⁇ 15>, wherein the thermal diffusivity of the filler-containing layer in the bonded body obtained is 2.0 ⁇ 10 ⁇ 7 m 2 s ⁇ 1 or more.
  • Production method. ⁇ 17> A method for manufacturing a semiconductor device, comprising a joined body obtained by the method for producing a joined body according to any one of ⁇ 1> to ⁇ 16>.
  • ⁇ 18> A resin composition used for forming the filler-containing layer in the method for producing a joined body according to any one of ⁇ 1> to ⁇ 16>.
  • a method for producing a joined body comprising a filler-containing layer having excellent thermal conductivity
  • a method for producing a semiconductor device comprising the joined body obtained by the above-mentioned production method
  • a resin composition used in the above-mentioned production method. goods are provided.
  • FIG. 1 is a cross-sectional view schematically showing the structure of a COC semiconductor device
  • FIG. FIG. 4 is a process explanatory view showing a schematic cross-sectional view of a process of bonding substrates in a method for manufacturing a bonded body according to an embodiment of the present invention.
  • FIG. 2A is a process explanatory view showing a schematic cross-sectional view of a process of bonding substrates in the method for manufacturing a bonded body according to an embodiment of the present invention (continuation of FIG. 2).
  • FIG. 4 is a process explanatory diagram showing a schematic cross-sectional view of a process for bonding substrates in the method for manufacturing a bonded body according to one embodiment of the present invention (continuation of FIG. 3).
  • 1 is a cross-sectional view schematically showing an example of a three-dimensionally mounted semiconductor device using TSVs;
  • FIG. It is a schematic cross-sectional view showing details of a substrate used in Examples.
  • an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • 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 method for producing a joined body of the present invention includes the steps of preparing a substrate A having a surface having convex portions and a substrate B having wiring terminals, and applying a binder and a filler to the surface having the convex portions of the substrate A. a step of forming a filler-containing layer containing the a step of bonding the surface having the filler-containing layer and at least part of the wiring terminals of the substrate B;
  • a layer having excellent thermal diffusibility can be formed by making the resin layer contain a filler to form a filler-containing layer.
  • the CTE (coefficient of thermal expansion) of the filler-containing layer can be lowered, making it possible to bring the CTE of the substrate and the CTE of the filler-containing layer closer, suppressing warping of the joined body. It is considered that effects such as suppressing delamination in the joined body can also be obtained.
  • NCF Non Conductive Film
  • the daughter chip (first substrate) is brought into contact with the mother chip (second substrate), then heated to melt the solder and connect to the electrodes on the mother chip (second substrate) side, and then
  • the adhesive film is heated at the same time to be softened, and the two are bonded and fixed.
  • the resin layer on the pillar is removed by lithography, there are problems such as an increase in the number of steps.
  • the protrusions and the resin layer (filler-containing layer) can be joined after the heights of the protrusions and the resin layer (filler-containing layer) are aligned to some extent by flattening. It is presumed that this makes it possible to manufacture a joined body that is resistant to peeling and that suppresses the generation of voids.
  • the manufacturing method of the joined body of the present invention includes a step (preparing step) of preparing a substrate A having a surface with projections and a substrate B having wiring terminals.
  • the substrate A and the substrate B may be manufactured, or may be obtained by means such as purchase.
  • the substrate A has a surface with protrusions.
  • 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 protrusions on the substrate A are preferably pillar electrodes.
  • the convex portion preferably contains a metal such as tin (Sn), gold (Au), silver (Ag), copper (Cu), palladium (Pd), platinum (Pt), cobalt (Co), nickel.
  • Ni zinc (Zn), ruthenium (Ru), iridium (Ir), rhodium (Rh), lead (Pb), bismuth (Bi), and at least one selected from the group consisting of indium (In) It more preferably contains a metal, and more preferably contains at least one metal selected from the group consisting of copper, tin and nickel.
  • metal X or an alloy containing that metal is generically simply referred to as "comprising metal X.”
  • the alloy may contain elements other than those exemplified above.
  • a copper alloy may contain silicon atoms to form a Corson alloy.
  • the convex portion may be a convex portion including a plurality of different members.
  • the 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 a metal layer such as copper
  • electrode an electrode
  • a part used as solder hereinafter also referred to as a "conducting path” made of metal such as nickel, tin, lead, or an alloy containing one or more of these is formed on the electrode and the conducting path may be present in series to form one convex portion.
  • the convex portion is a convex portion including at least a layer containing copper and a layer containing tin.
  • An example of the substrate A having such protrusions is the substrate b) used in the examples of the present application.
  • 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, 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. or higher, and even more preferably 800° 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 copper passage is preferably 400° C. or lower, more preferably 300° C. or lower, and even more preferably 250° C. or lower.
  • the lower limit of the melting point is not particularly limited as long as it is solid at room temperature. It is preferable that a plurality of protrusions are formed.
  • 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.
  • a semiconductor production substrate is particularly preferred, and a silicon substrate (silicon wafer) is more preferred.
  • Substrate A may have an electronic circuit area containing electronic circuits. Further, the electronic circuit may have elements such as semiconductors.
  • the electronic circuit is electrically connected to the protrusion.
  • the size of the substrate A for example, wafer size
  • the diameter maximum diameter if the substrate A is not circular
  • it is preferably 2,000 mm or less.
  • the substrate B has wiring terminals.
  • the thickness of the substrate B is preferably 0.1-5 mm, more preferably 0.2-1 mm.
  • Substrate B may be a wafer, single-sided chip, or double-sided chip.
  • at least part of the wiring terminal is electrically bonded to the convex portion of the substrate A described above.
  • 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.
  • Substrate A may have an electronic circuit area containing electronic circuits.
  • the electronic circuit may have an element such as a semiconductor.
  • the size of the substrate B (for example, wafer size)
  • the diameter can be 100 mm or more.
  • 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 manufacturing method of the joined body of the present invention includes a step of forming a filler-containing layer containing a binder and a filler on the surface of the substrate A having the protrusions (filler-containing layer forming step).
  • the filler-containing layer is preferably formed so as to be in contact with the convex portions, and more preferably formed so as to fill the concave portions between the convex portions.
  • the filler-containing layer may be formed on at least a part of the protrusions.
  • an aspect in which the layer is formed on all of the protrusions is also one of the preferred aspects of the present invention. .
  • the step of forming a filler-containing layer includes applying a resin composition containing at least one resin selected from the group consisting of a binder and a binder precursor and a filler onto the surface of the substrate A having the protrusions.
  • the step comprises applying.
  • the binder contained in the filler-containing layer is preferably an insulating binder.
  • the insulating binder has a volume resistivity of 1 ⁇ 10 15 ⁇ cm or more, preferably 1 ⁇ 10 16 ⁇ cm or more.
  • the upper limit is not particularly limited, for example, 1 ⁇ 10 18 ⁇ cm or less is preferable.
  • the dielectric breakdown voltage of the binder is preferably 1 kV/mm or more, more preferably 10 kV/mm or more.
  • the upper limit is not particularly limited, it is preferably 1000 kV/mm or less, for example.
  • volume resistivity and dielectric breakdown voltage can be measured according to JIS (Japanese Industrial Standards) C2151:2006 and JISC2318:2007.
  • the binder is not particularly limited, but polyimide, polybenzoxazole, polyamideimide, phenol resin, polyamide, epoxy resin, polysiloxane, resin containing siloxane structure, (meth)acrylic resin, (meth)acrylamide resin, urethane resin, butyral resins, styryl resins, polyether resins, polyester resins, and the like. These may be used individually by 1 type, and may use 2 or more types together.
  • the filler-containing layer preferably contains polyimide, polybenzoxazole, or polyamideimide, and more preferably contains polyimide. Details of these resins will be described as components contained in the resin composition described later.
  • the binder contained in the filler-containing layer preferably contains a polymerizable group, more preferably contains a radically polymerizable group, further preferably contains a group having an ethylenically unsaturated bond, a vinyl group, an acrylic It is particularly preferred to contain at least one group selected from the group consisting of groups and methacrylic groups. By having such a group in the binder, the adhesiveness between the substrate A and the substrate B can be further improved.
  • the content of the binder with respect to the total mass of the filler-containing layer is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more.
  • the upper limit of the content is not particularly limited, it can be, for example, 50% by mass or less.
  • the filler-containing layer contains two or more binders, the total amount thereof is preferably within the above range.
  • a filler content layer contains a filler.
  • the filler is preferably thermally conductive.
  • the filler may be electrically insulating, semiconducting, or electrically conductive.
  • the degree of electrical insulation and conductivity is appropriately selected according to the design and purpose.
  • the lower limit of the volume resistivity of the filler is preferably 1.0 ⁇ 10 11 ⁇ cm or more, more preferably 3.0 ⁇ 10 11 ⁇ cm or more. is more preferable, and 1.0 ⁇ 10 12 ⁇ cm or more is particularly preferable.
  • the upper limit of the volume resistivity is not particularly limited, it is preferably 1.0 ⁇ 10 18 or less ⁇ cm, for example.
  • the lower limit of the volume resistivity of the filler is not particularly limited, but practically it is 1.0 ⁇ 10 ⁇ 7 ⁇ cm or more.
  • the upper limit of the volume resistivity is preferably less than 1.0 ⁇ 10 11 ⁇ cm.
  • the thermal diffusivity of the filler is, for example, preferably 5.0 ⁇ 10 ⁇ 7 m 2 s ⁇ 1 or more, more preferably 1.0 ⁇ 10 ⁇ 6 m 2 s ⁇ 1 or more, and more preferably 2.0. It is more preferably 3.0 ⁇ 10 ⁇ 6 m 2 s ⁇ 1 or more, particularly preferably 3.0 ⁇ 10 ⁇ 6 m 2 s ⁇ 1 or more.
  • the upper limit of the thermal diffusivity of the filler is not particularly limited, it is preferably 1.0 ⁇ 10 ⁇ 4 m 2 s ⁇ 1 or less, for example.
  • the density of the filler is, for example, preferably 4.0 g/cm 3 or less, more preferably 3.0 g/cm 3 or less.
  • the lower limit of the density of the filler is not particularly limited, it is preferably 1.0 g/cm 3 or more, for example.
  • the density of the filler in this specification means the density of the solid content among the components constituting the filler. do.
  • the filler contains an electrically insulating material.
  • the electrically insulating filler material is, for example, an electrically insulating ceramic made of a nitrogen compound, an oxygen compound, a silicon compound, a boron compound, a carbon compound, or a composite compound thereof.
  • Nitrogen compounds include, for example, boron nitride, aluminum nitride, and silicon nitride.
  • oxygen compounds include metal oxides such as aluminum oxide (alumina), magnesium oxide (magnesia), zinc oxide, silicon oxide (silica), beryllium oxide, titanium oxide (titania), copper oxide and cuprous oxide.
  • Silicon compounds and carbon compounds include silicon carbide.
  • Boron compounds include, for example, metal borides such as titanium boride.
  • carbon compounds are, for example, carbon matrix materials with predominantly ⁇ bonds, such as diamond.
  • the composite compound include mineral ceramics such as magnesite (magnesium carbonate), perovskite (calcium titanate), talc, mica, kaolin, bentonite, and pyroferrite.
  • the electrically insulating filler material may also be a metal hydroxide such as magnesium hydroxide or aluminum hydroxide.
  • the filler material preferably contains at least one of ceramics made of nitrogen compounds, ceramics made of metal oxides, and metal hydroxides.
  • the filler material preferably contains, for example, boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, zinc oxide, and at least one selected from the group consisting of beryllium oxide and aluminum hydroxide.
  • the filler material particularly preferably contains at least one selected from the group consisting of boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, zinc oxide and beryllium oxide. More preferably, it contains at least one of silicon and aluminum oxide.
  • boron nitride has c-BN (cubic crystal structure), w-BN (wurtzite structure), h-BN (hexagonal crystal structure), r-BN (rhombohedral crystal structure), t-BN (turbulent structure ) or any other structure.
  • Boron nitride may have a spherical shape, a scaly shape, a nanotube shape, or the like, and any of them can be used.
  • the IX-3 series manufactured by Nippon Shokubai Co., Ltd., etc. can be suitably used.
  • Examples of conductive filler materials include carbon substrate materials in which ⁇ bonds are dominant, such as graphite, carbon black, graphite, carbon fibers (pitch-based, PAN-based), carbon nanotubes (CNT), and carbon nanofibers (CNF). is mentioned.
  • Such filler materials may be metals such as silver, copper, iron, nickel, aluminum and titanium, and alloys such as stainless steel (SUS).
  • conductive metal oxides such as zinc oxide doped with different elements and conductive ceramics such as ferrite can also be used as such filler materials.
  • the filler may have a structure in which semiconductor or conductive thermally conductive particles are coated or surface-treated with an electrically insulating material such as silica. According to such an aspect, it becomes easy to control the thermal conductivity and the electrical insulation individually, so that the adjustment of the thermal conductivity and the electrical insulation becomes easy.
  • methods for forming a silica film on the surface include a water glass method and a sol-gel method.
  • fillers can be used singly or in combination of two or more.
  • the shape of the filler is not particularly limited, and various shapes can be used.
  • the filler may be subjected to surface treatment such as silane coupling treatment, titanate coupling treatment, epoxy treatment, urethane treatment, and oxidation treatment.
  • Surface treatment agents used for surface treatment include, for example, polyol, aluminum oxide, aluminum hydroxide, silica (silicon oxide), hydrated silica, alkanolamine, stearic acid, organosiloxane, zirconium oxide, hydrogen dimethicone, silane coupling agent, Titanate coupling agents and the like. Among them, silane coupling agents are preferred.
  • the average particle size of the filler is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, and even more preferably 10 ⁇ m or less.
  • the average particle size of the filler is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, still more preferably 0.1 ⁇ m or more, and particularly preferably 0.3 ⁇ m or more. preferable.
  • the "average particle size" of the filler can be obtained by observing the filler in the filler-containing layer with a scanning electron microscope (SEM) and observing the portion (primary particles) where the particles of the filler are not aggregated.
  • the average particle size can be calculated as the average diameter of the smallest enclosing circle for the apparent outline of each particle observed by SEM. Specifically, it can be described by the method described in the examples described later.
  • the filler may contain a particulate mixture in which at least two types of particle groups with different particle sizes are mixed.
  • the "particle diameter" of a certain particle group is also determined by the same method as the "particle diameter” of the filler. With this configuration, the smaller particles are embedded between the larger particles, reducing the spacing between the fillers and thus increasing the number of contact points compared to only single-diameter fillers, thus increasing the thermal conductivity. improve sexuality. For example, when two types of particle groups with different particle sizes are mixed, two peaks are observed in the particle size distribution of the filler containing these particle groups.
  • the filler is a mixture containing particles with a relatively small aspect ratio, such as spherical, plate-like, curved plate-like, or scale-like particles, and particles with a relatively large aspect ratio, such as fibrous, rod-like, tube-like, and needle-like particles. There may be. According to such an aspect, the thermal diffusivity can be greatly improved in some cases.
  • the peak particle size ratio (the ratio of particle sizes corresponding to peak apexes) between at least two peaks is preferably 1.5 to 50. .
  • the lower limit is preferably 2 or more, more preferably 4 or more.
  • the upper limit is preferably 40 or less, more preferably 20 or less. If the peak ratio is within the above range, it becomes easy for the small-diameter filler to occupy the space between the large-diameter fillers while preventing the large-diameter filler from becoming coarse particles.
  • the peak intensity ratio of the peak with large particle size to the peak with small particle size is preferably 0.2 to 5.0.
  • the lower limit is preferably 0.2 or more, more preferably 0.5 or more.
  • the upper limit is preferably 5.0 or less, more preferably 3.0 or less.
  • the content of the filler in the filler-containing layer is preferably 1% by volume or more, more preferably 10% by volume or more, and particularly 20% by volume or more, relative to the volume of the filler-containing layer. Preferably, it is 50% by volume or more, most preferably. Further, from the viewpoint of improving the adhesiveness between the substrate A and the substrate B, it is more preferably 85% by volume or less, more preferably 81% by volume or less, and 75% by volume relative to the volume of the filler-containing layer. % or less. Moreover, the content of the filler in the filler-containing layer is preferably 10% by mass or more, more preferably 30% by mass or more, relative to the total mass of the filler-containing layer. Although the upper limit of the content is not particularly limited, it is preferably 90% by mass or less, more preferably 75% by mass or less, from the viewpoint of processability by lithography.
  • the ratio of the particle group having a particle diameter of 0.5 to 15 ⁇ m in the total filler is preferably 50% by mass or more, more preferably 80% by mass or more.
  • the upper limit of this ratio can be 100% by mass, or can be 99% by mass or less. This ratio is preferably 99% by mass or less, more preferably 95% by mass or less.
  • the filler can be used singly or in combination of two or more.
  • the total amount thereof is preferably within the above range.
  • the filler-containing layer may contain other components.
  • Other components include components other than binders, precursors thereof, and fillers contained in the resin composition described below.
  • the step of forming a filler-containing layer includes applying a resin composition containing at least one resin selected from the group consisting of a binder and a precursor of the binder and a filler onto the surface of the substrate A having the protrusions.
  • the step comprises applying.
  • the filler-containing layer is preferably a layer obtained by curing the resin composition.
  • the binder contained in the resin composition has the same meaning as the binder contained in the filler-containing layer described above, and preferred embodiments are also the same.
  • the precursor of the binder contained in the resin composition refers to, for example, a compound that becomes the above-described binder by heating or other operations described below, and the polyimide precursor, polybenzoxazole precursor, and polyamideimide precursor described below. etc.
  • the filler contained in the resin composition includes the filler contained in the filler-containing layer described above. Other details of the resin composition will be described later.
  • -Method of applying- Means for applying the resin composition onto the substrate include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, and slit coating.
  • a coating method, an inkjet method, and the like are exemplified.
  • a step of drying the layer made of the resin composition may be included after applying the resin composition to the substrate.
  • the drying temperature of the film in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, even more preferably 90 to 110°C.
  • the drying time is exemplified from 30 seconds to 20 minutes, preferably from 1 minute to 10 minutes, more preferably from 2 minutes to 7 minutes.
  • the thickness immediately after application (the thickness after drying when a drying step is performed) is not particularly limited, and may be adjusted as appropriate so that the thickness of the resulting filler-containing layer has the thickness described later.
  • the filler-containing layer may be formed not only on the substrate A but also on the substrate B (preferably, on the surface of the substrate B having the wiring terminals).
  • the method for forming the filler-containing layer on the substrate B is not particularly limited, but for example, the same method as the method for forming the filler-containing layer on the substrate A can be used. That is, in the step of forming a filler-containing layer on the substrate B, a resin composition containing at least one resin selected from the group consisting of a binder and a precursor of the binder and a filler is applied to the wiring of the substrate B.
  • the step includes applying on a surface having terminals.
  • the filler-containing layer on the substrate A and the filler-containing layer on the substrate B are bonded. Further, in this case, it is preferable that the filler-containing layer on the substrate B is also planarized by the planarization process described later.
  • the planarization method is the same as the planarization method for the filler-containing layer on the substrate A.
  • the filler-containing layer forming step may include a step of patterning the layer 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 filler-containing layer is formed, its surface is 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 production method of the present invention may include an exposure step of exposing the layer made of the resin composition.
  • the amount of exposure is not particularly defined as long as the layer made of the resin composition can be photosensitized. is more preferable.
  • the exposure wavelength can be appropriately determined in the range of 190-1000 nm, preferably 240-550 nm.
  • the exposure wavelength is (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 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 rays; EUV (wavelength: 13.6 nm), (6) electron beams, and the like.
  • exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is particularly preferred. Thereby, particularly high exposure sensitivity can be obtained.
  • the production method of the present invention may include a development treatment step of performing development treatment on the exposed layer composed of the resin composition.
  • the development removes the unexposed portions (unexposed portions) or the exposed portions (exposed portions).
  • the developing method is not particularly limited as long as a desired pattern can be formed.
  • Development is performed using a developer.
  • the developer can be used without any particular limitation as long as the unexposed portion (non-exposed portion) or the exposed portion (exposed portion) is removed.
  • the developer preferably contains an organic solvent.
  • the development time is preferably 10 seconds to 5 minutes.
  • the temperature at the time of development is not particularly defined, but it can usually be carried out at 20 to 40°C.
  • rinsing may be performed. Rinsing is preferably done with a solvent different from the developer.
  • the solvent contained in the resin composition can be used for rinsing. Rinsing time is preferably 5 seconds to 1 minute.
  • the filler-containing layer forming step preferably includes heating the composition at a temperature of 150 to 300° C. (heating step) after the application.
  • the heating for example, the precursor of the binder is used as the binder (for example, the precursor of the cyclized resin is ring-closed to become the cyclized resin), or the polymerizable compounds themselves, or the polymerizable compound and the binder. It is possible to proceed with polymerization between them.
  • the heating in this filler-containing layer forming step is also referred to as "additional baking".
  • the heating temperature (maximum heating temperature) in the heating step is preferably 150 to 300°C, more preferably 150 to 250°C, still more preferably 160 to 250°C, and particularly preferably 160 to 230°C.
  • Heating in the heating step is preferably carried out at a temperature rising rate of 1 to 12° C./min from the temperature at the start of heating to the maximum heating temperature.
  • the rate of temperature increase is more preferably 2 to 10°C/min, still more preferably 3 to 10°C/min.
  • By setting the temperature rise rate to 1°C/min or more it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity.
  • the residual stress of the object can be relaxed.
  • the temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C.
  • the temperature at the start of heating refers to the temperature at which the process of heating up to the maximum heating temperature is started.
  • the temperature of the film (layer) after drying is, for example, the boiling point of the solvent contained in the resin composition of the present invention.
  • the heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, even more preferably 15 to 240 minutes.
  • Heating may be done in stages. As an example, the temperature is raised from 25° C. to 120° C. at 3° C./min, held at 120° C. for 60 minutes, heated from 120° C. to 180° C. at 2° C./min, and held at 180° C. for 120 minutes. , may be performed. It is also preferable to carry out the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such a pretreatment process can improve the properties of the film.
  • the pretreatment step is preferably performed for a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
  • the pretreatment may be performed in two or more steps.
  • the first pretreatment step may be performed in the range of 100 to 150°C, and then the second pretreatment step may be performed in the range of 150 to 200°C. good. Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5°C/min.
  • the heating step is preferably carried out in an atmosphere of low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon, or under reduced pressure, in order to prevent decomposition of the resin.
  • the oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.
  • the heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, an infrared oven and the like.
  • the thickness of the filler-containing layer is not particularly limited, it is preferably 100 nm or more, and preferably 300 nm or more, in the state immediately before the flattening step to be described later, from the viewpoint of exhibiting the effect of its physical properties. is more preferably 500 nm or more, more preferably 1 ⁇ m or more, and even more preferably 2 ⁇ m or more. Although there is no particular upper limit, it is preferably 1 mm or less, more preferably 500 ⁇ m or less, and even more preferably 200 ⁇ m or less. The thickness of the film can be measured using a known film thickness measuring device.
  • the thermal diffusivity of the filler-containing layer in the joined body described later is preferably 2.0 ⁇ 10 ⁇ 7 m 2 s ⁇ 1 or more, and more preferably 3.0 ⁇ 10 ⁇ 7 m 2 s ⁇ 1 or more. More preferably, it is 5.0 ⁇ 10 ⁇ 7 m 2 s ⁇ 1 or more.
  • the thermal diffusivity of the filler-containing layer is, for example, the material type of the filler, the particle size of the filler (a combination of the particle sizes when two or more types of fillers are included), the thermal diffusivity of the filler, the content of the filler, and the binder. It can be adjusted by designing the material type, the thermal diffusivity of the binder, the content of the binder, and the like.
  • the filler-containing layer is preferably an insulating layer.
  • the insulating properties (electrical resistance) of the filler-containing layer are 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, measurement of volumetric efficiency and dielectric breakdown voltage shall comply with JIS C2151:2006 and JIS C2318:2007.
  • the method for producing a joined body of the present invention includes a step of flattening the filler-containing layer together with the protrusions to expose at least a part of the protrusions from the filler-containing layer to obtain a laminate (laminate manufacturing step). including.
  • the laminate has a configuration in which the filler-containing layer is laminated on the substrate A having the protrusions, and the protrusions are exposed on a part of the exposed surface of the filler-containing layer.
  • the planarization is preferably performed by a process including any one of cutting, mechanical polishing, chemical polishing, grinding, plasma treatment, and laser ablation, and more preferably by cutting.
  • these methods may be combined, such as performing chemical polishing after cutting.
  • the surface of the filler-containing layer is cut with a diamond cutting tool to expose a new surface of the filler-containing layer and the projections.
  • the protrusions and the filler-containing layer can be flattened at once to expose the protrusions. Flattening can be done, for example, with a surface planer.
  • a spindle with a diamond cutting tool is exemplified, and DFS8910, DFS8960, DAS8920 and DAS8930 (all trade names) manufactured by Disco Co., Ltd. are exemplified.
  • Other planarization techniques include chemical mechanical polishing (CMP).
  • the filler-containing layer is flattened together with the projections.
  • the TTV (Total Thickness Variation) of the filler-containing layer and the convex portion in the laminate 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 of the filler-containing layer is divided into 2 mm square sections (if the area of the filler containing layer is small, etc., it cannot be divided into 2 mm square sections, the filler containing The entire area inside 1 mm or more from the edge of the layer is defined as one section), and for each section, the maximum thickness between one surface and the other surface (T1) and the one surface and the other surface
  • T2 The minimum thickness (T2) between the Groups of partitions corresponding to 10% of the total number of partitions (rounded down if there is a decimal point) and lowest partitions (smallest thickness difference) in descending order of thickness difference from (largest film thickness difference) 10% of the total number of compartments (rounded down if there is a decimal point) in descending order of film thickness difference from the remaining compartment groups, and the arithmetic of each film thickness difference (T1-T2) mean value.
  • TTV of the filler-containing layer in the laminate when specifically referring to the TTV of the filler-containing layer in the laminate defined herein, it may be referred to as a "compartment evaluation TTV.” Other details of the measuring method are based on the measuring method shown in Examples below.
  • the filler-containing layer 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 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 roughness (Ra) of the filler-containing layer of the present invention is determined by the measuring method shown in Examples below. By setting the surface roughness of the filler-containing layer to the above lower limit or more, the anchor effect works and the adhesiveness to the substrate can be improved. Further, by setting the surface roughness to the above upper limit or less, it is possible to effectively suppress the occurrence of defects such as voids due to bubbles and the like being included in the bonding with the substrate B.
  • the manufacturing method of the bonded body of the present invention includes the step of bonding the surface of the laminate having the filler-containing layer and the substrate B. By bonding, the protrusions on the substrate A and the wiring terminals on the substrate B are electrically bonded. Bonding is preferably performed by means including at least one of heating and pressing, and more preferably performed by means including heating and pressing.
  • the temperature during bonding 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 350° C. or lower, even more preferably 300° C. or lower, and 280° 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. According to the manufacturing method of the bonded body of the present invention, since the bonding temperature can be lowered, the manufacturing cost can be reduced, and each member of the device can be prevented from being damaged.
  • the heating time in the bonding step is not particularly limited, but is preferably 30 seconds or longer, more preferably 1 minute or longer, and even more preferably 2 minutes or longer. A practical upper limit is 30 minutes or less.
  • the heating environment is not particularly limited, but it is preferable to perform the heating under a reduced pressure atmosphere while mechanically pressurizing the filler-containing layer.
  • 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 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 a form in which a plurality of substrates B are arranged in parallel with respect to the substrate A and bonded is described. 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 diagram schematically showing (a part of) a process of bonding substrates in a method for manufacturing a joined body according to an embodiment of the present invention, using cross-sectional views.
  • a substrate A (underlying substrate) 1 having an electronic circuit region 8 disposed on a silicon wafer 1x and having electrodes 3 and conduction paths 31 (projections 30) thereon is prepared (FIG. 2(a)).
  • An electronic circuit 81 made of a conductor or a semiconductor is already formed inside the electronic circuit area 8 of the substrate A1.
  • the method of forming the 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 layer (resin composition layer) 4 made of a 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)).
  • This embodiment shows an example in which a polyimide precursor is used for the resin composition layer.
  • the resin composition layer may be heated and dried (drying step). After pre-baking, the resin composition layer 4 may be patterned by photolithography, ion sputtering, or the like.
  • the polymer precursor is crosslinked by irradiation with ultraviolet rays and heated (heating step 2) to promote cyclization and to form a cured filler-containing layer 41 (FIG. 2(c)).
  • a filler-containing layer-provided substrate 1y in which the filler-containing layer 41 is provided on the substrate A1 is formed.
  • the filler-containing layer 41 may shrink compared to the resin composition layer 4 due to curing.
  • the shrinkage rate is not particularly limited, and a smaller shrinkage rate may be used, or no shrinkage may occur upon curing.
  • patterning may be performed before curing, and a conductive path may be formed in the patterned portion by plating or the like.
  • the heights h1 and h2 of the conduction paths 31 are varied.
  • the surface 4a of the filler-containing layer is also wavy and not flat.
  • planarization is performed to eliminate such variations in the height of the conductive path 31, expose the tip surface thereof, and planarize the surface of the filler-containing layer.
  • FIG. 3 shows the filler-containing layer-provided substrate (laminate) 1z after flattening.
  • the tip 31a of the conducting path 31 is exposed on the surface 4b of the filler-containing layer, and the entire surface 4b of the filler-containing layer is flattened.
  • a substrate B is separately prepared for the laminate (flattened filler-containing layer-provided 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 formed in the circuit wiring region 8.
  • alignment is performed so that the conductive paths 31 of the laminate and the electrodes 32 provided on the substrate B2 are aligned.
  • the aligned substrate B2 and the laminated body 1z are brought into contact with each other at the bonding surface P1 via the filler-containing layer 41 and bonded together (FIG. 4(b)).
  • a bonded body 100 in which two substrates are bonded is formed.
  • heat treatment reflow
  • the electrode 3 on the substrate A side and the electrode 32 on the substrate B side can be electrically connected through the conduction path 31 ( bonding process).
  • the filler-containing layer 41 is softened by the above heating, and the filler-containing layer surface 4b of the laminate 1z and the surface 2a of the substrate B (the surface having the electronic circuit region) are bonded to each other to form the joined body 100. do.
  • the substrate A and the substrate B can be electrically connected to each other, and both can be firmly fixed.
  • the electrode 3 and the conducting path 31 may be collectively referred to as a convex portion 30 .
  • the electrodes 32 on the substrate B are sometimes called pads.
  • the filler-containing layer 41 contains fillers and thus has excellent thermal conductivity. Therefore, for example, heat generated from the electronic circuit region 8 can be dissipated through the filler-containing layer 41 . Further, in the preferred embodiment of the present invention, since the flatness of the filler-containing layer surface P1 of the laminate 1z is high, it is possible to obtain a precise and accurate contact state with the substrate B2 on the contact surface. By realizing a more precise and accurate contact state, it is possible to effectively suppress voids that tend to occur on the contact surface.
  • a semiconductor device of the present invention includes a joined body obtained by the method of manufacturing a joined body of the present invention.
  • semiconductor devices for example, "Illustrated All of Cutting-edge 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.
  • 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. As shown in FIG.
  • Each of the plurality of semiconductor elements 101a-101d is made of a semiconductor wafer such as a silicon substrate.
  • a laminated body 101 has a structure in which a semiconductor element 101a having no through electrodes and semiconductor elements 101b to 101d having through electrodes 102b to 102d are flip-chip connected. Connection pads on the semiconductor element side having through electrodes are connected by metal bumps 103a, 103b, 103c such as solder bumps.
  • a resin layer 110 is formed between the semiconductor elements 101a to 101d.
  • 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 filler-containing layer described above.
  • a surface electrode 120 a is provided on one surface of the wiring board 120 .
  • An insulating layer 115 having a rewiring layer 105 formed thereon is arranged between the wiring substrate 120 and the laminate (substrate/substrate laminate) 101 .
  • One end of the rewiring layer 105 is connected to an electrode pad formed on the surface of the semiconductor element 101d facing the rewiring layer 105 via a metal bump 103d such as a solder bump.
  • the other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump.
  • a resin layer 110 a is formed between the insulating layer 115 and the laminate 101 .
  • the method for manufacturing a bonded body of the present invention can also be used for bonding the insulating layer 115 and the laminate 101 together. That is, for example, the resin layer 110a can be the filler-containing layer described above. A resin layer 110 b is formed between the insulating layer 115 and the wiring board 120 .
  • the method for manufacturing a bonded body according to the present invention can also be used for bonding the insulating layer 115 and the wiring substrate 120 together. That is, for example, the resin layer 110b can be the filler-containing layer described above.
  • the resin composition of the present invention is a resin composition used for forming the filler-containing layer in the method for producing a joined body of the present invention. Details of the resin composition (that is, the resin composition of the present invention) used for forming the filler-containing layer in the method for producing a joined body of the present invention are described below.
  • the resin composition of the present invention contains at least one resin selected from the group consisting of a binder and a binder precursor, and a filler.
  • the filler is the same as the resin composition of the present invention described above. However, the description "with respect to the total mass of the layer containing the filler" shall be read as "with respect to the total solid content of the resin composition.”
  • binders include the following cyclized resins, precursors thereof, and other resins. At least one resin selected from the group consisting of cyclized resins and precursors thereof (hereinafter also referred to as "specific resin" It preferably contains a precursor of the cyclized resin, more preferably a precursor of the cyclized resin.
  • the resin composition of the present invention preferably contains at least one resin (specific resin) selected from the group consisting of cyclized resins and precursors thereof.
  • the cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in its main chain structure.
  • the main chain represents the relatively longest connecting chain in the resin molecule.
  • cyclized resins include polyimide, polybenzoxazole, and polyamideimide.
  • the precursor of the cyclized resin refers to a resin that undergoes a change in chemical structure by an external stimulus to become a cyclized resin, preferably a resin that undergoes a change in chemical structure by heat to become a cyclized resin.
  • a resin that becomes a cyclized resin by forming a ring structure is more preferable.
  • Precursors of the cyclized resin include polyimide precursors, polybenzoxazole precursors, polyamideimide precursors, and the like. That is, the resin composition of the present invention contains, as a specific resin, at least one selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, polyamideimides, and polyamideimide precursors. It preferably contains a resin (specific resin).
  • the resin composition of the present invention preferably contains polyimide or a polyimide precursor as the specific resin.
  • the specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group.
  • the resin composition of the present invention preferably contains a radical polymerization initiator described later, and contains a radical polymerization initiator described later and a radical cross-linking agent described later. is more preferred.
  • a sensitizer described later can be included.
  • a negative photosensitive film is formed from the resin composition of the present invention.
  • the specific resin may have a polarity conversion group such as an acid-decomposable group.
  • the resin composition of the present invention preferably contains a photoacid generator, which will be described later. From such a resin composition of the present invention, for example, a chemically amplified positive photosensitive film or negative photosensitive film is formed.
  • polyimide precursor Although the type of the polyimide precursor used in the present invention is not particularly limited, it preferably contains a repeating unit represented by the following formula (2).
  • a 1 and A 2 each independently represent an oxygen atom or -NH-
  • R 111 represents a divalent organic group
  • R 115 represents a tetravalent organic group
  • R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group.
  • a 1 and A 2 in formula (2) each independently represent an oxygen atom or —NH—, preferably an oxygen atom.
  • R 111 in formula (2) represents a divalent organic group.
  • divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, linear or branched aliphatic groups having 2 to 20 carbon atoms, A cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable.
  • the hydrocarbon group in the chain may be substituted with a group containing a hetero atom, and in the cyclic aliphatic group and the aromatic group, the ring member hydrocarbon group is a hetero atom.
  • may be substituted with a group containing Groups represented by -Ar- and -Ar-L-Ar- are exemplified as preferred embodiments of the present invention, and groups represented by -Ar-L-Ar- are particularly preferred.
  • Ar is each independently an aromatic group
  • L is a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO -, -S-, -SO 2 - or -NHCO-, or a group consisting of a combination of two or more of the above. Preferred ranges for these are as described above.
  • R 111 is preferably derived from a diamine.
  • Diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferably a diamine containing, more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. In the straight-chain or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a heteroatom. may be substituted with a group containing Examples of groups containing aromatic groups include:
  • * represents a binding site with other structures.
  • diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 1,6-diaminohexane; ,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4- aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4′-diamino-3,3′-dimethylcyclohexylmethane or isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4′- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3, 3,3
  • diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598.
  • diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 are preferably used.
  • R 111 is preferably represented by -Ar-L-Ar- from the viewpoint of the flexibility of the resulting organic film.
  • Ar is each independently an aromatic group
  • L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- , —SO 2 — or —NHCO—, or a group consisting of a combination of two or more of the above.
  • Ar is preferably a phenylene group
  • L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- or -SO 2 - .
  • the aliphatic hydrocarbon group here is preferably an alkylene group.
  • R 111 is preferably a divalent organic group represented by the following formula (51) or (61).
  • a divalent organic group represented by Formula (61) is more preferable.
  • Equation (51) In formula (51), R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group or a trifluoro It is a methyl group, and each * independently represents a binding site to the nitrogen atom in formula (2).
  • the monovalent organic groups represented by R 50 to R 57 include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), A fluorinated alkyl group and the like can be mentioned.
  • R 58 and R 59 are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * is each independently a bonding site to the nitrogen atom in formula (2) show.
  • Diamines that give the structure of formula (51) or (61) include 2,2′-dimethylbenzidine, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 2,2′-bis (Fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like. These may be used alone or in combination of two or more.
  • R 115 in formula (2) represents a tetravalent organic group.
  • a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or (6) is more preferable.
  • each * independently represents a binding site to another structure.
  • R 112 is a single bond or a divalent linking group, a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, -CO-, -S-, -SO 2 -, and -NHCO-, and preferably a group selected from a combination thereof, having 1 to 1 carbon atoms optionally substituted by a single bond or a fluorine atom 3 alkylene group, -O-, -CO-, -S- and -SO 2 -, and -CH 2 -, -C(CF 3 ) 2 -, -C( It is more preferably a divalent group selected from the group consisting of CH 3 ) 2 -, -O-, -CO-, -S- and -SO 2 -.
  • R 115 specifically 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, or may contain two or more types thereof, as the structure corresponding to R115 .
  • the tetracarboxylic dianhydride is preferably represented by the following formula (O).
  • R 115 represents a tetravalent organic group.
  • the preferred range of R 115 is synonymous with R 115 in formula (2), and the preferred range is also the same.
  • tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′- Diphenyl sulfide tetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′ ,4,4′-diphenylmethanetetracarboxylic dianhydride, 2,2′,3,3′-diphenylmethanetetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride,
  • tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017/038598 are also preferred examples.
  • R 111 and R 115 has an OH group. More specifically, R 111 includes residues of bisaminophenol derivatives.
  • R 113 and R 114 in formula (2) each independently represent a hydrogen atom or a monovalent organic group.
  • the monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group.
  • At least one of R 113 and R 114 preferably contains a polymerizable group, more preferably both contain a polymerizable group. It is also preferred that at least one of R 113 and R 114 contains two or more polymerizable groups.
  • the polymerizable group is a group capable of undergoing a cross-linking reaction by the action of heat, radicals, or the like, and is preferably a radically polymerizable group.
  • the polymerizable group examples include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. be done.
  • a group having an ethylenically unsaturated bond is preferred.
  • Groups having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), and a (meth)acrylamide group.
  • a (meth)acryloyloxy group a group represented by the following formula (III), and the like, and a group represented by the following formula (III) is preferable.
  • R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, preferably a hydrogen atom or a methyl group.
  • * represents a binding site with another structure.
  • R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH(OH)CH 2 —, a cycloalkylene group or a polyalkyleneoxy group.
  • R 201 examples include ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, alkylene groups such as dodecamethylene, 1,2-butanediyl, 1, 3-butanediyl group, —CH 2 CH(OH)CH 2 —, polyalkyleneoxy group, ethylene group, alkylene group such as propylene group, —CH 2 CH(OH)CH 2 —, cyclohexyl group, polyalkylene An oxy group is more preferred, and an alkylene group such as an ethylene group, a propylene group, or a polyalkyleneoxy group is even more preferred.
  • alkylene groups such as dodecamethylene, 1,2-butanediyl, 1, 3-butanediyl group, —CH 2 CH(OH)CH 2 —, polyalkyleneoxy group, ethylene group, alkylene group such as propylene group, —CH 2 CH(OH)CH 2
  • a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded.
  • the alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
  • the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement or a block arrangement. Alternatively, it may be arranged in a pattern such as an alternating pattern.
  • the number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6.
  • the said alkylene group may have a substituent.
  • Preferred substituents include alkyl groups, aryl groups, and halogen atoms.
  • the number of alkyleneoxy groups contained in the polyalkyleneoxy group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
  • a group to which an oxy group is bonded is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is still more preferable.
  • the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, or may be arranged to form blocks. , may be arranged in a pattern such as alternately. Preferred embodiments of the number of repetitions of ethyleneoxy groups and the like in these groups are as described above.
  • the polyimide precursor when R 113 is a hydrogen atom, or when R 114 is a hydrogen atom, the polyimide precursor may form a tertiary amine compound having an ethylenically unsaturated bond and a counter salt. good.
  • tertiary amine compounds having ethylenically unsaturated bonds include N,N-dimethylaminopropyl methacrylate.
  • R 113 and R 114 may be a polarity conversion group such as an acid-decomposable group.
  • the acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxyl group. , a tertiary alkyl ester group and the like are preferable, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferable.
  • acid-decomposable groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, and tert-butoxycarbonylmethyl. groups, trimethylsilyl ether groups, and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.
  • the polyimide precursor preferably has a fluorine atom in its structure.
  • the content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
  • the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
  • an aliphatic group having a siloxane structure there is an embodiment using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like as the diamine.
  • the repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one polyimide precursor used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by the formula (2-A) in the polyimide precursor, it becomes possible to further widen the width of the exposure latitude.
  • a 1 and A 2 represent an oxygen atom
  • R 111 and R 112 each independently represent a divalent organic group
  • R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group
  • at least one of R 113 and R 114 is a group containing a polymerizable group, and both are preferably groups containing a polymerizable group.
  • a 1 , A 2 , R 111 , R 113 and R 114 are each independently synonymous with A 1 , A 2 , R 111 , R 113 and R 114 in formula (2), and preferred ranges are also the same.
  • R 112 has the same definition as R 112 in formula (5), and the preferred range is also the same.
  • the polyimide precursor may contain one type of repeating unit represented by formula (2), but may contain two or more types. It may also contain structural isomers of the repeating unit represented by formula (2). It goes without saying that the polyimide precursor may also contain other types of repeating units in addition to the repeating units of formula (2) above.
  • the content of the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units.
  • the total content is more preferably 70 mol % or more, still more preferably 90 mol % or more, and particularly preferably more than 90 mol %.
  • the upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor excluding terminals may be repeating units represented by formula (2).
  • the weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, still more preferably 15,000 to 40,000. Also, the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, still more preferably 4,000 to 20,000.
  • the polyimide precursor preferably has a molecular weight distribution of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. Although the upper limit of the polyimide precursor's molecular weight dispersity is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
  • the molecular weight dispersity is a value calculated by weight average molecular weight/number average molecular weight.
  • the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one polyimide precursor are preferably within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated from the plurality of types of polyimide precursors as one resin are within the ranges described above.
  • the polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer containing an organic solvent as a main component.
  • the alkali-soluble polyimide refers to a polyimide that dissolves in 100 g of a 2.38% by mass tetramethylammonium aqueous solution at 23° C. by 0.1 g or more, and from the viewpoint of pattern formation, 0.5 g or more. It is preferably a polyimide that dissolves, and more preferably a polyimide that dissolves 1.0 g or more. Although the upper limit of the dissolved amount is not particularly limited, it is preferably 100 g or less.
  • the polyimide is preferably a polyimide having a plurality of imide structures in its main chain from the viewpoint of the film strength and insulating properties of the resulting organic film.
  • the term "main chain” refers to the relatively longest linking chain in the molecule of the polymer compound that constitutes the resin, and the term “side chain” refers to the other linking chain.
  • the polyimide preferably has a fluorine atom.
  • a fluorine atom is preferably included in, for example, R 132 in a repeating unit represented by formula (4) described later or R 131 in a repeating unit represented by formula (4) described later, and the formula ( It is more preferably contained as a fluorinated alkyl group in R 132 in the repeating unit represented by 4) or R 131 in the repeating unit represented by formula (4) described later.
  • the amount of fluorine atoms relative to the total mass of polyimide is preferably 5% by mass or more and preferably 20% by mass or less.
  • the polyimide preferably has a silicon atom.
  • a silicon atom for example, is preferably contained in R 131 in a repeating unit represented by formula (4) described later, and R 131 in a repeating unit represented by formula (4) described later is an organic 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 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
  • the group having an ethylenically unsaturated bond includes a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acrylamide group, a (meth) Examples include an acryloyloxy group and a group represented by the following formula (IV).
  • R 20 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, preferably a hydrogen atom or a methyl group.
  • R 21 is an alkylene group having 2 to 12 carbon atoms, —O—CH 2 CH(OH)CH 2 —, —C( ⁇ O)O—, —O(C ⁇ O)NH— , a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, 1 to 6 are more preferable, and 1 to 3 are particularly preferable), or a group in which two or more of these are combined.
  • the alkylene group having 2 to 12 carbon atoms may be a linear, branched, cyclic, or a combination of these alkylene groups.
  • an alkylene group having 2 to 8 carbon atoms is preferable, and an alkylene group having 2 to 4 carbon atoms is more preferable.
  • R 21 is preferably a group represented by any one of the following formulas (R1) to (R3), more preferably a group represented by formula (R1).
  • L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are combined
  • X represents an oxygen atom or a sulfur atom
  • * represents a bonding site with another structure
  • ⁇ represents a bonding site with the oxygen atom to which R 21 in formula (IV) bonds.
  • a preferred embodiment of an alkylene group having 2 to 12 carbon atoms or a (poly)alkyleneoxy group having 2 to 30 carbon atoms in L is the above-mentioned R 21 having 2 to 12 carbon atoms. It is the same as the preferred embodiment of the 12 alkylene group or the (poly)alkyleneoxy group having 2 to 30 carbon atoms.
  • X is preferably an oxygen atom.
  • * has the same meaning as * in formula (IV), and preferred embodiments are also the same.
  • the structure represented by formula (R1) is, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group, and a compound having an isocyanato group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate, etc.). Obtained by reaction.
  • the structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (eg, 2-hydroxyethyl methacrylate, etc.).
  • the structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate, etc.) can get.
  • a polyimide having a hydroxy group such as a phenolic hydroxy group
  • a compound having a glycidyl group and an ethylenically unsaturated bond e.g., glycidyl methacrylate, etc.
  • * represents a binding site with another structure, preferably a binding site with the main chain of polyimide.
  • the amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001-0.1 mol/g, more preferably 0.0005-0.05 mol/g.
  • Polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond.
  • Polymerizable groups other than groups having an ethylenically unsaturated bond include cyclic ether groups such as an epoxy group and an oxetanyl group, alkoxymethyl groups such as a methoxymethyl group, and methylol groups.
  • a polymerizable group other than a group having an ethylenically unsaturated bond is preferably included, for example, in R 131 in a repeating unit represented by formula (4) described below.
  • the amount of the polymerizable group other than the group having an ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, preferably 0.001 to 0.05 mol / g. more preferred.
  • the polyimide may have a polarity conversion group such as an acid-decomposable group.
  • the acid-decomposable group in the polyimide is the same as the acid-decomposable group described for R 113 and R 114 in formula (2) above, and preferred embodiments are also the same.
  • Polar conversion groups are included, for example, at R 131 and R 132 in the repeating unit represented by formula (4) described later, the terminal of polyimide, and the like.
  • the acid value of polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more, from the viewpoint of improving developability. is more preferable. Also, 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.
  • the acid group contained in the polyimide preferably has a pKa of 0 to 10, more preferably 3 to 8, from the viewpoint of both storage stability and developability.
  • the pKa is expressed by the negative common logarithm pKa of the equilibrium constant Ka.
  • pKa is a value calculated by ACD/ChemSketch (registered trademark).
  • the values listed in the Chemical Society of Japan, Revised 5th Edition, Basics of Chemistry may be referred to.
  • the acid group is a polyvalent acid such as phosphoric acid
  • the pKa is the first dissociation constant.
  • the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, more preferably a phenolic hydroxy group.
  • the polyimide preferably has a phenolic hydroxy group from the viewpoint of making the development speed with an alkaline developer appropriate.
  • the polyimide may have a phenolic hydroxy group at the end of the main chain or in the side chain.
  • a phenolic hydroxy group is preferably contained in, for example, R 132 in a repeating unit represented by formula (4) described later or R 131 in a repeating unit represented by formula (4) described later.
  • the amount of phenolic hydroxy groups relative to the total weight of the polyimide is preferably 0.1-30 mol/g, more preferably 1-20 mol/g.
  • the polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it preferably contains a repeating unit represented by the following formula (4).
  • R 131 represents a divalent organic group and R 132 represents a tetravalent organic group.
  • the polymerizable group may be located on at least one of R 131 and R 132 , and the terminal of the polyimide as shown in the following formula (4-1) or (4-2) may be located in Formula (4-1)
  • R 133 is a polymerizable group, and other groups are the same as in formula (4).
  • Formula (4-2) At least one of R 134 and R 135 is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups are as defined in formula (4).
  • R 131 represents a divalent organic group.
  • Examples of the divalent organic group are the same as those for R 111 in formula (2), and the preferred range is also the same.
  • R 131 also includes a diamine residue remaining after removal of the amino group of the diamine.
  • Diamines include aliphatic, cycloaliphatic or aromatic diamines.
  • a specific example is the example of R 111 in formula (2) of the polyimide precursor.
  • R 131 is preferably a diamine residue having at least two alkylene glycol units in its main chain, from the viewpoint of more effectively suppressing 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, for example, a tetracarboxylic acid residue remaining after removal of an anhydride group from a tetracarboxylic dianhydride.
  • a specific example is the example of R 115 in formula (2) of the polyimide precursor.
  • 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 preferably 20% by mass or less.
  • the polyimide may be copolymerized with an aliphatic group having a siloxane structure.
  • the diamine component include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.
  • the main chain end of the polyimide is blocked with a terminal blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound. preferably.
  • monoamines examples include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7 -aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2 -hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6- Aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzoic acid
  • the imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, insulating properties, etc. of the resulting organic film. More preferably, it is 90% or more.
  • the upper limit of the imidization rate is not particularly limited, and may be 100% or less.
  • the imidization rate is measured, for example, by the method described below. The infrared absorption spectrum of the polyimide is measured, and the peak intensity P1 near 1377 cm ⁇ 1 , which is the absorption peak derived from the imide structure, is obtained. Next, after heat-treating the polyimide at 350° C.
  • the polyimide may contain repeating units represented by the above formula (4) that all contain one type of R 131 or R 132 , and the above formula ( 4) may contain a repeating unit. Moreover, the polyimide may contain other types of repeating units in addition to the repeating units represented by the above formula (4). Other types of repeating units include, for example, repeating units represented by formula (2) above.
  • polyimide for example, a method of reacting a tetracarboxylic dianhydride and a diamine (partially replaced with a monoamine terminal blocker) at a low temperature, a method of reacting a tetracarboxylic dianhydride (partially with an acid anhydride) at a low temperature a monoacid chloride compound or a monoactive ester compound) and a diamine, a diester is obtained by a tetracarboxylic dianhydride and an alcohol, and then a diamine (a part of which is a monoamine A method of reacting in the presence of a condensing agent) with a condensing agent, a diester is obtained by tetracarboxylic acid dianhydride and alcohol, then the remaining dicarboxylic acid is acid chloride, diamine (part of which is a monoamine Using a method such as a method of reacting with a terminal blocking agent) to obtain a polyimide precursor
  • the weight average molecular weight (Mw) of 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 kinds of polyimides as one resin are within the above ranges.
  • polybenzoxazole precursor Although the structure of the polybenzoxazole precursor used in the present invention is not particularly defined, it preferably contains a repeating unit represented by the following formula (3).
  • R 121 represents a divalent organic group
  • R 122 represents a tetravalent organic group
  • R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group. show.
  • R 123 and R 124 each have the same meaning as R 113 in formula (2), and the preferred ranges are also the same. That is, at least one is preferably a polymerizable group.
  • R 121 represents a divalent organic group.
  • the divalent organic group a group containing at least one of an aliphatic group and an aromatic group is preferred.
  • the aliphatic group a linear aliphatic group is preferred.
  • R 121 is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.
  • a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable.
  • the dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, a linear or branched (preferably linear) aliphatic group and two -COOH A dicarboxylic acid consisting of is more preferred.
  • the number of carbon atoms in the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, even more preferably 3 to 20, and 4 to 15 is more preferred, and 5-10 is particularly preferred.
  • the linear aliphatic group is preferably an alkylene group.
  • Dicarboxylic acids containing linear aliphatic groups include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberin acid, dodecanedioic acid, azelaic acid, sebacic acid, hexadecanedi
  • Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.
  • the dicarboxylic acid containing an aromatic group the following dicarboxylic acid having an aromatic group is preferable, and the following dicarboxylic acid consisting of only a group having an aromatic group and two -COOH is more preferable.
  • A is -CH 2 -, -O-, -S-, -SO 2 -, -CO-, -NHCO-, -C(CF 3 ) 2 -, and -C(CH 3 ) 2 - represents a divalent group selected from the group consisting of * independently represents a binding site to another structure.
  • dicarboxylic acids containing aromatic groups include 4,4'-carbonyl dibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.
  • R 122 represents a tetravalent organic group.
  • the tetravalent organic group has the same meaning as R 115 in the above formula (2), and the preferred range is also the same.
  • R 122 is also preferably a group derived from a bisaminophenol derivative.
  • bisaminophenol derivatives having the following aromatic groups are preferred.
  • X 1 represents -O-, -S-, -C(CF 3 ) 2 -, -CH 2 -, -SO 2 -, -NHCO-, and * and # respectively represent other structures and represents the binding site of R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group.
  • R 122 is also preferably a structure represented by the above formula.
  • any two of the total four * and # are binding sites with the nitrogen atom to which R 122 in formula (3) binds, and Another two are preferably bonding sites with the oxygen atom to which R 122 in formula (3) is bonded, and two * are bonding sites with the oxygen atom to which R 122 in formula (3) is bonded. and two #s are binding sites to the nitrogen atom to which R 122 in formula (3) binds, or two * are binding sites to the nitrogen atom to which R 122 in formula (3) binds and two #s are more preferably a binding site to the oxygen atom to which R 122 in formula (3) binds, and two * are the oxygen to which R 122 in formula (3) binds. More preferably, it is a bonding site with an atom and two #s are bonding sites with a nitrogen atom to which R 122 in formula (3) is bonded.
  • the bisaminophenol derivative is also preferably a compound represented by Formula (As).
  • R 1 is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO 2 -, -CO-, -NHCO-, a single bond, or the following formula (A- It is an organic group selected from the group of sc).
  • R2 is a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different.
  • R3 is a hydrogen atom , a linear or branched alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different.
  • R 1 is alkylene or substituted alkylene.
  • alkylene and substituted alkylene for R 1 include linear or branched alkyl groups having 1 to 8 carbon atoms, among which —CH 2 — and —CH(CH 3 ) -, -C(CH 3 ) 2 - have sufficient solubility in solvents while maintaining the effect of high i-line transparency and high cyclization rate when cured at low temperature. It is more preferable in that a polybenzoxazole precursor having excellent properties can be obtained.
  • the polybenzoxazole precursor may also contain other types of repeating units in addition to the repeating units of formula (3) above.
  • the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit in that warping due to ring closure can be suppressed.
  • Z has an a structure and a b structure
  • R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
  • R 2s is a hydrocarbon group having 1 to 10 carbon atoms.
  • At least one of R 3s , R 4s , R 5s and R 6s is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different.
  • Polymerization of a structure and b structure may be block polymerization or random polymerization.
  • the mol % of the Z portion is 5 to 95 mol % for the a structure, 95 to 5 mol % for the b structure, and 100 mol % for a+b.
  • preferred Z include those in which R 5s and R 6s in the b structure are phenyl groups.
  • the molecular weight of the structure represented by formula (SL) is preferably 400-4,000, more preferably 500-3,000.
  • tetracarboxylic acid residues include those of R 115 in formula (2).
  • the weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, still more preferably 22,000 to 28, 000. Also, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, still more preferably 9,200 to 11,200.
  • the molecular weight dispersity of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more.
  • the upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly defined, for example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and 2.3 or less. is more preferable, and 2.2 or less is even more preferable.
  • the resin composition contains a plurality of types of polybenzoxazole precursors as specific resins
  • the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polybenzoxazole precursor are within the above ranges. preferable. 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 polybenzoxazole precursors as one resin are within the ranges described above.
  • Polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but it is preferably a compound represented by the following formula (X), and a compound represented by the following formula (X) and more preferably a compound having a polymerizable group.
  • a radically polymerizable group is preferred.
  • it may be a compound represented by the following formula (X) and having a polarity conversion group such as an acid-decomposable group.
  • R 133 represents a divalent organic group and R 134 represents a tetravalent organic group.
  • the polar conversion group such as a polymerizable group or an acid-decomposable group
  • the polar conversion group may be located on at least one of R 133 and R 134 . It may be positioned at the end of the polybenzoxazole as shown in formula (X-1) or formula (X-2).
  • R 137 is a polar conversion group such as a polymerizable group or an acid-decomposable group, the others are substituents, and the other groups are the same as in formula (X).
  • the polarity conversion group such as a polymerizable group or an acid-decomposable group is synonymous with the polymerizable group described above for the polymerizable group possessed by the polyimide precursor.
  • R 133 represents a divalent organic group.
  • Divalent organic groups include aliphatic groups and aromatic groups.
  • a specific example is the example of R 121 in formula (3) of the polybenzoxazole precursor. Preferred examples thereof are the same as those of R121 .
  • R 134 represents a tetravalent organic group.
  • Tetravalent organic groups include examples of R 122 in the polybenzoxazole precursor formula (3). Moreover, the preferred examples thereof are the same as those of R122 .
  • four bonds of a tetravalent organic group exemplified as R 122 combine with the nitrogen atom and oxygen atom in the above formula (X) to form a condensed ring.
  • R 134 when R 134 is the following organic group, it forms the structure below. In the structures below, each * represents a bonding site with a nitrogen atom or an oxygen atom in formula (X).
  • Polybenzoxazole preferably has an oxazole conversion rate of 85% or more, more preferably 90% or more.
  • the upper limit is not particularly limited, and may be 100%.
  • the oxazolization rate is measured, for example, by the method described below.
  • An infrared absorption spectrum of polybenzoxazole is measured to obtain a peak intensity Q1 near 1650 cm ⁇ 1 which is an absorption peak derived from the amide structure of the precursor.
  • normalization is performed by the absorption intensity of the aromatic ring seen around 1490 cm ⁇ 1 .
  • the polybenzoxazole may contain repeating units of the above formula (X) that all contain one type of R 131 or R 132 , or may contain repeating units of the above formula (X) that contain two or more different types of R 131 or R 132 . ) repeating units.
  • the polybenzoxazole may also contain other types of repeating units in addition to the repeating units of formula (X) above.
  • Polybenzoxazole is obtained by, for example, reacting a bisaminophenol derivative with a dicarboxylic acid containing R 133 or a compound selected from dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above dicarboxylic acid to obtain a polybenzoxazole precursor. , which is obtained by oxazolating it using a known oxazolating reaction method.
  • a dicarboxylic acid an active ester type dicarboxylic acid derivative obtained by pre-reacting 1-hydroxy-1,2,3-benzotriazole or the like may be used in order to increase the reaction yield.
  • the weight average molecular weight (Mw) of polybenzoxazole is preferably from 5,000 to 70,000, more preferably from 8,000 to 50,000, even more preferably from 10,000 to 30,000.
  • the weight average molecular weight is particularly preferably 20,000 or more.
  • the weight average molecular weight of at least one kind of polybenzoxazole is within the above range.
  • the number average molecular weight (Mn) of polybenzoxazole is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, still more preferably 9,200 to 11,200. be.
  • the polybenzoxazole has a molecular weight dispersity of preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more.
  • the upper limit of the polybenzoxazole molecular weight dispersity is not particularly defined, for example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and even more preferably 2.3 or less.
  • 2.2 or less is even more preferable.
  • the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polybenzoxazole 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 polybenzoxazole as one resin are within the ranges described above.
  • the polyamideimide precursor preferably contains a repeating unit represented by the following formula (PAI-2).
  • R 117 represents a trivalent organic group
  • R 111 represents a divalent organic group
  • a 2 represents an oxygen atom or —NH—
  • R 113 represents a hydrogen atom or a monovalent represents an organic group.
  • R 117 is a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or two
  • the above-linked groups are exemplified, straight-chain aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, and 6 to 20 carbon atoms.
  • alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
  • halogenated alkylene group a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable.
  • the halogen atom in the halogenated alkylene group includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
  • the above halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms be substituted with halogen atoms.
  • preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group and the like.
  • the arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.
  • R 117 is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. Chlorination is preferable as the halogenation.
  • a compound having three carboxy groups is called a tricarboxylic acid compound. Two of the three carboxy groups of the tricarboxylic acid compound may be anhydrided.
  • the optionally halogenated tricarboxylic acid compound used in the production of the polyamideimide precursor include branched aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds. Only one of these tricarboxylic acid compounds may be used, or two or more thereof may be used.
  • the tricarboxylic acid compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a Tricarboxylic acid compounds containing 6 to 20 aromatic groups or groups in which two or more of these are combined via a single bond or a linking group are preferred, and aromatic groups having 6 to 20 carbon atoms or carbon atoms via a single bond or linking group are preferred. More preferred are tricarboxylic acid compounds containing groups in which two or more aromatic groups of numbers 6 to 20 are combined.
  • tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and phthalic acid.
  • (or phthalic anhydride) and benzoic acid are a single bond, —O—, —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —SO 2 — or a phenylene group
  • Linked compounds and the like are included.
  • These compounds may be compounds in which two carboxy groups are anhydrided (e.g., trimellitic anhydride), or compounds in which at least one carboxy group is halogenated (e.g., trimellitic anhydride chloride). There may be.
  • R 111 , A 2 and R 113 have the same meanings as R 111 , A 2 and R 113 in formula (2) above, and preferred embodiments are also the same.
  • Polyamideimide precursors may further comprise other repeating units.
  • Other repeating units include repeating units represented by the above formula (2) and repeating units represented by the following formula (PAI-1).
  • R 116 represents a divalent organic group and R 111 represents a divalent organic group.
  • R 116 is a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or two
  • the above-linked groups are exemplified, straight-chain aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, and 6 to 20 carbon atoms.
  • alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
  • halogenated alkylene group a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable.
  • the halogen atom in the halogenated alkylene group includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
  • the above halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms be substituted with halogen atoms.
  • preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group and the like.
  • the arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.
  • R 116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.
  • a compound having two carboxy groups is called a dicarboxylic acid compound
  • a compound having two halogenated carboxy groups is called a dicarboxylic acid dihalide compound.
  • the carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
  • the optionally halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound used in the production of the polyamideimide precursor includes linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acids. Examples include acid dihalide compounds. One of these dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used, or two or more thereof may be used.
  • the dicarboxylic acid compound or dicarboxylic acid dihalide compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 3 to 20 carbon atoms.
  • a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing a group, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined via a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms.
  • dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2- dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3, 3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexadecanedioic acid, 1,9
  • R 111 has the same definition as R 111 in formula (2) above, and preferred embodiments are also the same.
  • the polyamideimide precursor preferably has a fluorine atom in its structure.
  • the content of fluorine atoms in the polyamideimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
  • the polyamideimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
  • the diamine component bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. are used.
  • An aspect in which the total content of units is 50 mol % or more of all repeating units is exemplified.
  • 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 polyamideimide precursor excluding the terminal are the repeating units represented by the formula (PAI-2), represented by the formula (PAI-1).
  • the total content of repeating units represented by formula (PAI-2) and repeating units represented by formula (PAI-1) is An embodiment in which it is 50 mol % or more of all repeating units is mentioned.
  • 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 polyamideimide precursor excluding the terminal are repeating units represented by formula (PAI-2), or represented by formula (PAI-1) may be any of the repeating units provided.
  • the weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 50,000. .
  • the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, still more preferably 4,000 to 25,000.
  • the polyamidoimide 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.
  • the upper limit of the molecular weight dispersity of the polyamideimide precursor is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
  • the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polyamideimide precursor are preferably within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated from the plurality of types of polyamideimide precursors as one resin are within the ranges described above.
  • the polyamideimide used in the present invention may be an alkali-soluble polyamideimide or a polyamideimide soluble in a developer containing an organic solvent as a main component.
  • the alkali-soluble polyamideimide refers to a polyamideimide that dissolves at 23° C. in an amount of 0.1 g or more in 100 g of a 2.38 mass % tetramethylammonium aqueous solution.
  • a polyamideimide that dissolves 5 g or more is preferable, and a polyamideimide that dissolves 1.0 g or more is more preferable.
  • the upper limit of the dissolved amount is not particularly limited, it is preferably 100 g or less.
  • the polyamideimide is preferably a polyamideimide having a plurality of amide bonds and a plurality of imide structures in the main chain from the viewpoint of the film strength and insulating properties of the organic film to be obtained.
  • the polyamideimide preferably has a fluorine atom.
  • a fluorine atom is preferably contained in, for example, R 117 or R 111 in a repeating unit represented by formula (PAI-3) described later, and is preferably contained in a repeating unit represented by formula (PAI-3) described later It is more preferably contained in R 117 or R 111 as a fluorinated alkyl group.
  • the amount of fluorine atoms is preferably 5% by mass or more and preferably 20% by mass or less with respect to the total mass of polyamideimide.
  • the polyamideimide may have an ethylenically unsaturated bond.
  • Polyamideimide may have an ethylenically unsaturated bond at the end of the 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 117 or R 111 in the repeating unit represented by the formula (PAI-3) described later, and the repeating unit represented by the formula (PAI-3) described later.
  • R 117 or R 111 It is more preferably contained as a group having an ethylenically unsaturated bond in R 117 or R 111 in .
  • Preferred embodiments of the group having an ethylenically unsaturated bond are the same as the preferred embodiments of the group having an ethylenically unsaturated bond in the polyimide described above.
  • the amount of ethylenically unsaturated bonds relative to the total mass of polyamideimide is preferably 0.0001 to 0.1 mol/g, more preferably 0.001 to 0.05 mol/g.
  • Polyamideimide may have a polymerizable group other than the ethylenically unsaturated bond.
  • the polymerizable groups other than the ethylenically unsaturated bond in the polyamideimide include the same groups as the polymerizable groups other than the ethylenically unsaturated bond in the polyimide described above.
  • a polymerizable group other than an ethylenically unsaturated bond is preferably included in R 111 in a repeating unit represented by formula (PAI-3) described later, for example.
  • the amount of polymerizable groups other than ethylenically unsaturated bonds relative to the total mass of polyamideimide is preferably 0.05 to 10 mol/g, more preferably 0.1 to 5 mol/g.
  • -Polarity conversion group- Polyamideimide may have a polarity converting group such as an acid-decomposable group.
  • the acid-decomposable group in polyamideimide 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.
  • the acid value of the polyamideimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g, from the viewpoint of improving developability. g or more 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.
  • the acid value of the polyamideimide is preferably 2 to 35 mgKOH/g, 3 ⁇ 30 mg KOH/g is more preferred, and 5 to 20 mg KOH/g is even more preferred.
  • the acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.
  • the acid group contained in the polyamideimide the same groups as the acid group in the polyimide described above can be mentioned, and the preferred embodiments are also the same.
  • the polyamideimide preferably has a phenolic hydroxy group.
  • Polyamideimide may have a phenolic hydroxy group at the end of the main chain or in the side chain.
  • a phenolic hydroxy group is preferably included in, for example, R 117 or R 111 in a repeating unit represented by formula (PAI-3) described later.
  • the amount of phenolic hydroxy groups relative to the total mass of polyamideimide is preferably 0.1 to 30 mol/g, more preferably 1 to 20 mol/g.
  • the polyamideimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but it preferably contains a repeating unit represented by the following formula (PAI-3).
  • R 111 and R 117 have the same meanings as R 111 and R 117 in formula (PAI-2), respectively, and preferred embodiments are also the same.
  • the polymerizable group may be located on at least one of R 111 and R 117 , or may be located on the end of the polyamideimide.
  • the main chain end of the polyamideimide is blocked with a terminal blocker such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.
  • a terminal blocker such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.
  • Preferred aspects of the terminal blocker are the same as the preferred aspects of the terminal blocker in the polyimide described above.
  • the imidization rate (also referred to as "ring closure rate") of polyamideimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, insulating properties, etc. of the resulting organic film. , more preferably 90% or more.
  • the upper limit of the imidization rate is not particularly limited, and may be 100% or less.
  • the imidization rate is measured by the same method as the ring closure rate of the polyimide described above.
  • Polyamideimide may contain repeating units represented by the above formula (PAI-3), all of which contain one type of R 111 or R 117 , and two or more different types of R 131 or R 132 . It may contain a repeating unit represented by the above formula (PAI-3). Moreover, the polyamideimide may contain other types of repeating units in addition to the repeating units represented by the above formula (PAI-3). Other types of repeating units include repeating units represented by the above formula (PAI-1) or formula (PAI-2).
  • Polyamideimide is, for example, a method of obtaining a polyamideimide precursor by a known method and completely imidizing it using a known imidization reaction method, or stopping the imidization reaction in the middle and partially imidizing the imide structure and a method of partially introducing an imide structure by blending a completely imidized polymer with its polyamideimide precursor.
  • the weight average molecular weight (Mw) of polyamideimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, even more preferably 10,000 to 30,000. 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, the weight average molecular weight is particularly preferably 20,000 or more. Further, the number average molecular weight (Mn) of the polyamideimide is preferably 800 to 250,000, more preferably 2,000 to 50,000, still more preferably 4,000 to 25,000. .
  • the polyamidoimide 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 polyamidoimide 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 weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polyamideimide are preferably within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated from the plurality of types of polyamideimide as one resin are within the above ranges.
  • Polyimide precursors and the like for example, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature to obtain a polyamic acid, a condensing agent or an alkylating agent A method of esterification using a tetracarboxylic dianhydride and an alcohol to obtain a diester, followed by a reaction with a diamine in the presence of a condensing agent, a method of reacting a tetracarboxylic dianhydride and an alcohol to obtain a diester, After that, the remaining dicarboxylic acid can be acid-halogenated using a halogenating agent and reacted with a diamine.
  • the method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and reacting it with a diamine is more preferable.
  • the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N'-disuccinimidyl carbonate, trifluoroacetic anhydride and the like can be mentioned.
  • alkylating agent examples include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate and triethyl orthoformate.
  • halogenating agent examples include thionyl chloride, oxalyl chloride, phosphorus oxychloride and the like.
  • organic solvent In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction. One type of organic solvent may be used, or two or more types may be used.
  • the organic solvent can be appropriately determined depending on the raw material, but pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, ⁇ -butyrolactone, and the like. 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 step of depositing a solid may be included in the production of the polyimide precursor or the like. Specifically, after filtering off the water absorption by-products of the dehydration condensation agent coexisting in the reaction solution as necessary, water, aliphatic lower alcohol, or a poor solvent such as a mixture thereof, the obtained A polyimide precursor or the like can be obtained by adding a polymer component and depositing the polymer component, depositing it as a solid, and drying it. In order to improve the degree of purification, operations such as redissolution, reprecipitation, drying, etc. of the polyimide precursor may be repeated. Furthermore, a step of removing ionic impurities using an ion exchange resin may be included.
  • the content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total mass of the total solid content of the resin composition excluding the filler. It is more preferably 40% by mass or more, and even more preferably 50% by mass or more.
  • the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, preferably 99% by mass or less, relative to the total mass of the total solid content of the resin composition excluding the filler. is more preferably 98% by mass or less, still more preferably 97% by mass or less, and even more preferably 95% by mass or less.
  • the resin composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition of the present invention preferably contains at least two resins.
  • the resin composition of the present invention may contain a total of two or more of the specific resin and other resins described later, or may contain two or more of the specific resins. It is preferable to include two or more kinds.
  • the resin composition of the present invention contains two or more specific resins, for example, two or more polyimides that are polyimide precursors and have different dianhydride-derived structures (R 115 in the above formula (2)) It preferably contains a precursor.
  • the resin composition of the present invention may contain the specific resin described above and other resins different from the specific resin (hereinafter also simply referred to as "other resins").
  • Other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. etc.
  • a resin composition having excellent applicability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
  • a high polymerizable group value having a weight average molecular weight of 20,000 or less for example, the molar amount of the polymerizable group in 1 g of the resin is 1 ⁇ 10 ⁇ 3 mol/g or more
  • the coating properties of the resin composition, the solvent resistance of the pattern (cured product), etc. can be improved.
  • Other resins can also be added to the resin composition as dispersants for fillers. In such an embodiment, as the other resin, a known filler dispersant can be used without particular limitation.
  • the content of the other resins is preferably 0.01% by mass or more with respect to the total mass of the total solids of the resin composition excluding the filler, It is more preferably 0.05% by mass or more, still more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and 10% by mass. The above is even more preferable.
  • the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, and 75% by mass or less, relative to the total mass of the total solid content of the resin composition excluding the filler.
  • 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, relative to the total mass of the total solids of the resin composition excluding the filler. It is more preferably 5% by mass or less, even more preferably 1% by mass or less.
  • the lower limit of the content is not particularly limited as long as it is 0% by mass or more.
  • the resin composition of the present invention may contain only one kind of other resin, or may contain two or more kinds thereof. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition of the present invention preferably contains a polymerizable compound.
  • Polymerizable compounds include radical cross-linking agents or other cross-linking agents.
  • the resin composition of the present invention preferably contains a radical cross-linking agent.
  • a radical cross-linking agent is a compound having a radically polymerizable group.
  • the radically polymerizable group a group containing an ethylenically unsaturated bond is preferred.
  • Examples of the group containing an ethylenically unsaturated bond include groups containing an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
  • the group containing an ethylenically unsaturated bond is preferably a (meth)acryloyl group, a (meth)acrylamide group, or a vinylphenyl group, and more preferably a (meth)acryloyl group from the viewpoint of reactivity.
  • the radical cross-linking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more.
  • the radical cross-linking agent may have 3 or more ethylenically unsaturated bonds.
  • the compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and 2 to 6.
  • the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferred to include
  • the molecular weight of the radical cross-linking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
  • the lower limit of the molecular weight of the radical cross-linking agent is preferably 100 or more.
  • radical cross-linking agent examples include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. They are esters of saturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds.
  • addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxy group, an amino group, or a sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, or monofunctional or polyfunctional is also preferably used.
  • addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and halogeno groups
  • substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a tosyloxy group and monofunctional or polyfunctional alcohols, amines, and thiols.
  • paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated herein.
  • the radical cross-linking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure.
  • examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, glycerin, trimethylolethane, etc.
  • polyfunctional (meth)acrylate obtained by reacting polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth)acrylate and an ethylenically unsaturated bond can also be used.
  • JP-A-2010-160418, JP-A-2010-129825, JP-A-4364216, etc. have a fluorene ring and an ethylenically unsaturated bond. It is also possible to use compounds having two or more groups and cardo resins.
  • JP-B-46-043946 JP-B-01-040337, JP-B-01-040336, and JP-A-02-025493.
  • vinyl phosphonic acid compounds and the like can also be mentioned.
  • Compounds containing perfluoroalkyl groups described in JP-A-61-022048 can also be used.
  • the journal of the Japan Adhesive Association vol. 20, No. 7, pp. 300-308 (1984) as photopolymerizable monomers and oligomers can also be used.
  • dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (Nippon Kayaku ( Ltd.), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipenta Erythritol hexa(meth)acrylate (commercially available products are KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), and their (meth)acryloyl groups are ethylene glycol,
  • radical cross-linking agents examples include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, SR-209, a bifunctional methacrylate having four ethyleneoxy chains, manufactured by Sartomer. 231, 239, Nippon Kayaku Co., Ltd.
  • DPCA-60 a hexafunctional acrylate having 6 pentyleneoxy chains, TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS-10 , UAB-140 (manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Japan Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blenmer PME400 (manufactured by NOF Corporation) etc.
  • radical cross-linking agents examples include urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, JP-B-02-016765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also suitable.
  • compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 are used. can also
  • the radical cross-linking agent may be a radical cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group.
  • a radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. is more preferable.
  • the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol is a compound.
  • Examples of commercially available products include polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd. such as M-510 and M-520.
  • the acid value of the radical cross-linking agent having an acid group is preferably 0.1-300 mgKOH/g, particularly preferably 1-100 mgKOH/g. If the acid value of the radical cross-linking agent is within the above range, the handleability in production is excellent, and furthermore the developability is excellent. Moreover, the polymerizability is good. The acid value is measured according to JIS K 0070:1992.
  • the resin composition preferably uses a bifunctional methacrylate or acrylate.
  • Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, and PEG600 diacrylate.
  • PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula weight of about 200.
  • a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent from the viewpoint of suppressing warpage associated with the elastic modulus control of the pattern (cured product).
  • Monofunctional radical cross-linking agents include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, ) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc.
  • N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam
  • allyl glycidyl ether are preferably used.
  • the monofunctional radical cross-linking agent a compound having a boiling point of 100° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
  • Other di- or higher functional radical cross-linking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.
  • the content is preferably more than 0% by mass and 60% by mass or less with respect to the total mass excluding the filler from the total solid content of the resin composition of the present invention. More preferably, the lower limit is 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.
  • a single radical cross-linking agent may be used alone, or two or more may be used in combination. When two or more are used in combination, the total amount is preferably within the above range.
  • the resin composition of the present invention contains another cross-linking agent different from the radical cross-linking agent described above.
  • the other cross-linking agent refers to a cross-linking agent other than the above-described radical cross-linking agent, and the above-described photoacid generator or photobase generator reacts with other compounds in the composition or reacts with them.
  • the compound has a plurality of groups in the molecule that promote the reaction forming covalent bonds with the product, and covalent bonds are formed with other compounds in the composition or reaction products thereof. Compounds having a plurality of groups in the molecule, the reaction of which is promoted by the action of an acid or base, are preferred.
  • the acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
  • compounds having at least one group selected from the group consisting of acyloxymethyl groups, methylol groups and alkoxymethyl groups are preferred, and the compounds are preferably selected from the group consisting of acyloxymethyl groups, methylol groups and alkoxymethyl groups. More preferred is a compound having a structure in which at least one group is directly bonded to a nitrogen atom.
  • cross-linking agents include, for example, an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, and benzoguanamine, which is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is converted to an acyloxymethyl group, methylol group, or A compound having a structure substituted with an alkoxymethyl group can be mentioned.
  • the method for producing these compounds is not particularly limited as long as they have the same structure as the compounds produced by the above methods. Oligomers formed by self-condensation of methylol groups of these compounds may also be used.
  • a melamine-based crosslinking agent is a melamine-based crosslinking agent
  • a glycoluril, urea or alkyleneurea-based crosslinking agent is a urea-based crosslinking agent
  • an alkyleneurea-based crosslinking agent is an alkyleneurea-based crosslinking agent.
  • a cross-linking agent using benzoguanamine is called a benzoguanamine-based cross-linking agent.
  • the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based cross-linking agents and melamine-based cross-linking agents. More preferably, it contains at least one compound selected from the group consisting of agents.
  • an alkoxymethyl group or an acyloxymethyl group is directly substituted on the nitrogen atom of an aromatic group or the following urea structure, or on a triazine.
  • the alkoxymethyl group or acyloxymethyl group of the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.
  • the total number of alkoxymethyl groups and acyloxymethyl groups in the above compound is preferably 1-10, more preferably 2-8, and particularly preferably 3-6.
  • the molecular weight of the compound is preferably 1500 or less, preferably 180-1200.
  • R 100 represents an alkyl group or an acyl group.
  • R 101 and R 102 each independently represent a monovalent organic group and may combine with each other to form a ring.
  • Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted by an aromatic group include compounds represented by the following general formula.
  • X represents a single bond or a divalent organic group
  • each R 104 independently represents an alkyl group or an acyl group
  • R 103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group , or a group that decomposes under the action of an acid to produce an alkali-soluble group (e.g., a group that leaves under the action of an acid, a group represented by —C(R 4 ) 2 COOR 5 (R 4 is independently It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 represents a group that leaves under the action of an acid.)).
  • R 105 each independently represents an alkyl group or alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3 , a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less.
  • R 5 in the group represented by —C(R 4 ) 2 COOR 5 a group that is decomposed by the action of an acid to produce an alkali-soluble group, a group that is eliminated by the action of an acid, and —C(R 36 )(R 37 )(R 38 ), —C(R 36 )(R 37 )(OR 39 ), —C(R 01 )(R 02 )(OR 39 ), and the like.
  • R 36 to R 39 each independently represent an alkyl group, cycloalkyl group, aryl group, aralkyl group or alkenyl group.
  • R 36 and R 37 may combine with each other to form a ring.
  • alkyl group an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
  • the alkyl group may be linear or branched.
  • a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable.
  • the cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring.
  • the aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a phenyl group.
  • an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable.
  • the aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as the preferred embodiments of the alkyl and aryl groups described above.
  • the alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, more preferably an alkenyl group having 3 to 16 carbon atoms. Moreover, these groups may further have a known substituent within the range in which the effects of the present invention can be obtained.
  • R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
  • the group that is decomposed by the action of an acid to form an alkali-soluble group or the group that is eliminated by the action of an acid is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, or the like. More preferred are tertiary alkyl ester groups and acetal groups.
  • compounds having an alkoxymethyl group include the following structures.
  • Examples of the compound having an acyloxymethyl group include compounds obtained by changing the alkoxymethyl group of the following compounds to an acyloxymethyl group.
  • Compounds having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds.
  • the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group a commercially available one or a compound synthesized by a known method may be used. From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or an 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 the occurrence of warping.
  • benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (these are trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, phenol novolac-type dihydrobenzoxazines, oxazine compounds. These may be used alone or in combination of two or more.
  • the content of the other cross-linking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total mass excluding the filler from the total solid content of the resin composition of the present invention. is more preferable, 0.5 to 15% by mass is more preferable, and 1.0 to 10% by mass is particularly preferable.
  • 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.
  • a polymerization initiator capable of initiating polymerization by light and/or heat.
  • the resin composition according to the present invention preferably also contains a thermal polymerization initiator.
  • the thermal polymerization initiator can be selected depending on the type of polymerizable compound, but a thermal radical polymerization initiator is preferred.
  • a thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes a polymerization reaction of a polymerizable compound.
  • the photopolymerization initiator described above may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.
  • thermal polymerization initiators include known azo compounds and known peroxide compounds.
  • azo-based compounds include azobis-based compounds.
  • the azo compound may be a compound having a cyano group or a compound having no cyano group.
  • Peroxide compounds include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters, and the like.
  • thermal polymerization initiator such as V-40, V-601, and VF-096 manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., perhexyl O manufactured by NOF Corporation, per Hexyl D, Perhexyl I, Perhexa 25O, Perhexa 25Z, Percmyl D, Percmyl D-40, Percmyl D-40MB, Percmyl H, Percmyl P, Percmyl ND and the like.
  • specific examples of thermal radical polymerization initiators include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein.
  • the content of the thermal polymerization initiator in the resin composition is preferably 0.05% by mass or more and 10% by mass or less, and 0.1% by mass or more and 10% by mass, based on the total mass of the total solid content of the composition excluding the filler. % by mass or less is more preferable, 0.1% by mass or more and 5% by mass or less is still more preferable, and 0.5% by mass or more and 3% by mass or less is particularly preferable.
  • the resin composition (particularly, the second resin composition) may contain one type of thermal polymerization initiator alone, or two or more types thereof. When two or more types are included, the total amount is preferably within the above range.
  • the 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.
  • 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 preferably measured at a concentration of 0.01 g/L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
  • any known compound can be used as the photoradical polymerization initiator.
  • halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
  • acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc.
  • ketone compounds include compounds described in paragraph 0087 of JP-A-2015-087611, the content of which is incorporated herein.
  • Kayacure-DETX-S manufactured by Nippon Kayaku Co., Ltd. is also suitably used.
  • a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be suitably used as the radical photopolymerization initiator. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used. incorporated.
  • ⁇ -hydroxyketone initiators include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE -2959 and IRGACURE 127 (trade names: both manufactured by BASF) can be used.
  • ⁇ -aminoketone initiators examples include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all BASF company) can be used.
  • the compound described in JP-A-2009-191179 whose maximum absorption wavelength is matched to a wavelength light source such as 365 nm or 405 nm, can also be used, the content of which is incorporated herein.
  • Acylphosphine oxide initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
  • Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), IRGACURE-819 and IRGACURE-TPO (trade names: all manufactured by BASF) can also be used.
  • metallocene compounds examples include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF) and Keycure VIS 813 (manufactured by King Brother Chem).
  • the photoradical polymerization initiator is more preferably an oxime compound.
  • an oxime compound By using an oxime compound, the exposure latitude can be improved more effectively.
  • Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.
  • oxime compound examples include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp.1653-1660); C. S. Compounds described in Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2017-019766, compounds described in Patent No.
  • Preferred oxime compounds include, for example, compounds having the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy( imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino)) -1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one, etc.
  • an oxime compound an oxime-based radical photopolymerization initiator
  • DFI-091 manufactured by Daito Chemix Co., Ltd.
  • SpeedCure PDO manufactured by SARTOMER ARKEMA
  • an oxime compound having the following structure can be used.
  • An oxime compound having a fluorene ring can also be used as the photoradical polymerization initiator.
  • Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466 and compounds described in Japanese Patent No. 06636081, the contents of which are incorporated herein.
  • an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
  • Specific examples of such oxime compounds include compounds described in WO2013/083505, the contents of which are incorporated herein.
  • oxime compound having a fluorine atom examples include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. and compound (C-3) described in paragraph 0101 of JP-A-164471, the contents of which are incorporated herein.
  • An oxime compound having a nitro group can be used as the photopolymerization initiator.
  • the oxime compound having a nitro group is also preferably a dimer.
  • Specific examples of the oxime compound having a nitro group include the compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249 and paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466; Included are compounds described in paragraphs 0007-0025 of Japanese Patent No. 4223071, the contents of which are incorporated herein.
  • the oxime compound having a nitro group also includes ADEKA Arkles NCI-831 (manufactured by ADEKA Co., Ltd.).
  • An oxime compound having a benzofuran skeleton can also be used as the photoradical polymerization initiator.
  • Specific examples include OE-01 to OE-75 described in WO 2015/036910.
  • an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used.
  • photoinitiators include compounds such as those described in WO2019/088055, the contents of which are incorporated herein.
  • an oxime compound having an aromatic ring group Ar 2 OX1 in which an electron-withdrawing group is introduced into the aromatic ring (hereinafter also referred to as oxime compound OX) can be used.
  • the electron-withdrawing group 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. .
  • the photoradical polymerization initiator includes benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone such as N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), 2-benzyl -aromatic ketones such as 2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, alkylanthraquinones, etc.
  • benzophenone N,N'-tetraalkyl-4,4'-diaminobenzophenone
  • 2-benzyl -aromatic ketones such as 2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, alkylanthr
  • benzoin ether compounds such as benzoin alkyl ether
  • benzoin compounds such as benzoin and alkylbenzoin
  • benzyl derivatives such as benzyl dimethyl ketal
  • a compound represented by the following formula (I) can also be used.
  • R 100 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, Alternatively, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, a carbon number interrupted by one or more oxygen atoms a phenyl group or a biphenyl group substituted with at least one of an alkyl group having 2 to 18 carbon atoms and an alkyl group having 1 to 4 carbon atoms, and R I01 is a group represented by formula (II); R 102 to R 104 are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an
  • R 105 to R 107 are the same as R 102 to R 104 in formula (I) above.
  • radical photopolymerization initiator a difunctional or trifunctional or higher radical photopolymerization initiator may be used.
  • a radical photopolymerization initiator two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained.
  • the crystallinity is lowered, the solubility in a solvent or the like is improved, and precipitation becomes difficult over time, and the stability over time of the resin composition can be improved.
  • Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No.
  • the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1, based on the total mass of the resin composition of the present invention excluding the filler. to 20% by mass, more preferably 0.5 to 15% by mass, and even 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.
  • the total amount is preferably within the above range.
  • the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking by the photopolymerization initiator may be further advanced by heating with an oven, a hot plate, or the like.
  • the resin composition may contain a sensitizer.
  • a sensitizer absorbs specific actinic radiation and enters an electronically excited state.
  • the sensitizer in an electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and causes electron transfer, energy transfer, heat generation, or the like.
  • the thermal radical polymerization initiator and the photoradical polymerization initiator undergo chemical changes and are decomposed to generate radicals, acids or bases.
  • Usable sensitizers include benzophenones, Michler's ketones, coumarins, pyrazole azos, anilinoazos, triphenylmethanes, anthraquinones, anthracenes, anthrapyridones, benzylidenes, oxonols, and pyrazolotriazole azos. , pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo compounds.
  • Sensitizers include, for example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal) Cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyl denindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)iso naphthothiazole,
  • the content of the sensitizer is preferably 0.01 to 20% by mass relative to the total mass excluding the filler from the total solid content of the resin composition. It is more preferably 1 to 15% by mass, even 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 0.01 when the total mass of the resin composition of the present invention excluding the filler is 100 parts by mass. 20 parts by mass is preferable, 0.1 to 10 parts by mass is more preferable, and 0.5 to 5 parts by mass is even more preferable.
  • One type of chain transfer agent may be used, or two or more types may be used. When two or more chain transfer agents are used, the total is preferably within the above range.
  • the resin composition of the present invention preferably contains a photoacid generator.
  • a photoacid generator is a compound that generates at least one of Bronsted acid and Lewis acid upon irradiation with light of 200 nm to 900 nm.
  • the light to be irradiated is preferably light with a wavelength of 300 nm to 450 nm, more preferably light with a wavelength of 330 nm to 420 nm.
  • the photoacid generator is preferably a photoacid generator capable of generating an acid upon exposure.
  • generated acids include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acid, phosphoric monoesters, phosphoric diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, Sulfonamide and the like are preferred.
  • Examples of the photoacid generator used in the resin composition of the present invention include quinone diazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfone compounds, and onium salt compounds.
  • Organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred from the viewpoint of sensitivity and storage stability, and oxime esters are preferred from the viewpoint of the mechanical properties of the film to be formed.
  • quinonediazide compounds include monovalent or polyvalent hydroxy compounds in which quinonediazide sulfonic acids are ester-bonded, monovalent or polyvalent amino compounds in which quinonediazide sulfonic acids are sulfonamide-bonded, and polyhydroxypolyamino compounds with quinonediazide. and/or sulfonic acid having an ester bond and/or a sulfonamide bond.
  • hydroxy compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, t-Bu alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP- PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR -CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML -PFP, DML-PSBP, DML-MTrisPC, TriML
  • amino compounds include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, and the like, but are not limited thereto.
  • polyhydroxypolyamino compounds include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3′-dihydroxybenzidine, but are not limited to these. .
  • the quinonediazide compound preferably contains a phenol compound and an ester with a 4-naphthoquinonediazide sulfonyl group. This makes it possible to obtain higher sensitivity to i-line exposure and higher resolution.
  • the content of the quinonediazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, based on 100 parts by mass of the resin.
  • the content of the quinonediazide compound is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, based on 100 parts by mass of the resin.
  • the photoacid generator is preferably a compound containing an oximesulfonate group (hereinafter also simply referred to as "oximesulfonate compound").
  • the oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group. 105) is preferably an oxime sulfonate compound.
  • X3 represents an alkyl group, an alkoxy group, or a halogen atom. When there are multiple X3's, they may be the same or different.
  • the alkyl group and alkoxy group in X3 above may have a substituent.
  • the alkyl group for X 3 above is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
  • the alkoxy group for X 3 is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
  • halogen atom for X3 a chlorine atom or a fluorine atom is preferable.
  • m3 represents an integer of 0 to 3, preferably 0 or 1.
  • R 34 represents an alkyl group or an aryl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a carbon It is preferably a halogenated alkoxy group of number 1 to 5, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W or an anthranyl group optionally substituted with W.
  • W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms; group, an aryl group having 6 to 20 carbon atoms, and an aryl halide group having 6 to 20 carbon atoms.
  • m3 is 3
  • X 3 is a methyl group
  • the substitution position of X 3 is the ortho position
  • R 34 is a linear alkyl group having 1 to 10 carbon atoms
  • Compounds with a 7-dimethyl-2-oxonorbornylmethyl group or a p-tolyl group are particularly preferred.
  • oxime sulfonate compound represented by formula (OS-1) are described in paragraph numbers 0064 to 0068 of JP-A-2011-209692 and paragraph numbers 0158-0167 of JP-A-2015-194674.
  • the following compounds are exemplified, the contents of which are incorporated herein.
  • R s1 represents an alkyl group, an aryl group or a heteroaryl group
  • each R s2 which may be present in plurality, is independently a hydrogen atom, an alkyl group, or an aryl represents a group or a halogen atom
  • each R s6 which may be present in plurality independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group
  • Xs represents O or S.
  • ns represents 1 or 2
  • ms represents an integer of 0-6.
  • an alkyl group preferably having 1 to 30 carbon atoms
  • an aryl group preferably having 6 to 30 carbon atoms
  • a heteroaryl group preferably having 6 to 30 carbon atoms represented by R s1 Numbers 4 to 30 are preferable
  • R s1 Numbers 4 to 30 may have a known substituent as long as the effects of the present invention can be obtained.
  • R s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms). , a hydrogen atom or an alkyl group.
  • R s2 that may be present in the compound at least two times, one or two are preferably an alkyl group, an aryl group or a halogen atom, and one is more preferably an alkyl group, an aryl group or a halogen atom.
  • one is an alkyl group and the rest are hydrogen atoms.
  • the alkyl group or aryl group represented by R s2 may have a known substituent as long as the effects of the present invention can be obtained.
  • Xs represents O or S, preferably O.
  • the ring containing Xs as a ring member is a 5- or 6-membered ring.
  • ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is 2 is preferred.
  • the alkyl group (preferably having 1 to 30 carbon atoms) and alkyloxy group (preferably having 1 to 30 carbon atoms) represented by R s6 are substituents. may have.
  • ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0 is particularly preferred.
  • the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111).
  • the compound represented by the formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is a compound represented by the following formula (OS -108) or a compound represented by the formula (OS-109).
  • R t1 represents an alkyl group, an aryl group or a heteroaryl group
  • R t7 represents a hydrogen atom or a bromine atom
  • R t8 represents a hydrogen atom, the number of carbon atoms 1 to 8 alkyl group, halogen atom, chloromethyl group, bromomethyl group, bromoethyl group, methoxymethyl group, phenyl group or chlorophenyl group
  • R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group
  • t2 represents a hydrogen atom or a methyl group.
  • R t7 represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.
  • R t8 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group. or represents a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms is more preferred, and a methyl group is particularly preferred.
  • R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, preferably a hydrogen atom.
  • R t2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
  • the oximes may have either one of the three-dimensional structures (E, Z) or may be a mixture.
  • Specific examples of the oxime sulfonate compounds represented by the formulas (OS-103) to (OS-105) include paragraphs 0088 to 0095 of JP-A-2011-209692 and paragraphs of JP-A-2015-194674. Compounds described in numbers 0168-0194 are exemplified, the contents of which are incorporated herein.
  • oximesulfonate compound containing at least one oximesulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).
  • R u9 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, It represents an aryl group or a heteroaryl group.
  • An aspect in which Ru9 is a cyano group or an aryl group is more preferred, and an aspect in which Ru9 is a cyano group, a phenyl group or a naphthyl group is even more preferred.
  • R u2a represents an alkyl group or an aryl group.
  • Xu is -O-, -S-, -NH-, -NR u5 -, -CH 2 -, -CR u6 H- or CR u6 R u7 —, and R u5 to R u7 each independently represent an alkyl group or an aryl group.
  • R u1 to R u4 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group. , arylcarbonyl group, amido group, sulfo group, cyano group or aryl group.
  • Two of R u1 to R u4 may each combine to form a ring. At this time, the ring may be condensed to form a condensed ring together with the benzene ring.
  • R u1 to R u4 are preferably hydrogen atoms, halogen atoms or alkyl groups, and an aspect in which at least two of R u1 to R u4 are bonded to each other to form an aryl group is also preferable. Among them, an aspect in which all of R u1 to R u4 are hydrogen atoms is preferable. Any of the substituents described above may further have a substituent.
  • the compound represented by formula (OS-101) is more preferably a compound represented by formula (OS-102).
  • the stereostructures (E, Z, etc.) of the oxime and benzothiazole rings may be either one or a mixture.
  • Specific examples of the compound represented by formula (OS-101) include compounds described in paragraph numbers 0102 to 0106 of JP-A-2011-209692 and paragraph numbers 0195-0207 of JP-A-2015-194674. and the contents of which are incorporated herein.
  • the following b-9, b-16, b-31 and b-33 are preferred.
  • Examples of commercially available products include WPAG-336 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), MBZ-101 (manufactured by Midori Chemical Co., Ltd.), and the like. can be done.
  • organic halogenated compounds include those described by Wakabayashi et al., "Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. 48-36281, JP-A-55-32070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241 , JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, M.P. P. Hutt "Journal of Heterocyclic Chemistry” 1 (No 3), (1970), the contents of which are incorporated herein.
  • Particularly preferred examples include an oxazole compound substituted with a trihalomethyl group: an S-triazine compound. More preferably, s-triazine derivatives having at least one mono-, di-, or trihalogen-substituted methyl group attached to the s-triazine ring, specifically, for example, 2,4,6-tris(monochloromethyl)- s-triazine, 2,4,6-tris(dichloromethyl)-s-triazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)- s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, 2-( ⁇ , ⁇ , ⁇ -trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine , 2-phenyl-4,6-bis(trichloromethyl)-
  • organic borate compounds include JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, and JP-A-9-188710. Publications, JP-A-2000-131837, JP-A-2002-107916, JP-A-2764769, JP-A-2002-116539, etc., and Kunz, Martin "Rad Tech'98. Proceeding April 19-22 , 1998, Chicago", etc., organic boron sulfonium complexes or organic boron oxosulfonium described in JP-A-6-157623, JP-A-6-175564, and JP-A-6-175561.
  • JP-A-6-175554 organic boron-iodonium complexes described in JP-A-6-175553, organic boron-phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-H9 No. 7-128785, JP-A-7-140589, JP-A-7-306527, JP-A-7-292014 and the like organoboron transition metal coordination complexes are mentioned as specific examples. incorporated herein.
  • disulfone compound examples include compounds described in JP-A-61-166544, Japanese Patent Application No. 2001-132318, and diazodisulfone compounds.
  • onium salt compound for example, S.I. I. Schlesinger, Photograph. Sci. Eng. , 18, 387 (1974); S. Bal et al, Polymer, 21,423 (1980), diazonium salts, US Pat. , 055, 4,069,056, EP 104,143, US Pat. 2-150848, iodonium salts described in JP-A-2-296514, European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, U.S. Pat. Nos. 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827 German Patent Nos.
  • Onium salts include onium salts represented by the following general formulas (RI-I) to (RI-III).
  • Ar 11 represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents. ⁇ 12 alkenyl groups, alkynyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryloxy groups having 1 to 12 carbon atoms, halogen atoms, and 1 to 12 carbon atoms.
  • an alkylamino group having 2 to 12 carbon atoms a dialkylamino group having 2 to 12 carbon atoms, an alkylamide group having 1 to 12 carbon atoms in the alkyl group or an arylamide group having 6 to 20 carbon atoms in the aryl group, a carbonyl group, a carboxy group, cyano groups, sulfonyl groups, thioalkyl groups having 1 to 12 carbon atoms, and thioaryl groups having 1 to 12 carbon atoms.
  • Z 11 - represents a monovalent anion such as a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, a sulfate ion, and a stable Perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, and sulfinate ion are preferred from the aspect.
  • Ar 21 and Ar 22 each independently represent an aryl group having 1 to 20 carbon atoms which may have 1 to 6 substituents, and preferred substituents are 1 to 12 carbon atoms.
  • an alkyl group having 2 to 12 carbon atoms an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen an atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having an alkyl group having 1 to 12 carbon atoms, an alkylamido group or an arylamide group having an alkyl group having 1 to 12 carbon atoms, carbonyl group, carboxy group, cyano group, sulfonyl group, thioalkyl group having 1 to 12 carbon atoms.
  • Z21 ⁇ represents a monovalent anion, and is a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, reaction Perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, and carboxylate ions are preferred from the viewpoint of their properties.
  • R 31 , R 32 and R 33 each independently represents an aryl group, an alkyl group, an alkenyl group or an alkynyl group having 6 to 20 carbon atoms which may have 1 to 6 substituents. In terms of reactivity and stability, it is preferably an aryl group.
  • Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms in each alkyl group, and an alkyl group having 1 to 12 carbon atoms; 1 to 12 alkylamide or arylamido groups, carbonyl groups, carboxy groups, cyano groups, sulfonyl groups, C1 to C12 thioalkyl groups, and C1 to C12 thioaryl groups.
  • Z 31 ⁇ represents a monovalent anion and is a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, From the viewpoint of reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, and carboxylate ion are preferred.
  • preferred photoacid generators include the following.
  • the photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, based on the total mass of the resin composition excluding the filler. It is more preferable to use 0.5 to 10% by mass, even more preferably to use 0.5 to 3% by mass, and even more preferably to use 0.5 to 1.2% by mass.
  • a photo-acid generator may be used individually by 1 type, or may be used in combination of multiple types. In the case of a combination of multiple types, the total amount thereof is preferably within the above range.
  • the resin composition of the present invention may contain a base generator.
  • the base generator is a compound capable of generating a base by physical or chemical action.
  • Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators.
  • the resin composition when the resin composition contains a cyclized resin precursor, the resin composition preferably contains a base generator.
  • the base generator may be an ionic base generator or a non-ionic base generator.
  • bases generated from base generators include secondary amines and tertiary amines. There are no particular restrictions on the base generator used in the present invention, and known base generators can be used. Examples of known base generators include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, and amine imides.
  • Nonionic base generator examples include compounds represented by Formula (B1), Formula (B2), or Formula (B3).
  • Rb 1 , Rb 2 and Rb 3 are each independently an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb 1 and Rb 2 are not hydrogen atoms at the same time. Also, none of Rb 1 , Rb 2 and Rb 3 has a carboxy group.
  • the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when forming an amide group together with the nitrogen atom, this is not the case.
  • Rb 1 , Rb 2 and Rb 3 preferably contains a cyclic structure, and more preferably at least two of them contain a cyclic structure.
  • the cyclic structure may be either a single ring or a condensed ring, preferably a single ring or a condensed ring in which two single rings are condensed.
  • the monocyclic ring is preferably a 5- or 6-membered ring, more preferably a 6-membered ring.
  • the monocyclic ring is preferably a cyclohexane ring and a benzene ring, more preferably a cyclohexane ring.
  • Rb 1 and Rb 2 are a hydrogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms). , more preferably 2 to 18, more preferably 3 to 12), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 10), or an arylalkyl group (7 carbon atoms to 25 are preferred, 7 to 19 are more preferred, and 7 to 12 are even more preferred). These groups may have substituents to the extent that the effects of the present invention are exhibited. Rb 1 and Rb 2 may combine with each other to form a ring.
  • the ring to be formed is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring.
  • Rb 1 and Rb 2 are particularly linear, branched or cyclic alkyl groups (having preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms) which may have a substituent.
  • Rb 3 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 10 are more preferred), alkenyl groups (preferably 2 to 24 carbon atoms, more preferably 2 to 12, more preferably 2 to 6), arylalkyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 19 preferably 7 to 12), arylalkenyl groups (preferably 8 to 24 carbon atoms, more preferably 8 to 20, more preferably 8 to 16), alkoxyl groups (preferably 1 to 24 carbon atoms, 2 to 18 is more preferred, and 3 to 12 are even more preferred), an aryloxy group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12), or an arylalkyloxy group (preferably 7 to 12 carbon atoms).
  • an aryl group preferably
  • Rb 3 may further have a substituent as long as the effects of the present invention are exhibited.
  • the compound represented by formula (B1) is preferably a compound represented by formula (B1-1) or formula (B1-2) below.
  • Rb 11 and Rb 12 and Rb 31 and Rb 32 are respectively the same as Rb 1 and Rb 2 in formula (B1).
  • Rb 13 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, 7 to 12 are more preferable), and may have a substituent within the range in which the effects of the present invention are exhibited.
  • Rb 13 is preferably an arylalkyl group.
  • Rb 33 and Rb 34 each independently represents a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms , more preferably 2 to 8, more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10), an arylalkyl group (7 to 23 is preferred, 7 to 19 are more preferred, and 7 to 11 are even more preferred), and a hydrogen atom is preferred.
  • an alkyl group preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 3 carbon atoms
  • an alkenyl group preferably 2 to 12 carbon atoms , more preferably 2 to 8, more preferably 2 to 3
  • an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10
  • Rb 35 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 , 7 to 12 are more preferred), and aryl groups are preferred.
  • the compound represented by formula (B1-1) is also preferably the compound represented by formula (B1-1a).
  • Rb 11 and Rb 12 have the same definitions as Rb 11 and Rb 12 in formula (B1-1).
  • Rb 15 and Rb 16 are hydrogen atoms, alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6, even more preferably 1 to 3), alkenyl groups (preferably 2 to 12 carbon atoms, 2 to 6 more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 10), an arylalkyl group (preferably 7 to 23 carbon atoms, 7 to 19 are more preferred, and 7 to 11 are even more preferred), and a hydrogen atom or a methyl group is preferred.
  • Rb 17 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, 7 to 12 are more preferable), and aryl groups are particularly preferable.
  • an alkyl group preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms
  • an alkenyl group preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred
  • an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12
  • L is a divalent hydrocarbon group having a saturated hydrocarbon group on a linking chain path connecting adjacent oxygen atoms and carbon atoms, wherein the number of atoms on the linking chain path is represents a hydrocarbon group of 3 or more.
  • R N1 and R N2 each independently represent a monovalent organic group.
  • the term “connected chain” refers to the shortest (minimum number of atoms) of atomic chains on a path connecting two atoms or groups of atoms to be connected.
  • L is composed of a phenylene ethylene group, has an ethylene group as a saturated hydrocarbon group
  • the linking chain is composed of four carbon atoms, and on the route of the linking chain
  • the number of atoms of (that is, the number of atoms constituting the linked chain, hereinafter also referred to as "linked chain length" or "linked chain length”) is 4.
  • the number of carbon atoms in L (including carbon atoms other than carbon atoms in the connecting chain) in formula (B3) is preferably 3-24.
  • the upper limit is more preferably 12 or less, still more preferably 10 or less, and particularly preferably 8 or less. More preferably, the lower limit is 4 or more.
  • the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and 5 The following are particularly preferred.
  • the linking chain length of L is preferably 4 or 5, most preferably 4.
  • Specific preferred compounds of the base generator include, for example, compounds described in paragraph numbers 0102 to 0168 of WO2020/066416, and compounds described in paragraph numbers 0143 to 0177 of WO2018/038002. mentioned.
  • the base generator preferably contains a compound represented by the following formula (N1).
  • R N1 and R N2 each independently represent a monovalent organic group
  • RC1 represents a hydrogen atom or a protecting group
  • L represents a divalent linking group
  • L is a divalent linking group, preferably a divalent organic group.
  • the linking chain length of the linking group is preferably 1 or more, more preferably 2 or more.
  • the upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less.
  • the linking chain length is the number of atoms present in the atomic arrangement that provides the shortest path between two carbonyl groups in the formula.
  • R 1 N1 and R 2 N2 each independently represent a monovalent organic group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, more preferably 3 to 12 carbon atoms), and a hydrocarbon group ( preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms), specifically, an aliphatic hydrocarbon group (preferably 1 to 24 carbon atoms, 1 to 12 is more preferable, 1 to 10 is more preferable) or an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10), and an aliphatic hydrocarbon groups are preferred.
  • a monovalent organic group preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, more preferably 3 to 12 carbon atoms
  • a hydrocarbon group preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms
  • an aliphatic hydrocarbon group
  • an aliphatic hydrocarbon group as R N1 and R N2 because the generated base has high basicity.
  • the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group are in the aliphatic hydrocarbon chain or in the aromatic ring, You may have an oxygen atom in the substituent.
  • an aspect in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.
  • Aliphatic hydrocarbon groups constituting R N1 and R N2 include linear or branched chain alkyl groups, cyclic alkyl groups, groups related to combinations of chain alkyl groups and cyclic alkyl groups, and oxygen atoms in the chains.
  • Alkyl groups having The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms.
  • Linear or branched chain alkyl groups are, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl group, isobutyl group, secondary butyl group, tertiary butyl group, isopentyl group, neopentyl group, tertiary pentyl group, isohexyl group and the like.
  • the cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
  • Cyclic alkyl groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.
  • Groups associated with a combination of a chain alkyl group and a cyclic alkyl group preferably have 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms.
  • Groups related to combinations of chain alkyl groups and cyclic alkyl groups include, for example, a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, and an ethylcyclohexylethyl group.
  • the alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
  • An alkyl group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched.
  • R 1 N1 and R 2 N2 are preferably alkyl groups having 5 to 12 carbon atoms.
  • a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.
  • RN1 and RN2 may be linked to each other to form a ring structure.
  • the chain may have an oxygen atom or the like.
  • the cyclic structure formed by R N1 and R N2 may be a monocyclic ring or a condensed ring, but is preferably a monocyclic ring.
  • the cyclic structure to be formed is preferably a 5- or 6-membered ring containing a nitrogen atom in formula (N1), such as pyrrole ring, imidazole ring, pyrazole ring, pyrroline ring, pyrrolidine ring, imidazolidine ring, A pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring and the like can be mentioned, and a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring and a morpholine ring are preferably mentioned.
  • N1 nitrogen atom in formula (N1)
  • R C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.
  • the protective group is preferably a protective group that is decomposed by the action of an acid or a base, and preferably includes a protective group that is decomposed by an acid.
  • protecting groups include chain or cyclic alkyl groups or chain or cyclic alkyl groups having an oxygen atom in the chain.
  • Chain or cyclic alkyl groups include methyl group, ethyl group, isopropyl group, tert-butyl group, cyclohexyl group and the like.
  • the chain alkyl group having an oxygen atom in the chain specifically includes an alkyloxyalkyl group, more specifically a methyloxymethyl (MOM) group, an ethyloxyethyl (EE) group, and the like. mentioned.
  • Cyclic alkyl groups having an oxygen atom in the chain include epoxy group, glycidyl group, oxetanyl group, tetrahydrofuranyl group, tetrahydropyranyl (THP) group and the like.
  • the divalent linking group constituting L is not particularly defined, but is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group.
  • the hydrocarbon group may have substituents and may have atoms of types other than carbon atoms in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group which may have an oxygen atom in the chain, and a divalent aliphatic hydrocarbon which may have an oxygen atom in the chain group, a divalent aromatic hydrocarbon group, or a group related to a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group, A divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is more preferred.
  • the divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms.
  • the divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
  • the divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
  • a group related to a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and 7 to 10 is more preferred.
  • linking group L examples include a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, and an alkylene group having an oxygen atom in the chain.
  • a linear or branched chain alkenylene group, a cyclic alkenylene group, an arylene group and an arylene alkylene group are preferred.
  • the linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
  • the cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
  • the group associated with the combination of a chain alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms.
  • An alkylene group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched.
  • the alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms.
  • the linear or branched chain alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 3 carbon atoms.
  • the cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
  • the number of C ⁇ C bonds in the cyclic alkenylene group is preferably 1-6, more preferably 1-4, even more preferably 1-2.
  • the arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms.
  • the arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.
  • a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylene alkylene group are preferable, and a 1,2-ethylene group and a propanediyl group (especially 1, 3-propanediyl group), cyclohexanediyl group (especially 1,2-cyclohexanediyl group), vinylene group (especially cis-vinylene group), phenylene group (1,2-phenylene group), phenylenemethylene group (especially 1,2-phenylene methylene group) and ethyleneoxyethylene group (especially 1,2-ethyleneoxy-1,2-ethylene group) are more preferred.
  • base generators include the following, but the present invention should not be construed as being limited thereto.
  • the molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less.
  • the lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
  • Specific preferred compounds of the ionic base generator include, for example, compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.
  • ammonium salts include the following compounds, but the present invention is not limited thereto.
  • iminium salts include the following compounds, but the present invention is not limited thereto.
  • the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition of the present invention.
  • the lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more.
  • the upper limit is more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less.
  • One or two or more base generators can be used. When two or more 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 , ⁇ -caprolactone, ⁇ -valerolactone, alkyl alkyloxyacetates (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g.
  • 3-alkyloxypropionic acid alkyl esters e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
  • 2-alkyloxypropionate alkyl esters e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl propyl oxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)
  • 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.
  • ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol Preferred examples include monobutyl ether acetate
  • Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like.
  • Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene.
  • Suitable sulfoxides include, for example, dimethyl sulfoxide.
  • Suitable ureas include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like.
  • Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, diacetone alcohol and the like.
  • a combination of dimethyl sulfoxide and ⁇ -butyrolactone or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly
  • the content of the solvent is preferably an amount such that the total solid concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass. More preferably, the amount is from 10 to 70% by mass, and even more preferably from 20 to 70% by mass.
  • the solvent content may be adjusted according to the desired thickness of the coating and the method of application.
  • the resin composition of the present invention may contain only one type of solvent, or may contain two or more types. When two or more solvents are contained, the total is preferably within the above range.
  • the resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used for electrodes, wiring, and the like.
  • metal adhesion improvers include alkoxysilyl group-containing silane coupling agents, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, and ⁇ -ketoesters. compounds, amino compounds, and the like.
  • silane coupling agent examples include compounds described in paragraph 0167 of WO 2015/199219, compounds described in paragraphs 0062 to 0073 of JP 2014-191002, and paragraphs of WO 2011/080992.
  • Compounds described in 0063-0071, compounds described in paragraphs 0060-0061 of JP-A-2014-191252, compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/097594 Compounds described in paragraph 0055, compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein.
  • silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycid.
  • xypropyltrimethoxysilane 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2 -(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimeth
  • Aluminum-based adhesion aids include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.
  • the content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.5 parts by mass with respect to 100 parts by mass of the resin. ⁇ 5 parts by mass.
  • the adhesiveness between the pattern and the metal layer is improved, and when it is at most the above upper limit value, the heat resistance and mechanical properties of the pattern are improved.
  • One type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, the total is preferably within the above range.
  • the resin composition of the present invention preferably further contains a migration inhibitor.
  • a migration inhibitor By including the migration inhibitor, it becomes possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the film.
  • Migration inhibitors are not particularly limited, but heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and sulfanyl groups, hindered phenolic compounds , salicylic acid derivative-based compounds, and hydrazide derivative-based compounds.
  • heterocyclic rings pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring,
  • triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 1H-tetrazole, 5- Tetrazole compounds such as phenyltetrazole and 5-amino-1H-tetrazole can be preferably used.
  • an ion trapping agent that traps anions such as halogen ions can be used.
  • Other migration inhibitors include rust inhibitors described in paragraph 0094 of JP-A-2013-015701, compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, and JP-A-2011-059656.
  • the compound described in paragraph 0052, the compound described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, the compound described in paragraph 0166 of WO 2015/199219, etc. can be used, and these The contents are incorporated herein.
  • migration inhibitors include the following compounds.
  • the content of the migration inhibitor is 0.01 to 5.0 mass with respect to the total mass of the resin composition of the present invention excluding the filler from the total solid content. %, more preferably 0.05 to 2.0% by mass, 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 polymerization inhibitors include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4,4′-thiobis(3-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenyl hydroxylamine cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2, 6-di-tert-butyl-4-methylphenol,
  • the content of the polymerization inhibitor is 0.01 to 20% by mass with respect to the total mass excluding the filler from the total solid content of the resin composition of the present invention. preferably 0.02 to 15% by mass, even more preferably 0.05 to 10% by mass.
  • polymerization inhibitor Only one type of polymerization inhibitor may be used, or two or more types may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.
  • the resin composition of the present invention preferably contains an acid scavenger in order to reduce performance changes over time from exposure to heating.
  • the acid scavenger refers to a compound that can scavenge the generated acid when present in the system, and is preferably a compound with low acidity and high pKa.
  • the acid scavenger is preferably a compound having an amino group, preferably a primary amine, secondary amine, tertiary amine, ammonium salt, tertiary amide, etc. Primary amine, secondary amine, tertiary amine, ammonium salt. are preferred, and secondary amines, tertiary amines and ammonium salts are more preferred.
  • acid scavengers include compounds having an imidazole structure, diazabicyclo structure, onium structure, trialkylamine structure, aniline structure or pyridine structure, alkylamine derivatives having hydroxyl groups and/or ether bonds, and anilines having hydroxyl groups and/or ether bonds. Derivatives and the like can be mentioned preferably.
  • the acid scavenger is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, etc., and an anion of an acid less acidic than the acid generated by the acid generator. is preferred.
  • acid scavengers having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzimidazole and the like.
  • Acid scavengers having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, 1,8-diazabicyclo[5,4 ,0]undecar-7-ene and the like.
  • Acid scavengers having an onium structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxides having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris ( t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide and the like.
  • acid scavengers having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine.
  • Acid scavengers having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline and N,N-dihexylaniline.
  • acid scavengers having a pyridine structure include pyridine and 4-methylpyridine.
  • alkylamine derivatives having hydroxyl groups and/or ether bonds include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tris(methoxyethoxyethyl)amine and the like.
  • aniline derivatives having hydroxyl groups and/or ether bonds include N,N-bis(hydroxyethyl)aniline.
  • preferred acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N , N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexyl
  • composition according to the present invention may or may not contain an acid scavenger, but if it does contain an acid scavenger, the content of the acid scavenger is based on the total mass of the composition excluding the filler from the total solids, It is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass.
  • the acid generator/acid scavenger (molar ratio) is more preferably 5.0-200, still more preferably 7.0-150.
  • the resin composition of the present invention may contain various additives such as surfactants, higher fatty acid derivatives, ultraviolet absorbers, organic titanium compounds, antioxidants, Aggregation inhibitors, phenolic compounds, other polymer compounds, plasticizers and other auxiliaries (for example, antifoaming agents, flame retardants, etc.), etc., can be blended. Properties such as film physical properties can be adjusted by appropriately containing these components. These components are described, for example, from paragraph number 0183 of JP-A-2012-003225 (paragraph number 0237 of corresponding US Patent Application Publication No. 2013/0034812), paragraph of JP-A-2008-250074 The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated herein. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.
  • additives such as surfactants, higher fatty acid derivatives, ultraviolet absorbers, organic titanium compounds, antioxidants
  • surfactant various surfactants such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants can be used.
  • the surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
  • the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and liquid saving are further improved.
  • a surfactant in the resin composition of the present invention, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and liquid saving are further improved.
  • the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved.
  • the coatability to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with little unevenness in thickness.
  • fluorosurfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (manufactured by DIC Corporation), Florado FC430, FC431, FC171, Novec FC4430, FC4432 (manufactured by 3M Japan Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (Asahi Glass Co., Ltd.
  • Fluorinated surfactants compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327, compounds described in paragraphs 0117-0132 of JP-A-2011-132503 can also be used, the contents of which are incorporated herein.
  • a block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090, the contents of which are incorporated herein.
  • the fluorosurfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meta)
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.
  • the weight average molecular weight of the above compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
  • a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used as a fluorine-based surfactant. Specific examples include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, the contents of which are incorporated herein.
  • Commercially available products include Megafac RS-101, RS-102 and RS-718K manufactured by DIC Corporation.
  • the fluorine content in the fluorine-based surfactant is preferably 3-40% by mass, more preferably 5-30% by mass, and particularly preferably 7-25% by mass.
  • a fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and saving liquid, and has good solubility in the composition.
  • silicone-based surfactants examples include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (the above, Toray Dow Corning Co., Ltd.
  • TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 manufactured by Momentive Performance Materials
  • KP341, KF6001, KF6002 manufactured by Shin-Etsu Silicone Co., Ltd.
  • BYK307, BYK323, and BYK330 manufactured by BYK-Chemie Co., Ltd.
  • Hydrocarbon surfactants include, for example, Pionin A-76, Nucalgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, Pionin D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, Pionin P-4050-T and the like (manufactured by Takemoto Oil & Fat Co., Ltd.), and the like.
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Examples include polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester.
  • cationic surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 77, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.
  • anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.), and Sandet BL (manufactured by Sanyo Kasei Co., Ltd.).
  • the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total mass excluding the filler from 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 0.1 to 10% by mass based on the total mass of the resin composition of the present invention excluding the filler.
  • the total is preferably within the above range.
  • the composition of the present invention may contain an ultraviolet absorber.
  • an ultraviolet absorber As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used.
  • salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate, and the like.
  • benzophenone-based UV absorbers examples include 2,2'-dihydroxy-4- Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- and hydroxy-4-octoxybenzophenone.
  • benzotriazole-based UV absorbers examples include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3 '-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-( 2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2 -(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5' -(1,
  • Examples of substituted acrylonitrile UV absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate.
  • examples of triazine-based UV absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl )-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) -mono(hydroxyphenyl)triazine compounds such as 1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(
  • the above various ultraviolet absorbers may be used singly or in combination of two or more.
  • the composition of the present invention may or may not contain an ultraviolet absorber, but when it does, the content of the ultraviolet absorber is based on the total mass of the composition of the present invention excluding the filler from the total solid mass. is preferably 0.001% by mass or more and 1% by mass or less, more preferably 0.01% by mass or more and 0.1% by mass or less.
  • 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, based on 100 parts by mass of the resin.
  • the amount is 0.05 parts by mass or more, the resulting cured pattern exhibits good heat resistance and chemical resistance more effectively. Excellent.
  • compositions of the present invention may contain antioxidants.
  • an antioxidant By containing an antioxidant as an additive, it is possible to improve the elongation properties of the cured film and the adhesion to metal materials.
  • Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound.
  • Preferred phenolic compounds include hindered phenolic compounds.
  • a compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred.
  • a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable as the above substituent.
  • the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule.
  • Phosphorus-based antioxidants can also be suitably used as antioxidants.
  • a phosphorus antioxidant tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl ) oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like.
  • antioxidants examples include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Corporation) and the like.
  • compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used, the contents of which are incorporated herein.
  • the composition of the present invention may also contain latent antioxidants, if desired.
  • the latent antioxidant is a compound in which the site functioning as an antioxidant is protected with a protective group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst.
  • a compound that functions as an antioxidant by removing the protective group by the reaction is exemplified.
  • latent antioxidants include compounds described in WO 2014/021023, WO 2017/030005, and JP 2017-008219, the contents of which are incorporated herein.
  • Commercially available latent antioxidants include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.).
  • Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds of formula (3).
  • R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R 6 represents alkylene having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). represents a group.
  • R 7 represents a monovalent to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom and a nitrogen atom.
  • k represents an integer of 1 to 4;
  • the compound represented by formula (3) suppresses oxidative deterioration of the aliphatic groups and phenolic hydroxyl groups of the resin. In addition, metal oxidation can be suppressed by the antirust action on the metal material.
  • R7 includes an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, combinations thereof, and the like, which may further have a substituent.
  • Examples of compounds represented by general formula (3) include the following, but are not limited to the structures below.
  • the amount of antioxidant to be added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin.
  • the addition amount 0.1 parts by mass or more By making the addition amount 0.1 parts by mass or more, the effect of improving elongation characteristics and adhesion to metal materials can be easily obtained even in a high-temperature and high-humidity environment.
  • the interaction with the agent improves the sensitivity of the resin composition.
  • Only one kind of antioxidant may be used, or two or more kinds thereof may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
  • the resin composition of the present embodiment may contain an anti-aggregation agent as necessary.
  • Anti-aggregation 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 based on the total mass excluding the filler from the total solid mass of the composition of the present invention. is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.02% by mass or more and 5% by mass or less.
  • 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 based on the total mass of the composition of the present invention excluding the filler from the total solid mass. 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.
  • 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 the total solid mass of the composition of the present invention minus the filler. It is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less, relative to the total mass.
  • 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) from the viewpoint of insulation, and 1 mass Less than ppm is more preferred, and less than 0.5 mass ppm is even more preferred.
  • metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are included, the total of these metals is preferably within the above range.
  • a raw material having a low metal content is selected as a raw material constituting the resin composition of the present invention.
  • the raw material constituting the product is filtered through a filter, or the inside of the apparatus is lined with polytetrafluoroethylene or the like to perform distillation under conditions in which contamination is suppressed as much as possible.
  • the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and less than 200 ppm by mass from the viewpoint of wiring corrosion. is more preferred.
  • those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass.
  • Halogen atoms include chlorine and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms or chlorine ions and bromine ions is within the above ranges.
  • ion exchange treatment and the like are preferably mentioned.
  • a conventionally known container can be used as the container for the resin composition of the present invention.
  • the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resin are used. It is also preferred to use bottles with a seven-layer structure. Examples of such a container include the container described in JP-A-2015-123351.
  • a precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
  • the resulting reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of crude polymer.
  • the resulting crude polymer was collected by filtration and dissolved in 200 ml of tetrahydrofuran to obtain a crude polymer solution.
  • the resulting crude polymer solution was dropped into 3 liters of water to precipitate the polymer, and the resulting precipitate was collected by filtration and vacuum dried to obtain a powdery polymer P-2.
  • the weight average molecular weight (Mw) of this polymer was measured and found to be 23,000.
  • Polymer P-2 is a resin having the following structure. Subscripts in parentheses represent the molar ratio of each repeating unit.
  • composition was obtained by mixing the components shown in the table below. Specifically, the contents of the components described in the table were the amounts (parts by mass) described in the table. In the table, the description of "-" indicates that the composition does not contain the corresponding component.
  • ⁇ resin ⁇ ⁇ P-1 Upia (registered trademark) -LB 1001 (manufactured by Ube Industries, Ltd.)
  • ⁇ P-2 to P-5 P-2 to P-5 synthesized above
  • F-1 Alumina / Sumitomo Chemical
  • F-2 Alumina / Sumitomo Chemical
  • F-3 Silica nanoparticle dispersion (average particle size: 0.02 ⁇ m)
  • F-4 Boron nitride / manufactured by 3M, Platelets001 SPC1 manufactured by ESK Ceramics
  • F-5 Alumina / manufactured by Admatechs, fine alumina dispersion
  • AO-502 ⁇ F-6 Carbon fiber (Dialead K223 manufactured by Mitsubishi Chemical Corporation)
  • F-7 Boron nitride nanotubes (BN Nanobarbs manufactured by BNNano Inc.)
  • ⁇ F-8 Fiber-like aluminum nitride (thermal night powder type manufactured by U-MAP)
  • ⁇ B-1 Tetraethylene glycol dimethacrylate (manufactured by Arkema)
  • B-2 Dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical)
  • B-3 OGSOL EA-0300 acrylate (manufactured by Osaka Gas Chemicals)
  • B-4 OGSOL EA-0200 (manufactured by Osaka Gas Chemicals)
  • the average particle size of the filler was measured by cross-sectional SEM (scanning electron microscope) observation of a film that had been soft-baked and pre-cured after coating the composition on a substrate.
  • SEM scanning electron microscope
  • S-4800 manufactured by Hitachi High Tech was used, and the average diameter of the minimum enclosing circle with respect to the apparent outline of each particle was calculated to obtain the average particle diameter.
  • Pillar substrates having the following sizes and metal types were fabricated on 8-inch silicon wafers by plating.
  • the pillars of both substrates were in a square array.
  • Pitch 25 ⁇ m
  • copper pillar diameter 10 ⁇ m
  • copper pillar height 10 ⁇ m
  • Pitch 45 ⁇ m
  • copper/tin pillar diameter 20 ⁇ m
  • copper/tin pillar height 2/8 ⁇ m
  • silicon wafer copper and tin are formed in this order.
  • FIG. 6(a) is a schematic sectional view of the above a) and c).
  • 10 denotes a substrate
  • 12 denotes a projection (pillar) made of copper.
  • the arithmetic mean value of the pillar diameters d in each pillar is the pillar diameter, which is 10 ⁇ m in a) and 20 ⁇ m in c).
  • the arithmetic average value of the pillar spacing p in each pillar is the pitch, which is 10 ⁇ m in a) and 20 ⁇ m in c).
  • FIG. 6A is a schematic sectional view of the above a) and c).
  • 10 denotes a substrate
  • 12 denotes a projection (pillar) made of copper.
  • the arithmetic mean value of the pillar diameters d in each pillar is the pillar diameter, which is 10 ⁇ m in a) and 20 ⁇ m in c).
  • FIG. 6(a) the arithmetic mean value of the pillar height h of each pillar is the pillar height, which is 10 ⁇ m in a) and 10 ⁇ m in c).
  • FIG. 6(b) is a schematic sectional view of the above b).
  • 10 denotes a substrate and 12 denotes a projection.
  • the projection 12 is formed of pillars (conducting paths) made of tin and pillars (electrodes) 16 made of copper. ing.
  • the arithmetic mean value of the pillar diameters d in each pillar is the pillar diameter, which is 20 ⁇ m in b).
  • the arithmetic mean value of the pillar spacing p of each pillar is the pitch, which is 45 ⁇ m in b).
  • the arithmetic mean value of the height h1 of the conduction path in each pillar is the tin pillar height, and in b) it is 8 ⁇ m.
  • the arithmetic mean value of the electrode height h2 in each pillar is the copper pillar height, which is 2 ⁇ m in b).
  • the bonding temperature is 250° C. or 300° C. (the temperature described in the “bonding temperature” column of the table), the pressure is 14 kN, the heating time is 10 min, and the atmospheric pressure is 1 ⁇ 10 ⁇ 3 mbar.
  • a substrate laminate (bonded body) was obtained. It was confirmed that the substrates of each joined body were electrically connected to each other. 1 mbar is 100 Pa.
  • a joined body (substrate laminate) was produced under the same conditions as those used for the evaluation of the maximum peel resistance.
  • the joined body was held in an environment of 120° C./100% RH (relative humidity)/0.1 MPa for 168 hours.
  • the bonded body after being held was evaluated for the maximum peeling force, and those showing a value of 50% or more of the maximum peeling force (A), those showing a value of 25% or more and less than 50% ( B), and those showing a value of less than 25% were designated as (C).
  • the evaluation results are shown in the "environmental resistance" column of the table.
  • Thermal conductivity was evaluated based on thermal diffusivity.
  • the thermal diffusivity was measured with a thermal diffusivity measuring device FTC-RT (manufactured by Advance Riko) based on the periodic heating method (according to ISO 22007-3 international standards for plastics). It was measured by obtaining reference data of a silicon wafer having the same thickness and calculating the difference.
  • the thermal diffusivity was measured by contacting the coating surface with an apparatus, and evaluated in the following four stages. The evaluation results are shown in the "thermal conductivity" column of the table. It can be said that the higher the thermal diffusivity, the better the thermal conductivity of the filler-containing layer.
  • the thermal diffusivity was 5.0 ⁇ 10 ⁇ 7 m 2 s ⁇ 1 or more.
  • D Thermal diffusivity was less than 2.0 ⁇ 10 ⁇ 7 m 2 s ⁇ 1 .
  • CTE coefficient of thermal expansion
  • the composition used in each example was coated on the substrate in such a thickness that the film thickness of the resulting cured film was 1 ⁇ m, and heated at the thickness shown in the “additional bake” column of the table.
  • the cured film (model of the filler-containing layer) obtained after heating was tested in J. Phys. A.
  • the linear expansion coefficient (CTE value) in the film thickness direction was measured using a Woollam variable temperature spectroscopic ellipsometry.
  • the linear expansion coefficient (CTE-C) in the range of 50 to 200° C. of the cured film obtained by applying composition 9 to the above thickness and heating at 200° C. for 30 minutes was measured.
  • the relative CTE value (%) of each composition was calculated by the following formula and evaluated in the following three stages.
  • Relative CTE value (%) CTE value of each composition/CTE-C ⁇ 100 -Evaluation criteria-
  • C The relative CTE value was 70% or more.
  • the bonded body obtained by the manufacturing method of the bonded body of the present invention the bonded body provided with the filler layer having excellent thermal conductivity was obtained. It can be seen that in Comparative Examples 1 and 2 in which the adhesive layer was formed using the composition containing no filler, the thermal conductivity of the resulting adhesive layer was poor.
  • Substrate A (underlying substrate, daughter chip) 1x silicon wafer 1y filler-containing layer-provided substrate 1z laminate 2 substrate B (mother chip) 2a Surface of substrate B 2x Silicon wafer 2y Through-hole electrode 3 Electrode 30 Projection 31 Conducting path 31a End of conducting path 32 Electrode (pad) (metal part) 4 Resin composition layer 4a Surface of filler-containing layer (before flattening) 4b Surface of filler-containing layer (after flattening) 41 filler-containing layer 8 electronic circuit region 10 substrate 12 convex portion 14 conducting path 16 electrode 81 electronic circuit 90 semiconductor device 91 bonding film 93 solder electrode (bump) 94 underfill 95 sealing resin 96 wire bonding 97a substrate electrode 97b wire bonding pad 98 base substrate 99 solder ball 100 bonded body 101a to 101d semiconductor element 101 bonded body 102b to 102d through electrode 103a to 103e metal bump 105 rewiring layer 110, 110a, 110b resin layer (filler-containing layer) 115 insulating layer

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacturing Of Printed Wiring (AREA)
PCT/JP2022/018934 2021-04-28 2022-04-26 接合体の製造方法、半導体デバイスの製造方法、及び、樹脂組成物。 Ceased WO2022230899A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020237036904A KR102906195B1 (ko) 2021-04-28 2022-04-26 접합체의 제조 방법, 반도체 디바이스의 제조 방법, 및, 수지 조성물
JP2023517573A JPWO2022230899A1 (https=) 2021-04-28 2022-04-26
CN202280031212.9A CN117203746A (zh) 2021-04-28 2022-04-26 接合体的制造方法、半导体器件的制造方法及树脂组合物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021-076040 2021-04-28
JP2021076040 2021-04-28

Publications (1)

Publication Number Publication Date
WO2022230899A1 true WO2022230899A1 (ja) 2022-11-03

Family

ID=83848490

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/018934 Ceased WO2022230899A1 (ja) 2021-04-28 2022-04-26 接合体の製造方法、半導体デバイスの製造方法、及び、樹脂組成物。

Country Status (5)

Country Link
JP (1) JPWO2022230899A1 (https=)
KR (1) KR102906195B1 (https=)
CN (1) CN117203746A (https=)
TW (1) TW202311406A (https=)
WO (1) WO2022230899A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024219502A1 (ja) * 2023-04-19 2024-10-24 Ｈｄマイクロシステムズ株式会社 絶縁膜形成材料、半導体装置の製造方法及び半導体装置

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008084951A (ja) * 2006-09-26 2008-04-10 Fujitsu Ltd 半導体装置の製造方法
JP2008235527A (ja) * 2007-03-20 2008-10-02 Fujitsu Ltd 部品内蔵基板の製造方法
JP2011216565A (ja) * 2010-03-31 2011-10-27 Fujitsu Ltd 電子部品、電子機器及びそれらの製造方法
WO2017175481A1 (ja) * 2016-04-05 2017-10-12 リンテック株式会社 三次元集積積層回路製造用シートおよび三次元集積積層回路の製造方法
JP2017206620A (ja) * 2016-05-18 2017-11-24 パナソニックＩｐマネジメント株式会社 封止用アクリル樹脂組成物、半導体装置及び半導体装置の製造方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4337358B2 (ja) * 2003-02-17 2009-09-30 日立化成工業株式会社 積層用中間配線部材、配線板及びそれらの製造方法
JP4353845B2 (ja) * 2004-03-31 2009-10-28 富士通株式会社 半導体装置の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008084951A (ja) * 2006-09-26 2008-04-10 Fujitsu Ltd 半導体装置の製造方法
JP2008235527A (ja) * 2007-03-20 2008-10-02 Fujitsu Ltd 部品内蔵基板の製造方法
JP2011216565A (ja) * 2010-03-31 2011-10-27 Fujitsu Ltd 電子部品、電子機器及びそれらの製造方法
WO2017175481A1 (ja) * 2016-04-05 2017-10-12 リンテック株式会社 三次元集積積層回路製造用シートおよび三次元集積積層回路の製造方法
JP2017206620A (ja) * 2016-05-18 2017-11-24 パナソニックＩｐマネジメント株式会社 封止用アクリル樹脂組成物、半導体装置及び半導体装置の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024219502A1 (ja) * 2023-04-19 2024-10-24 Ｈｄマイクロシステムズ株式会社 絶縁膜形成材料、半導体装置の製造方法及び半導体装置

Also Published As

Publication number Publication date
KR102906195B1 (ko) 2026-01-05
TW202311406A (zh) 2023-03-16
CN117203746A (zh) 2023-12-08
JPWO2022230899A1 (https=) 2022-11-03
KR20230162964A (ko) 2023-11-29

Similar Documents

Publication Publication Date Title
JP7558278B2 (ja) 硬化性樹脂組成物、硬化物、積層体、硬化物の製造方法、及び、半導体デバイス
JP7825572B2 (ja) 樹脂組成物、硬化物、積層体、硬化物の製造方法、及び、半導体デバイス
JP7504213B2 (ja) 硬化物の製造方法、積層体の製造方法、及び、半導体デバイスの製造方法
JP7300511B2 (ja) 硬化膜の製造方法、光硬化性樹脂組成物、積層体の製造方法、及び、半導体デバイスの製造方法
JP7576617B2 (ja) 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイス
JP7756110B2 (ja) 樹脂組成物、硬化物、積層体、硬化物の製造方法、及び、半導体デバイス
JP7612698B2 (ja) 硬化性樹脂組成物、硬化物、積層体、硬化物の製造方法、及び、半導体デバイス、並びに、光塩基発生剤
JP7595062B2 (ja) 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイス
JP7799007B2 (ja) 感光性樹脂組成物、硬化物、積層体、硬化物の製造方法、及び、半導体デバイス
WO2023120037A1 (ja) 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
WO2022244717A1 (ja) ポリイミド含有部形成用組成物、接合体の製造方法、接合体、デバイスの製造方法、及び、デバイス。
JP7712424B2 (ja) 樹脂組成物、硬化物、積層体、硬化物の製造方法、及び、半導体デバイス
JP7808591B2 (ja) 樹脂組成物、硬化物、積層体、硬化物の製造方法、及び、半導体デバイス
JP7558293B2 (ja) 樹脂組成物、硬化物、積層体、硬化物の製造方法、及び、半導体デバイス
JP7573026B2 (ja) 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイス
WO2022210225A1 (ja) 樹脂組成物、硬化物、積層体、硬化物の製造方法、及び、半導体デバイス
JP7620024B2 (ja) 複合パターンの製造方法、樹脂組成物、積層体の製造方法、及び、半導体デバイスの製造方法
WO2022265030A1 (ja) 永久膜の製造方法、積層体の製造方法、及び、デバイスの製造方法、並びに、永久膜
JP7498281B2 (ja) 硬化性樹脂組成物、硬化物、積層体、硬化物の製造方法、及び、半導体デバイス
WO2022176869A1 (ja) 永久膜の製造方法、積層体の製造方法、及び、半導体デバイスの製造方法
KR102906195B1 (ko) 접합체의 제조 방법, 반도체 디바이스의 제조 방법, 및, 수지 조성물
WO2021157643A1 (ja) 樹脂組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイス
JP7500740B2 (ja) 硬化性樹脂組成物、硬化物、積層体、硬化物の製造方法、及び、半導体デバイス、並びに、化合物
JP7641975B2 (ja) 樹脂組成物、硬化物、積層体、硬化物の製造方法、及び、半導体デバイス
JP7653442B2 (ja) 樹脂組成物、硬化物、積層体、硬化物の製造方法、及び、半導体デバイス

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22795812

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023517573

Country of ref document: JP

ENP Entry into the national phase

Ref document number: 20237036904

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 202280031212.9

Country of ref document: CN

Ref document number: 1020237036904

Country of ref document: KR

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22795812

Country of ref document: EP

Kind code of ref document: A1