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
  • C08K9/00—Use of pretreated ingredients
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/62—Alcohols or phenols
  • C08G59/621—Phenols
• • 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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
• • 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
  • C08K3/30—Sulfur-, selenium- or tellurium-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
  • C08K3/34—Silicon-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
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances
  • C08K9/06—Ingredients treated with organic substances with silicon-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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
  • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • 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
• • 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
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
• • 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
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
• • 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
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/011—Nanostructured additives

Definitions

• the present invention relates to a composition, a transfer film, a method for producing a laminate, a laminate, and a cured film.
• a touch panel such as a capacitive input device
• conductive patterns such as an electrode pattern corresponding to the sensor of the visual recognition area
• wiring of the peripheral wiring section and the extraction wiring section are provided inside the touch panel.
• insulating films are provided between each layer.
• Patent Document 1 discloses an epoxy resin composition of a specific composition.
• the inventors formed a film using a composition having the structure described in Patent Document 1, and discovered that it was difficult to obtain a film having both good dielectric properties and good migration resistance.
• a composition comprising a resin and a filler X surface-modified with a surface modifier,
• the content of the filler X is 50.0 mass% or more based on the total solid content of the composition,
• the average particle size of the filler X is 300 nm or less
• the composition, wherein the content of the surface modifier is 3.0 mass% or less based on the total mass of the filler X.
• the filler X comprises at least one selected from the group consisting of silicon dioxide, boron nitride, barium sulfate, and silicates.
• the composition according to [1] or [2], wherein the average particle size of the filler X is 150 nm or less.
• content of the surface modifier is 2.5 mass% or less based on the total mass of the filler X.
• the resin comprises at least one selected from the group consisting of a phenolic resin, an epoxy resin, a polyphenylene ether resin, a silicone resin, a benzocyclobutene resin, a fluorene resin, an acrylic resin, a methacrylic resin, a liquid crystal polymer, polyethersulfone, polyarylate, polyetherimide, polybenz
• the present invention there can be provided a composition capable of forming a film having excellent dielectric properties and excellent migration resistance. Further, the present invention can provide a transfer film, a method for producing a laminate, a laminate, and a cured film relating to the composition.
• FIG. 2 is a diagram (nomograph) explaining a method for measuring the boiling point of compound Y.
• FIG. 2 is a schematic diagram showing an example of a layer structure of a transfer film.
• a numerical range expressed using “to” means a range that includes the numerical values before and after “to” as the lower and upper limits.
• the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described in a certain stepwise manner.
• the upper limit or lower limit described in a certain numerical range may be replaced with a value shown in the examples.
• process in this specification does not only refer to an independent process, but also includes processes that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.
• the temperature condition may be 25°C.
• the temperature when performing each of the above steps may be 25°C unless otherwise specified.
• the term "transparent" means that the average transmittance of visible light having a wavelength of 400 to 700 nm is 80% or more, and preferably 90% or more.
• the average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.
• actinic rays or “radiation” refers to the emission line spectrum of mercury lamps such as g-rays, h-rays, and i-rays, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams (EB).
• Light refers to actinic rays or radiation.
• exposure includes not only exposure to mercury lamps, far ultraviolet light such as excimer lasers, extreme ultraviolet light, X-rays, and EUV light, but also drawing with particle beams such as electron beams and ion beams.
• the refractive index is the value measured by an ellipsometer at a wavelength of 550 nm.
• the molecular weight is the weight average molecular weight (Mw).
• Mw weight average molecular weight
• Mn number average molecular weight
• (meth)acrylic acid is a concept that includes both acrylic acid and methacrylic acid
• (meth)acryloyl group is a concept that includes both acryloyl group and methacryloyl group
• (meth)acrylate is a concept that includes both acrylate and methacrylate
• (meth)acrylic resin is a concept that includes both acrylic resin and methacrylic resin.
• water-soluble means that the solubility in 100 g of water at pH 7.0 and a liquid temperature of 22°C is 0.1 g or more.
• solids of a composition refers to the components that form the composition layer formed using the composition, and in the case where the composition contains a solvent (e.g., an organic solvent and water), refers to all components excluding the solvent.
• a solvent e.g., an organic solvent and water
• liquid components are also considered to be solids if they form a composition layer.
• the layer thickness is the average thickness measured using a scanning electron microscope (SEM) for thicknesses of 0.5 ⁇ m or more, and the average thickness measured using a transmission electron microscope (TEM) for thicknesses of less than 0.5 ⁇ m.
• SEM scanning electron microscope
• TEM transmission electron microscope
• the above average thickness is determined by cutting the sample to be measured using an ultramicrotome, measuring the thickness at any five points, and calculating the arithmetic average of the measured thicknesses.
• composition of the present invention is a composition comprising a resin and a filler X surface-modified with a surface modifier, the content of the filler X being 50.0 mass% or more relative to the total solid content of the composition, the average particle size of the filler X being 300 nm or less, and the content of the surface modifier being 3.0 mass% or less relative to the total mass of the filler X.
• the present inventors speculate as follows. Since the composition of the present invention contains a characteristic filler X, it is speculated that the film obtained by using the composition of the present invention has excellent dielectric properties and migration resistance. In addition, since the composition of the present invention contains a resin, the film can be formed. The film formed may be patterned. Hereinafter, the achievement of at least one of the effects of the formed film being superior in dielectric properties and superior in migration resistance will also be referred to as "the effect of the present invention being superior.”
• the composition includes a resin.
• the resin is different from the various components described below.
• the resin may be either a thermoplastic resin or a thermosetting resin.
• the resin may have a polymerizable group.
• the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloyl group, a vinyl group or a styryl group, and further preferably a (meth)acryloyl group.
• the resin may be either an unmodified product or a modified product.
• an epoxy resin is a resin having an epoxy group, and may further have a functional group other than the epoxy group and a structure containing the functional group.
• the resin may be, for example, a known resin.
• the resin is preferably at least one selected from the group consisting of a phenolic resin, an epoxy resin, a polyphenylene ether resin, a silicone resin, a benzocyclobutene resin, a fluorene resin, a (meth)acrylic resin, a liquid crystal polymer, a polyethersulfone, a polyarylate, a polyetherimide, a polybenzimidazole, a polyphenylsulfone, a polycarbonate, an acrylonitrile-butadiene-styrene resin (ABS resin) and a polyphenylene sulfide, more preferably at least one selected from the group consisting of a phenolic resin, an epoxy resin, a polyphenylene ether resin, a silicone resin, a benzocyclobutene resin, a fluorene resin, a (meth)acrylic resin and a liquid crystal polymer, more preferably
• the phenolic resin is a resin having a phenolic hydroxyl group.
• examples of the phenol resin include phenol novolac resin, cresol novolac resin, biphenyl aralkyl type phenol resin, naphthol aralkyl resin, and naphthol novolac resin.
• phenolic resins include AV Light series such as TR4020G, TR4050G, TR4080G, TR5020G, TR5050G, TR6020G, TR6050G, and TR6080G manufactured by Asahi Organic Chemicals Co., Ltd.; photoresist resin series manufactured by Sumitomo Bakelite Co., Ltd.; Resitop series manufactured by Gun-ei Chemical Industry Co., Ltd.; PR-30-40P, PR-100L, PR-100H, PR-50, PR-55, PR-56-1, PR-56-2, Phenolite series such as WR-101, WR-102, WR-103 and WR-104 manufactured by DIC Corporation; photoresist resins such as LF-100, LF-110, LF-120, LF-200, LF-400 and LF-500 manufactured by Lignite Corporation; MEHC-7851SS, MEHC-78004S, MEHC-7851-SS, MEHC-7851-S, MEHC-7851-M, MEHC-
• the epoxy resin is a resin having an epoxy group.
• the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol epoxy resin, naphthol novolac epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane dimethanol type epoxy resin, naphthylene ether type epoxy resin, and trimethylol type epoxy resin.
• the epoxy resin preferably contains an epoxy resin that is liquid at a temperature of 20°C (hereinafter also referred to as “liquid epoxy resin”) and an epoxy resin that is solid at a temperature of 20°C (hereinafter also referred to as “solid epoxy resin”), in terms of excellent flexibility and improved breaking strength of the resulting cured layer.
• liquid epoxy resin an epoxy resin that is liquid at a temperature of 20°C
• solid epoxy resin an epoxy resin that is solid at a temperature of 20°C
• liquid epoxy resin bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin or naphthalene type epoxy resin is preferred, and bisphenol A type epoxy resin, bisphenol F type epoxy resin or naphthalene type epoxy resin is more preferred.
• liquid epoxy resins examples include HP4032, HP4032D, EXA4032SS, and HP4032SS (naphthalene type epoxy resins) manufactured by DIC Corporation; jER828EL (bisphenol A type epoxy resin), jER807 (bisphenol F type epoxy resin), and jER152 (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and ZX1059 (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical Co., Ltd.
• HP4032SS or ZX1059 is preferred.
• solid epoxy resin tetrafunctional naphthalene type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol epoxy resin, naphthol novolac epoxy resin, biphenyl type epoxy resin or naphthylene ether type epoxy resin is preferable, tetrafunctional naphthalene type epoxy resin, biphenyl type epoxy resin or naphthylene ether type epoxy resin is more preferable, and biphenyl type epoxy resin is further preferable.
• solid epoxy resins examples include HP-4700, HP-4710 (tetrafunctional naphthalene type epoxy resin), N-690 (cresol novolac type epoxy resin), N-695 (cresol novolac type epoxy resin), HP7200, HP7200H, HP7200K-65I (dicyclopentadiene type epoxy resin), EXA7311, EXA7311-G3 and HP6000 (naphthylene ether type epoxy resin), EPPN-502H (trisphenol A type epoxy resin) manufactured by DIC Corporation
• epoxy resins include NC7000L (naphthol novolac epoxy resin), NC3000H, NC3000, NC3000L and NC3100 (biphenyl type epoxy resin), manufactured by Nippon Kayaku Co., Ltd.; ESN475 (naphthol novolac type epoxy resin) and ESN485 (naphthol novolac type epoxy resin), manufactured by Nippon Steel Chemical Co., Ltd.; YX4000H,
• the polyphenylene ether resin is a resin having a phenylene ether group.
• the polyphenylene ether resin may have either a linear structure or a branched structure, and preferably has a branched structure.
• ether bonds are directly bonded to at least three positions, i.e., the ipso-, ortho- and para-positions, of the benzene ring.
• the polyphenylene ether resin having a branched structure can be obtained, for example, by polymerizing two or more kinds of phenol compounds.
• the above-mentioned phenol compound is preferably a phenol compound having hydrogen atoms at the ortho and para positions and having a polymerizable group, or a mixture of a phenol compound having hydrogen atoms at the ortho and para positions and no polymerizable group and a phenol compound having no hydrogen atom at the ortho position, a hydrogen atom at the para position and having a polymerizable group.
• phenol compounds used in the synthesis of polyphenylene ether resins include o-vinylphenol, m-vinylphenol, o-allylphenol, m-allylphenol, 3-vinyl-6-methylphenol, 3-vinyl-6-ethylphenol, 3-vinyl-5-methylphenol, 3-vinyl-5-ethylphenol, 3-allyl-6-methylphenol, 3-allyl-6-ethylphenol, 3-allyl-5-methylphenol, 3-allyl-5-ethylphenol, phenol, o-cresol, m-cresol, o-ethylphenol, m-ethylphenol, 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, o-tert-butylphenol, m-tert-butylphenol, o-phenylphenol, m-phenylphenol, and 2-dodecylphenol.
• phenol examples include 2-allyl-6-methylphenol, 2-allyl-6-ethylphenol, 2-allyl-6-phenylphenol, 2-allyl-6-styrylphenol, 2,6-divinylphenol, 2,6-diallylphenol, 2,6-diisopropenylphenol, 2,6-dibutenylphenol, 2,6-diisobutenylphenol, 2,6-diisopentenylphenol, 2-methyl-6-styrylphenol, 2-vinyl-6-methylphenol, 2-vinyl-6-ethylphenol, 2,6-dimethylphenol, 2,3,6-trimethylphenol, 2-methyl-6-ethylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-n-butylphenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, and 2,6-ditolylphenol.
• the phenol compound is preferably 2,6-dimethylphenol or 2-allylphenol.
• the polyphenylene ether resin also preferably has a polymerizable group.
• the polymerizable group is preferably an ethylenically unsaturated group, more preferably a vinylphenyl group or a (meth)acryloyl group.
• the composition preferably contains a maleimide compound described below. The maleimide compound reacts with the polyphenylene ether resin to obtain a modified polyphenylene ether.
• modified polyphenylene ethers include resins obtained by curing the resin compositions described in WO 2022/102756.
• polyphenylene ether resins include poly(2,6-diethyl-1,4-phenylene) ether, poly(2-ethyl-6-n-propyl-1,4-phenylene) ether, poly(2,6-di-n-propyl-1,4-phenylene) ether, poly(2-methyl-6-n-butyl-1,4-phenylene) ether, poly(2-ethyl-6-isopropyl-1,4-phenylene) ether, poly(2-methyl-6-chloroethyl-1,4-phenylene) ether, poly(2-methyl-6-hydroxyethyl-1,4-phenylene) ether, and poly(2-methyl-6-chloroethyl-1,4-phenylene) ether.
• polyphenylene ether resins include those described in JP-A-2022-157695.
• the silicone resin is a resin having an organosiloxane structure.
• the silicone resin include curable silicone resins, silicone graft resins, and modified silicone resins such as alkyl-modified silicone resins, with curable silicone resins being preferred.
• the curable silicone resin include an addition reaction type silicone resin, a condensation reaction type silicone resin, and an ultraviolet or electron beam curable silicone resin.
• An example of an addition reaction type silicone resin is a resin obtained by reacting and curing polydimethylsiloxane having vinyl groups introduced at the terminals or side chains with hydrogen siloxane using a platinum catalyst.
• An example of a condensation reaction type silicone resin is a resin having a three-dimensional crosslinked structure formed by condensing polydimethylsiloxane having a hydroxyl group at its terminal with polydimethylsiloxane having a hydrogen atom at its terminal using an organotin catalyst.
• ultraviolet-curable silicone resins include those that utilize the same radical reaction as silicone rubber crosslinking, those that introduce unsaturated groups to cause photocuring, those that use ultraviolet light or electron beams to decompose onium salts to generate strong acids and cleave epoxy groups to cause crosslinking, and those that crosslink by addition reaction of thiols to vinyl siloxanes.
• Specific examples include acrylate-modified polydimethylsiloxanes and glycidoxy-modified polydimethylsiloxanes.
• silicone resins include a dimethylsiloxane-methylvinylsiloxane copolymer capped at both molecular chain terminals with trimethylsiloxy groups, a dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymer capped at both molecular chain terminals with trimethylsiloxy groups, and a dimethylsiloxane-diphenylsiloxane copolymer capped at both molecular chain terminals with dimethylvinylsiloxy groups.
• the silicone resin preferably has an aromatic ring.
• the aromatic ring is preferably an aromatic hydrocarbon ring, more preferably an aromatic hydrocarbon ring having 6 to 12 carbon atoms, and further preferably a benzene ring.
• the silicone resin a modified silicone resin obtained by reacting an organosilicon compound with a hydrosilylation agent is also preferred.
• the organosilicon compound preferably further has a polymerizable group, for example, a polymerizable group contained in the resin.
• the organosilicon compound may, for example, be a compound having a silyl group, and 1,4-bis(dimethylsilyl)benzene or trivinylphenylsilane is preferred.
• hydrosilylation agent examples include platinum-based catalysts such as carbon powder supporting platinum metal, platinum black, platinic chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and olefins, and platinum bisacetoacetate; and platinum group metal catalysts such as palladium-based catalysts and rhodium-based catalysts.
• the reaction temperature is preferably 100 to 200° C., and the reaction time is preferably 1 to 10 hours.
• silicone resins examples include resins obtained from organosiloxanes and curable compositions described in JP 2020-026502 A.
• the benzocyclobutene resin is a resin having a benzocyclobutene ring.
• Benzocyclobutene resins include, for example, divinylsiloxane-bisbenzocyclobutene resins (eg, CYCLOTENE resins, manufactured by The Dow Chemical Company).
• the (meth)acrylic resin is a resin having a repeating unit derived from a compound selected from (meth)acrylic acid and a (meth)acrylic acid ester.
• the repeating units derived from a (meth)acrylic acid ester include repeating units derived from a (meth)acrylic acid alkyl ester.
• the number of carbon atoms in the alkyl group (—COOR, the alkyl group in the R portion) constituting the (meth)acrylic acid alkyl ester is preferably 1 to 50, more preferably 1 to 10, and even more preferably 1 to 6.
• the alkyl group may be linear, branched, or cyclic.
• alkyl (meth)acrylate is methyl (meth)acrylate.
• the total content of the repeating units derived from (meth)acrylic acid and (meth)acrylic acid esters is preferably 20% by mass or more, more preferably 50% by mass or more, based on the total repeating units of the (meth)acrylic resin, and the upper limit is preferably 100% by mass or less, more preferably 90% by mass or less.
• the (meth)acrylic resin may have a repeating unit having an aromatic ring.
• the repeating unit having an aromatic ring may be a repeating unit derived from a (meth)acrylic acid ester.
• the repeating unit having an aromatic ring may be a repeating unit derived from a (meth)acrylic acid ester having an aromatic ring group.
• the aromatic ring is preferably an aromatic hydrocarbon ring, more preferably an aromatic hydrocarbon ring having 6 to 12 carbon atoms, and further preferably a benzene ring.
• repeating unit having an aromatic ring examples include a repeating unit derived from a (meth)acrylate having an aromatic ring, a repeating unit derived from styrene, and a repeating unit derived from a polymerizable styrene derivative.
• examples of the (meth)acrylate having an aromatic ring include benzyl (meth)acrylate, phenethyl (meth)acrylate, and phenoxyethyl (meth)acrylate.
• Styrene and polymerizable styrene derivatives include, for example, styrene, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene dimer, and styrene trimer.
• the (meth)acrylic resin may have a repeating unit having an alicyclic group.
• the repeating unit having an alicyclic group may be a repeating unit derived from a (meth)acrylic acid ester.
• the repeating unit having an alicyclic group may be a repeating unit derived from a (meth)acrylic acid ester having an alicyclic group.
• the alicyclic ring may be either a monocyclic ring or a polycyclic ring. Examples of the alicyclic ring include a dicyclopentanyl ring, a dicyclopentenyl ring, an isobornyl ring, an adamantane ring, and a cyclohexyl ring.
• Examples of monomers from which repeating units having an alicyclic ring are derived include dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, and cyclohexyl (meth)acrylate.
• a liquid crystal polymer is a resin that exhibits liquid crystallinity.
• the liquid crystal polymer is preferably a thermotropic liquid crystal polymer, which means a polymer that exhibits liquid crystallinity within a certain temperature range.
• the thermotropic liquid crystal polymer may be any liquid crystal polymer that can be melt-molded, and examples thereof include thermoplastic liquid crystal polyesters and thermoplastic polyester amides in which amide bonds are introduced into thermoplastic liquid crystal polyesters.
• the liquid crystal polymer preferably has a repeating unit having an aromatic ring.
• the aromatic ring is preferably an aromatic hydrocarbon ring, more preferably an aromatic hydrocarbon ring having 6 to 12 carbon atoms, and further preferably a benzene ring.
• the monomer from which the repeating unit having an aromatic ring is derived is preferably p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone, terephthalic acid or isophthalic acid.
• the liquid crystal polymer preferably contains two or more repeating units derived from a compound selected from p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone, terephthalic acid, and isophthalic acid, and more preferably contains four or five repeating units derived from the above compounds.
• the liquid crystal polymer may contain repeating units derived from compounds other than the above compounds.
• Other compounds include, for example, aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 3,3'-diphenyldicarboxylic acid, and 2,2'-diphenyldicarboxylic acid; aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid; alicyclic dicarboxylic acids such as hexahydroterephthalic acid, 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl,
• liquid crystal polymers examples include those described in JP 2006-299254 A and WO 2015/064437 A.
• resins examples include polyethersulfone, polyarylate, polyetherimide, polybenzimidazole, polyphenylsulfone, polycarbonate, acrylonitrile-butadiene-styrene resin, and polyphenylene sulfide.
• resins examples include known resins other than the various resins mentioned above.
• the weight average molecular weight (Mw) of the resin is preferably from 2,000 to 500,000, and more preferably from 5,000 to 100,000.
• the number average molecular weight (Mn) of the resin is preferably from 800 to 250,000, and more preferably from 2,000 to 50,000.
• the dispersity (Mw/Mn) of the resin is preferably from 1.0 to 3.5, and more preferably from 2.0 to 3.0.
• the resins may be used alone or in combination of two or more.
• the resin content is preferably 5.0% by mass or more, more preferably 10.0% by mass or more, based on the total solid content of the composition, and the upper limit is preferably 50.0% by mass or less, more preferably 40.0% by mass or less.
• the composition comprises a filler X.
• Filler X is a filler whose surface has been modified with a surface modifier. In other words, the filler constituting filler X has been surface-modified with a surface modifier.
• the content of filler X is 50.0% by mass or more, preferably 60.0% by mass or more, and more preferably 70.0% by mass or more, based on the total solid content of the composition.
• the upper limit is preferably 90.0% by mass or less, and more preferably 80.0% by mass or less.
• the average particle size of the filler X is 300 nm or less, preferably 200 nm or less, and more preferably 150 nm or less.
• the lower limit is preferably more than 0 nm, more preferably 5 nm or more, and even more preferably 10 nm or more.
• the average particle size of the filler X is calculated by the following particle size measurement method. Particle size measurement method: The composition is applied onto a substrate to form a coating film, and a rectangular region of 3 ⁇ m ⁇ 10 ⁇ m in a cross section along the normal direction of the coating film surface is observed with a scanning electron microscope.
• the operation of measuring the major axes of all filler X particles observed within the above-mentioned region is performed at five different points on the coating film, and the arithmetic mean value of the major axes of all filler X particles measured in each operation is defined as the average particle size of filler X.
• the composition is applied onto a substrate to form a coating film.
• the thickness of the coating film is preferably 3 ⁇ m or more.
• a glass substrate is used as the substrate.
• a drying treatment may be performed as necessary.
• a cross section along the normal direction of the surface (surface opposite to the substrate side) of the obtained coating film is cut out, and a rectangular region of 3 ⁇ m ⁇ 10 ⁇ m of the cross section is observed with a scanning electron microscope, and the major axis of all filler X observed within the region is measured.
• S-4800 manufactured by Hitachi High-Tech Corporation is used. The magnification during observation is 50,000 times.
• the above operation is carried out at five different locations on the coating film, and the average value (arithmetic mean value) of all the major axis values of the filler X measured in each operation is defined as the average particle size of the filler X.
• the above-mentioned major axis refers to the length of the longest line segment among the line segments connecting any two points on the contour line of the filler X in the observed image. Furthermore, when the filler X is aggregated to form an aggregate in the observed image, the major axis of each filler X constituting the aggregate is measured.
• the content of the surface modifier is 3.0% by mass or less, preferably 2.5% by mass or less, more preferably less than 2.0% by mass, and even more preferably 1.5% by mass or less, based on the total mass of the filler X.
• the lower limit is preferably more than 0% by mass, and more preferably 0.5% by mass or more.
• the content of the surface modifier means the total content of the surface modifier covering at least a part of the surface of the filler constituting Filler X and the components derived from the surface modifier. In other words, the content of the surface modifier does not include the surface modifier that does not cover the surface of the filler constituting Filler X, i.e., the value does not include the surface modifier that is free in the composition.
• the content of the surface modifier can be measured, for example, by Method Z.
• Method Z A composition layer is formed by applying the composition onto a substrate and drying the composition so that the thickness after drying is 10 ⁇ m.
• the temperature in the drying is preferably 50 to 150° C., more preferably 70 to 100° C.
• the heating time in the drying is preferably 1 to 10 minutes, more preferably 2 to 7 minutes.
• MEK methyl ethyl ketone
• NMP N-methylpyrrolidone
• the temperature in the above drying is preferably 50 to 150 ° C, more preferably 70 to 100 ° C.
• the heating time in the above drying is preferably 1 to 120 minutes, more preferably 5 to 30 minutes.
• the above filter can be appropriately selected according to the average particle size of the filler X.
• the weight loss rate of the measurement filler is measured three times in an air atmosphere under the condition of heating from room temperature to 1000° C. (10° C./min) using a TG-DTA device (TG/DTA7300) manufactured by Hitachi High-Tech Science Corporation, and the content of the surface modifier is calculated from the average value of the measured weight loss rates.
• the filler constituting the filler X is surface-modified with a surface modifier.
• the fact that the filler constituting filler X has been surface-treated with a surface modifier means that at least a part of the surface of the filler constituting filler X is covered with the surface modifier or a component derived from the surface modifier.
• filler X means that at least a part of the surface of the filler constituting filler X is covered with the surface modifier or a component derived from the surface modifier.
• the component derived from the surface modifier include, when the surface modifier is a hydrolyzable compound, a hydrolyzate of the surface modifier and a hydrolysis condensate thereof.
• At least a part of the surface of the filler constituting filler X is covered with a surface modifier or a component derived from a surface modifier via a chemical bond, and it is more preferable that at least a part of the surface of the filler constituting filler X is covered with a surface modifier via a "-Si-O-" bond.
• the surface modifier examples include known surface modifiers such as silane coupling agents, titanate coupling agents, and silazane compounds.
• the silane coupling agent is a compound having a hydrolyzable group directly bonded to a silicon atom.
• the hydrolyzable group include an alkoxy group (preferably having 1 to 10 carbon atoms) and a halogen atom such as a chlorine atom.
• the number of hydrolyzable groups directly bonded to Si atoms in the silane coupling agent is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more.
• the upper limit is preferably 10,000 or less. It is also preferable that the silane coupling agent has a functional group other than the hydrolyzable group.
• Examples of the functional group include a (meth)acryloyl group, a phenyl group, a silazane group, an epoxy group, an oxetanyl group, a vinyl group, a styryl group, an amino group, an isocyanate group, a mercapto group, and an acid anhydride group.
• the number of functional groups that the silane coupling agent has may be one or more.
• Methods for surface-modifying the filler constituting Filler X with a surface modifier include, for example, a dry method in which the surface is modified in the gas phase, and a wet method in which the surface is modified in the liquid phase, with the dry method being preferred in terms of superior dielectric properties.
• the shape of the filler X may be either spherical or non-spherical (e.g., crushed or fibrous), with spherical being preferred.
• filler X examples include organic fillers and inorganic fillers whose surfaces have been modified with a surface modifier, and inorganic fillers whose surfaces have been modified with a surface modifier are preferred.
• fillers constituting filler X include silicon dioxide (silica); silicates such as kaolinite, kaolin clay, calcined clay, talc, and glass fillers such as chion-doped glass; alumina, barium sulfate, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, zirconium phosphate, cordierite, zirconium tungstate, and manganese nitride.
• Filler X preferably contains at least one selected from the group consisting of silicon dioxide (silica), boron nitride, barium sulfate, and silicates, more preferably contains silicon dioxide (silica), and even more preferably contains silicon dioxide (silica).
• Filler X and fillers constituting Filler X include, for example, NHM-3N, NHM-4N, NHM-5N, NHM-24D, NP-3N, NP-4N, NP-5N and NP-24D (all manufactured by Tokuyama Corporation, silicon dioxide, solids concentration 100% by mass); YA050C-MJE, Y50SP-AM1 and Y50SZ-AM1 (all manufactured by Admatechs Corporation, silicon dioxide, MEK slurry with a solids concentration of 50% by mass); MEK-ST-ZL, MEK-ST-L, MEK- AC-5140Z, MEK-EC-2130Y and MEK-EC-2430Z (all manufactured by Nissan Chemical Industries, Ltd., solid content concentration 30% by mass); Seahoster KE-S30 (manufactured by Nippon Shokubai Co., Ltd., silicon dioxide, solid content concentration 100% by mass), SFP-20M (manufactured by Denka Co., Ltd., silicon dioxide, solid content concentration 100% by mass), PMA
• the refractive index of the filler is preferably from 0.5 to 3.0, and more preferably from 1.2 to 1.8.
• the refractive index can be measured by the method described above.
• the fillers may be used alone or in combination of two or more types.
• the composition may include a polymerizable compound.
• the polymerizable compound is a compound different from the above-mentioned various components.
• the composition contains a polymerizable compound (preferably a compound having an ethylenically unsaturated group), the composition preferably further contains a photopolymerization initiator described below.
• the polymerizable compound is a compound having one or more polymerizable groups in one molecule.
• a compound having an ethylenically unsaturated group is preferable, a compound having a (meth)acryloyl group, a vinyl group or a styryl group is more preferable, and a compound having a (meth)acryloyl group is even more preferable.
• the number of polymerizable groups that the polymerizable compound has is preferably 1 or 2 or more, more preferably 2 to 10, and even more preferably 2 to 6.
• the polymerizable compound include a polymerizable compound having one polymerizable group in one molecule (hereinafter also referred to as a "monofunctional polymerizable compound”), a polymerizable compound having two polymerizable groups in one molecule (hereinafter also referred to as a "bifunctional polymerizable compound”), and a polymerizable compound having three or more polymerizable groups in one molecule (hereinafter also referred to as a "trifunctional or higher functional polymerizable compound”).
• the polymerizable compound is preferably a difunctional polymerizable compound or a tri- or higher functional polymerizable compound.
• bifunctional polymerizable compounds include polyethylene glycol (meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, tricyclodecane dimenanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate.
• bifunctional polymerizable compounds include, for example, diethylene glycol dimethacrylate (2G, manufactured by Shin-Nakamura Chemical Co., Ltd.), triethylene glycol dimethacrylate (3G, manufactured by Shin-Nakamura Chemical Co., Ltd.), polyethylene glycol #200 dimethacrylate (4G, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimenanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), SR205NS (manufactured by Sartomer Co.,
• tri- or higher functional polymerizable compound examples include dipentaerythritol (tri/tetra/penta/hexa)(meth)acrylate, pentaerythritol (tri/tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton.
• (tri/tetra/penta/hexa)(meth)acrylate is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate
• (tri/tetra)(meth)acrylate” is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.
• polymerizable compounds examples include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20, etc., manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040, etc., manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300, etc., manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL (registered trademark) 135, etc., manufactured by Daicel-Allnex Corporation), and ethoxylated glycerin triacrylate (A-GLY-9E, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.).
• Examples of the polymerizable compound include urethane (meth)acrylates (preferably tri- or higher functional urethane (meth)acrylates).
• the number of polymerizable groups in the urethane (meth)acrylate is preferably 6 or more, more preferably 8 or more.
• the upper limit is preferably 20 or less.
• trifunctional or higher urethane (meth)acrylates examples include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.); UA-32P, U-15HA and UA-1100H (all manufactured by Shin-Nakamura Chemical Co., Ltd.); AH-600 (manufactured by Kyoeisha Chemical Co., Ltd.); UA-306H, UA-306T, UA-306I, UA-510H and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).
• the polymerizable compounds may be used alone or in combination of two or more.
• the content of the polymerizable compound is preferably 30.0% by mass or less, more preferably 25.0% by mass or less, and even more preferably 20.0% by mass or less, based on the total solid content of the composition.
• the lower limit is preferably 1.0% by mass or more.
• the composition may include a photoinitiator.
• the photopolymerization initiator is a compound different from the above-mentioned various components. Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoanionic polymerization initiator, and a photoradical polymerization initiator is preferred.
• the photopolymerization initiator examples include oxime ester compounds (photopolymerization initiators having an oxime ester structure), aminoacetophenone compounds (photopolymerization initiators having an aminoacetophenone structure), hydroxyacetophenone compounds (photopolymerization initiators having a hydroxyacetophenone structure), acylphosphine oxide compounds (photopolymerization initiators having an acylphosphine oxide structure), and bistriphenylimidazole compounds (photopolymerization initiators having a bistriphenylimidazole structure).
• an oxime ester compound or an aminoacetophenone compound is preferable, and an oxime ester compound is more preferable.
• oxime ester compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (product name: IRGACURE OXE-01, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (product name: IRGACURE OXE-02, manufactured by BASF), [ 8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazoyl][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyloxime) (trade name: IRGACURE OXE-03, manufactured by BASF Corporation), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl
• aminoacetophenone compounds include 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, Omnirad (Irgacure) series, manufactured by IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907), and APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.).
• photopolymerization initiators examples include 2-hydroxy-1- ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl ⁇ -2-methyl-propan-1-one (trade name: Omnirad 127), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (trade name: Omnirad 369), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: Omnirad 1 173), 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Omnirad 184), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H), and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819) are also included.
• photopolymerization initiators include those described in paragraphs 0031 to 0042 of JP2011-095716A and paragraphs 0064 to 0081 of JP2015-014783A.
• the photopolymerization initiator may be used alone or in combination of two or more.
• the content of the photopolymerization initiator is preferably 10.0% by mass or less, more preferably 5.0% by mass or less, and even more preferably 1.0% by mass or less, based on the total solid content of the composition.
• the lower limit is preferably 0.1% by mass or more.
• the composition may comprise a compound Y.
• Compound Y is a compound that does not have an ethylenically unsaturated group and has a boiling point of 300° C. or higher.
• the compound Y is a compound different from the various components (for example, the photopolymerization initiator, etc.) described above.
• composition contains compound Y
• a transfer film having a composition layer formed using the composition is laminated onto an object to be laminated, and a pattern is formed by exposure treatment, development treatment, and heat treatment after development
• compound Y functions as a component for ensuring the plasticity of a resin such as resin X in the photosensitive layer, and is removed by volatilization when heat treatment after development is performed, and is less likely to remain in the pattern system.
• the boiling point of compound Y is 300° C. or higher, and preferably 350° C. or higher.
• the upper limit is preferably 500° C. or lower, more preferably 480° C. or lower, and even more preferably 450° C. or lower.
• the boiling point of the compound Y is a value determined by the following measurement method.
• the gas temperature at the point when the evaporated gas starts to condense is defined as the boiling point (measured from 23 to 300° C., temperature rise rate 1° C./min).
• the distillation of compound Y is carried out using a Liebig condenser, and if distillation does not start at 300°C under normal pressure, distillation is carried out under reduced pressure.
• distillation is carried out at pressures of 100 mmHg, 50 mmHg, and 5 mmHg in that order, and the boiling point at normal pressure calculated from the temperature and pressure at which condensation of the evaporated gas begins using the nomograph shown in Figure 1 (source: Science of Petroleum, Vol. II. p. 1281 (1938)). If distillation does not start at 300°C under 5 mmHg, the boiling point at normal pressure is considered to be greater than 500°C.
• the method of using the nomograph is well known.
• step 1 draw a straight line to connect the boiling point at reduced pressure on line A and the degree of reduced pressure on line C (step 1), read the numerical value at the intersection of the line drawn in step 1 with line B (step 2), and regard this as the boiling point at normal pressure.
• the molecular weight of compound Y is preferably 200 or more, more preferably 250 or more, and even more preferably 300 or more.
• the upper limit is preferably 1,000 or less, more preferably 800 or less, and even more preferably 600 or less.
• the above molecular weight of compound Y refers to the weight average molecular weight.
• the viscosity of compound Y at 25° C. is preferably 500 mPa ⁇ s or less, more preferably 300 mPa ⁇ s or less, and even more preferably 100 mPa ⁇ s or less.
• the lower limit is preferably 0.01 mPa ⁇ s or more, more preferably 0.05 mPa ⁇ s or more, and even more preferably 0.1 mPa ⁇ s or more.
• the viscosity can be measured by a B-type viscometer.
• compound Y examples include ethyl phthalyl ethyl glycolate, dihexyl phthalate, tributyl o-acetylcitrate, benzyl 2-ethylhexyl phthalate, benzyl benzoate, hexaethylene glycol monomethyl ether, pentaethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, heptaethylene glycol monomethyl ether, octaethylene glycol monomethyl ether, nonaethylene glycol monomethyl ether, pentaethylene glycol dimethyl ether, hexaethylene glycol dimethyl ether, heptaethylene glycol dimethyl ether, octaethylene glycol dimethyl ether, nonaethylene glycol dimethyl ether, bis(2-ethylhexyl) isophthalate, triamyl phosphate, tris(2-butoxyethyl) phosphate, triethylene glycol bis(2-ethylhexan
• the compound Y may be used alone or in combination of two or more.
• the content of compound Y is preferably 1.0% by mass or more, more preferably 3.0% by mass or more, and even more preferably 5.0% by mass or more, based on the total solid content of the composition.
• the upper limit is preferably less than 50.0% by mass, more preferably 35.0% by mass or less, and even more preferably 25.0% by mass or less.
• the total content of the polymerizable compound and compound Y is preferably less than 50.0% by mass, more preferably 30.0% by mass or less, and even more preferably 25.0% by mass or less, based on the total solid content of the composition.
• the composition may include a photoacid generator.
• the photoacid generator is a compound that generates an acid when exposed to light (eg, exposure light).
• photoacid generators include ionic photoacid generators and non-ionic photoacid generators.
• the ionic photoacid generator include a compound having a sulfonium structure, an onium salt compound having a diaryliodonium or triarylsulfonium structure, and an ammonium salt compound having a quaternary ammonium structure.
• Examples of the ionic photoacid generator include the ionic photoacid generators described in paragraphs 0114 to 0133 of JP2014-085643A.
• nonionic photoacid generators examples include trichloromethyl-s-triazine and its derivatives (trichloromethyl-s-triazine which may have a substituent), compounds having a diazomethane structure, compounds having an imide sulfonate structure, and compounds having an oxime sulfonate structure.
• examples of trichloromethyl-s-triazine and its derivatives, diazomethane compounds, and imide sulfonate compounds include the compounds described in paragraphs 0083 to 0088 of JP 2011-221494 A.
• Examples of oxime sulfonate compounds include the compounds described in paragraphs 0084 to 0088 of WO 2018/179640 A.
• the photoacid generators may be used alone or in combination of two or more.
• the content of the photoacid generator is preferably from 0.1 to 10.0% by mass, and more preferably from 0.5 to 5.0% by mass, based on the total solid content of the composition.
• the composition may also include a surfactant.
• a surfactant examples include those described in paragraph 0017 of Japanese Patent No. 04502784 and paragraphs 0060 to 0071 of JP-A-2009-237362.
• the surfactant examples include a hydrocarbon surfactant, a fluorine surfactant, and a silicone surfactant. From the viewpoint of improving environmental compatibility, it is preferable that the surfactant does not contain a fluorine atom.
• the surfactant is preferably a hydrocarbon surfactant or a silicone surfactant.
• fluorine-based surfactants include, for example, Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575 and F-780 (all manufactured by DIC Corporation); EXP. MFS-324, EXP. MFS-330, EXP. MFS-578, EXP. MFS-578-2, EXP.
• fluorosurfactants include acrylic compounds that have a molecular structure containing a functional group having a fluorine atom, and when heat is applied, the functional group having the fluorine atom is cleaved and the fluorine atom is volatilized.
• fluorosurfactants include the Megafac DS series (manufactured by DIC Corporation, Chemical Daily (February 22, 2016), Nikkei Business Daily (February 23, 2016), Megafac DS-21, etc.).
• the fluorosurfactant may be a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
• the fluorosurfactant may be a block polymer.
• the fluorine-based surfactant may be a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups).
• examples of the fluorine-based surfactant include fluorine-containing polymers having a group having an ethylenically unsaturated group in the side chain, specifically, Megafac RS-101, RS-102, RS-718K and RS-72-K (all manufactured by DIC Corporation).
• fluorosurfactants from the viewpoint of improving environmental compatibility, surfactants derived from alternative materials to compounds having a linear perfluoroalkyl group with seven or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are preferred.
• PFOA perfluorooctanoic acid
• PFOS perfluorooctanesulfonic acid
• hydrocarbon surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate and glycerol ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters.
• glycerol trimethylolpropane
• trimethylolethane trimethylolethane
• propoxylates e.g., glycerol propoxylate and glycerol ethoxylate
• polyoxyethylene lauryl ether polyoxyethylene stearyl ether
• polyoxyethylene oleyl ether polyoxyethylene octylphenyl
• hydrocarbon surfactants examples include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2 and 25R2, Tetronic 304, 701, 704, 901, 904 and 150R1, and HYDROPALAT WE 3323 (all manufactured by BASF Corporation); Solsperse 20000 (manufactured by Lubrizol Japan); NCW-101, NCW-1001 and NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); Paionin D-1105, D-6112, D-6112-W and D-6315 (manufactured by Takemoto Oil Co., Ltd.); Olfine E1010, Surfynol 104, 400 and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).
• silicone surfactants include linear polymers consisting of siloxane bonds, modified siloxane polymers with organic groups introduced into the side chains and/or ends, and polymers having repeating units with hydrophilic groups in the side chains and repeating units with groups with siloxane bonds in the side chains.
• silicone surfactants polymers having repeating units with hydrophilic groups in the side chains and repeating units with groups with siloxane bonds in the side chains are preferred.
• the above polymers may be either random copolymers or block copolymers.
• the repeating unit having a group with a siloxane bond in the side chain is preferably a repeating unit represented by formula (SX1) or a repeating unit represented by formula (SX2).
• R each independently represents an alkyl group having 1 to 3 carbon atoms
• R1 represents a hydrogen atom or a methyl group
• L1 represents a single bond or a divalent organic group.
• the R's may be the same or different.
• R 1 represents a hydrogen atom or a methyl group.
• R 2 represents an alkylene group having 1 to 10 carbon atoms.
• R 3 represents an alkyl group having 1 to 4 carbon atoms.
• n represents an integer of 5 to 50.
• the repeating unit having a hydrophilic group in the side chain is preferably a repeating unit represented by formula (SX3).
• R4 and R5 each independently represent a hydrogen atom or a methyl group, n represents an integer of 1 to 4, and m represents an integer of 1 to 100.
• silicone surfactants include EXP. S-309-2, EXP. S-315, EXP. S-503-2, EXP. S-505-2 and EXP. S-506 (all manufactured by DIC Corporation); DOWSIL 8032 ADDITIVE, 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 (all manufactured by Dow Corning Toray Co., Ltd.); X-22-4952 , X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-12 1, KP-124, KP-125,
• Surfactants include nonionic surfactants.
• the surfactants may be used alone or in combination of two or more.
• the content of the surfactant is preferably from 0.01 to 3.0 mass %, more preferably from 0.01 to 1.0 mass %, and even more preferably from 0.05 to 0.8 mass %, based on the total solid content of the composition.
• the composition may also include a curing agent.
• the curing agent is not particularly limited as long as it is a compound that promotes the curing of various components contained in the composition.
• Hardeners include, for example, active ester hardeners, cyanate ester hardeners, and benzoxazine hardeners.
• active ester curing agents include EPICLON series, EXB9451, EXB9460, EXB9460S, HPC8000-65T, and EXB9416-70BK (manufactured by DIC Corporation); DC808, and YLH1026 (manufactured by Mitsubishi Chemical Corporation).
• Examples of the curing agent include those described in JP-A-2020-154325 and JP-A-2004-277460.
• the composition may contain other additives in addition to the various components described above.
• other additives include heterocyclic compounds (e.g., triazole, benzotriazole, and tetrazole, and derivatives thereof, and rust inhibitors), aliphatic thiol compounds, thermal crosslinking compounds, polymerization inhibitors, hydrogen donor compounds, solvents, impurities, plasticizers, sensitizers, alkoxysilane compounds, and maleimide compounds.
• heterocyclic compound, the aliphatic thiol compound, the thermal crosslinking compound, the polymerization inhibitor, and the hydrogen donor compound include various components described in WO 2022/039027.
• plasticizer, sensitizer, and alkoxysilane compound examples include those described in paragraphs 0097 to 0119 of WO 2018/179640.
• maleimide compound examples include known maleimide compounds and the maleimide compounds described in WO 2022/102756.
• the solvent is not particularly limited as long as it can dissolve or disperse various components other than the solvent that may be contained in the composition.
• the solvent include water, alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g., methanol and ethanol), ketone solvents (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (e.g., toluene), aprotic polar solvents (e.g., N,N-dimethylformamide), cyclic ether solvents (e.g., tetrahydrofuran), ester solvents (e.g., n-propyl acetate), amide solvents, lactone solvents, and solvents containing two or more of these.
• alcohol solvents e.g., methanol and ethanol
• ketone solvents e.g., acetone and methyl ethyl ketone
• the solvent may be used alone or in combination of two or more.
• the content of the solvent is preferably from 50 to 1,900 parts by mass, more preferably from 100 to 1,200 parts by mass, and even more preferably from 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.
• the composition may contain impurities.
• impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof.
• Halide ions, sodium ions, and potassium ions are easily mixed in as impurities, so the following contents are preferred.
• the content of the impurities is often 100 ppm by mass or less, preferably 80 ppm by mass or less, more preferably 50 ppm by mass or less, even more preferably 20 ppm by mass or less, and particularly preferably 10 ppm by mass or less, based on the total solid content of the composition.
• the lower limit is often 0 ppb by mass or more, preferably 1 ppb by mass or more, and more preferably 0.1 ppm by mass or more, based on the total solid content of the composition.
• Methods for adjusting the impurity content include, for example, a method of using raw materials with low impurity contents as raw materials for various components that may be contained in the composition, a method of purifying various components that may be contained in the composition, and a method of preventing the inclusion of impurities during preparation of the composition.
• examples of the method for adjusting the contents of sodium ions and chloride ions include a method for reducing the content of the surface modifier and a method for surface-treating the filler constituting Filler X with a surface modifier having a low content of impurities.
• the impurity content can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.
• ICP Inductively Coupled Plasma
• ion chromatography for example, a Thermo Fisher ICS-2100 is used as the analyzer, and a Thermo Fisher IonPac AS11HC column is used when the measurement target is an anion, and a Thermo Fisher IonPac CS12 column is used when the measurement target is a cation, and the measurement can be performed at a column temperature of 35°C.
• the content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane is preferably low.
• the content of each of these compounds is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less, based on the total solid content of the composition.
• the lower limit may be 10 ppb by mass or more, or 100 ppb by mass or more, based on the total solid content of the composition.
• the content of these compounds can be adjusted in the same manner as for the above-mentioned impurities, and the content of these compounds can be quantified by known measurement methods.
• a preferred embodiment of the composition is, for example, the following embodiment A.
• Aspect A It is preferable that the composition satisfies at least one of the following conditions: the composition contains a resin having a polymerizable group (preferably an ethylenically unsaturated group) and the composition contains a polymerizable compound (preferably a polymerizable compound having an ethylenically unsaturated group). In the above case, it is preferable that the composition further contains a photopolymerization initiator.
• the resin having an ethylenically unsaturated group is one aspect of the above-mentioned resin.
• the transfer film has a temporary support and a composition layer formed using the above-mentioned composition.
• FIG. 2 is a schematic cross-sectional view showing an example of an embodiment of the transfer film.
• the transfer film 100 has a configuration in which a temporary support 12, a composition layer 14, and a cover film 16 are laminated in this order.
• the transfer film 100 does not necessarily have to have the cover film 16.
• the transfer film 100 may further have an intermediate layer described later and/or a thermoplastic resin layer described later. Each component of the transfer film will be described in detail below.
• the transfer film has a temporary support.
• the temporary support is a member that supports the composition layer, and is ultimately removed by a peeling treatment.
• the temporary support may have either a single-layer structure or a multi-layer structure.
• the temporary support is preferably a film, more preferably a resin film.
• the temporary support is preferably a film that is flexible and does not significantly deform, shrink, or stretch under pressure or under pressure and heat. Examples of the film include polyethylene terephthalate film (e.g., biaxially stretched polyethylene terephthalate film, etc.), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film, and polyethylene terephthalate film is preferred.
• the temporary support preferably has no deformation such as wrinkles, scratches, or the like.
• the temporary support is preferably highly transparent, because it can be pattern-exposed through the temporary support.
• the transmittance at any wavelength of 313 nm, 365 nm, 405 nm and 436 nm is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and most preferably 90% or more.
• the upper limit is preferably less than 100%.
• Preferred values of the transmittance at any wavelength are, for example, 87%, 92% and 98%.
• the haze of the temporary support is preferably small.
• the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less.
• the lower limit is preferably 0% or more.
• the number of fine particles, foreign matter, and defects contained in the temporary support is small.
• the number of fine particles, foreign matter, and defects having a diameter of 1 ⁇ m or more in the temporary support is preferably 50 pieces/ 10 mm2 or less, more preferably 10 pieces/ 10 mm2 or less, even more preferably 3 pieces/ 10 mm2 or less, and particularly preferably 0 pieces/ 10 mm2.
• the thickness of the temporary support is preferably from 5 to 200 ⁇ m, and from the viewpoints of ease of handling and versatility, it is more preferably from 5 to 150 ⁇ m, further preferably from 5 to 50 ⁇ m, and particularly preferably from 5 to 35 ⁇ m.
• the thickness of the temporary support can be calculated as the average value of any five points measured by cross-sectional observation using a SEM (scanning electron microscope).
• the surface of the temporary support which comes into contact with the composition layer may be surface-modified by UV irradiation, corona discharge, plasma, or the like.
• the exposure dose of UV irradiation is preferably 10 to 2000 mJ/ cm2 , more preferably 50 to 1000 mJ/ cm2 .
• Examples of light sources for UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes that emit light in the wavelength range of 150 to 450 nm. The lamp power and illuminance can be adjusted as appropriate.
• Examples of the temporary support include a biaxially oriented polyethylene terephthalate film having a thickness of 16 ⁇ m, a biaxially oriented polyethylene terephthalate film having a thickness of 12 ⁇ m, and a biaxially oriented polyethylene terephthalate film having a thickness of 9 ⁇ m.
• the temporary support may be a recycled product. Examples of recycled products include those obtained by cleaning and chipping used films and forming the resulting materials into films. Examples of commercially available recycled products include the Ecouse series (manufactured by Toray Industries, Inc.).
• Examples of temporary supports include those described in paragraphs 0017 to 0018 of JP 2014-085643 A, paragraphs 0019 to 0026 of JP 2016-027363 A, paragraphs 0041 to 0057 of WO 2012/081680 A, and paragraphs 0029 to 0040 of WO 2018/179370 A, the contents of which are incorporated herein by reference.
• the temporary support may have a layer containing fine particles (lubricant layer) on one or both sides of the temporary support in order to provide handleability.
• the average diameter of the fine particles contained in the lubricant layer is preferably 0.05 to 0.8 ⁇ m.
• the thickness of the lubricant layer is preferably 0.05 to 1.0 ⁇ m.
• temporary supports include, for example, Lumirror 16FB40, Lumirror 16KS40, Lumirror #38-U48, Lumirror #75-U34, and Lumirror #25T60 (all manufactured by Toray Industries, Inc.); and Cosmoshine A4100, Cosmoshine A4160, Cosmoshine A4300, Cosmoshine A4360, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).
• composition layer is a layer formed using the above-mentioned composition.
• various components that may be contained in the composition layer include various components other than the solvent that may be contained in the composition.
• the preferred numerical range of the content of each component in the composition layer is the same as the preferred range obtained by replacing the above "content (% by mass) of each component relative to the total solid content of the composition” with “content (% by mass) of each component relative to the total mass of the composition layer.”
• the resin content is preferably 5.0% by mass or more relative to the total solid content of the composition” should be replaced with "The resin content is preferably 5.0% by mass or more relative to the total mass of the composition layer.”
• the average thickness of the composition layer is preferably 0.5 to 40 ⁇ m, more preferably 0.5 to 25 ⁇ m, and even more preferably 3 to 20 ⁇ m. When the average thickness of the composition layer is 40 ⁇ m or less, this is preferred in terms of excellent pattern resolution. When the average thickness of the composition layer is 0.5 ⁇ m or more, this is preferred in terms of excellent reliability.
• the transfer film may have an intermediate layer and/or a thermoplastic resin layer.
• the transfer film preferably has the intermediate layer and/or the thermoplastic resin layer between the temporary support and the composition layer.
• the intermediate layer and the thermoplastic resin layer are described, for example, in paragraphs 0164 to 0204 of WO 2021/166719, the contents of which are incorporated herein by reference.
• the transfer film may have a cover film.
• the number of fish eyes having a diameter of 80 ⁇ m or more contained in the cover film is preferably 5 or less per square meter, more preferably 0 or less per square meter.
• Fish eyes are foreign matter, unmelted matter, and/or oxidized deterioration products of the material that are introduced into the film when the material is thermally melted and the film is produced by a method such as kneading, extrusion and/or biaxial stretching and casting.
• the number of particles having a diameter of 3 ⁇ m or more contained in the cover film is preferably 30 pieces/ mm2 or less , more preferably 10 pieces/mm2 or less, even more preferably 5 pieces/ mm2 or less, and particularly preferably 0 pieces/mm2 or less. This makes it possible to suppress defects caused by unevenness due to the particles contained in the cover film being transferred to the composition layer.
• the arithmetic mean roughness Ra of the surface of the cover film is preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, and even more preferably 0.03 ⁇ m or more. If Ra is within the above range, for example, when the transfer film is long, the winding property of the transfer film is excellent. Furthermore, from the viewpoint of suppressing defects during transfer, the arithmetic mean roughness Ra is preferably less than 0.50 ⁇ m, more preferably 0.40 ⁇ m or less, and even more preferably 0.30 ⁇ m or less.
• cover film examples include a polyethylene terephthalate film, a polypropylene film, a polystyrene film, and a polycarbonate film.
• cover film examples include those described in paragraphs 0083 to 0087 and 0093 of JP-A-2006-259138.
• the cover film examples include Alphan (registered trademark) FG-201 (manufactured by Oji F-Tex Co., Ltd.), Alphan (registered trademark) E-201F (manufactured by Oji F-Tex Co., Ltd.), Therapeel (registered trademark) 25WZ (manufactured by Toray Advanced Film Co., Ltd.), and Lumirror (registered trademark) 16QS62 (16KS40) (manufactured by Toray Industries, Inc.).
• the cover film may be a recycled product.
• a recycled product may be a product obtained by cleaning and chipping a used film, and then forming the obtained material into a film.
• a commercially available recycled product may be the Ecouse series (manufactured by Toray Industries, Inc.).
• the transfer film may have other layers in addition to the layers described above.
• Other layers include, for example, high refractive index layers.
• high refractive index layers include those described in paragraphs 0168 to 0188 of WO 2021/187549, the contents of which are incorporated herein by reference.
• the transfer film can be produced by a known production method.
• a preferred method for producing the transfer film is to coat a composition on a temporary support to form a composition layer.
• the method for producing the transfer film includes a method including a step of applying a composition to the surface of a temporary support to form a coating film, and drying the coating film to form a composition layer. It is also preferable that the method for producing the transfer film further includes a step of pressing a cover film onto the obtained composition layer.
• the obtained transfer film may be wound up and stored in a roll form. If it is in a roll form, it can be provided in that form for the lamination step with the substrate in a roll-to-roll system.
• the transfer film may have an intermediate layer and/or a thermoplastic resin layer.
• the composition for forming an intermediate layer the method for forming an intermediate layer, the composition for forming a thermoplastic resin layer, and the method for forming a thermoplastic resin layer are described in paragraphs 0133 to 0136 and 0143 to 0144 of International Publication No. 2021/033451, the contents of which are incorporated herein by reference.
• composition layer for example, a method of forming the composition by applying and drying the composition.
• the composition is the composition of the present invention described above.
• the coating method examples include slit coating, spin coating, curtain coating, and inkjet coating.
• the composition preferably further contains a solvent.
• the solvent has the same meaning as the solvent that the composition may contain, and the preferred embodiments are also the same.
• the pattern (film) obtained from the composition layer formed by using the composition or the transfer film can be used in various applications, such as electrode protective films, insulating films, planarizing films, overcoat films, hard coat films, passivation films, partitions, spacers, microlenses, optical filters, anti-reflection films, etching resists, and plating members. More specifically, examples of the material include protective or insulating films for touch panel electrodes, protective or insulating films for printed wiring boards, protective or insulating films for TFT substrates, interlayer insulating films in build-up substrates for semiconductor packages, organic interposers, color filters, overcoat films for color filters, and etching resists and plating members for wiring formation.
• the method for producing the laminate is not particularly limited as long as it is a method using the composition or the transfer film.
• Examples of the method for producing the laminate include known production methods such as a production method for a build-up substrate, and a production method including steps Z1 to Z3 is preferable, and a production method including steps Z1 to Z4 is more preferable.
• Step Z1 a step of forming a composition layer on a substrate using a composition or a transfer film
• Step Z2 a step of forming a pattern having vias in the composition layer
• Step Z3 a step of heating or exposing the pattern
• Step Z4 a step of forming a circuit pattern on the obtained pattern.
• the method for producing a laminate includes steps Z1 to Z4, and further includes step Z5 of forming a composition layer on the laminate produced by step Z4 using a composition or a transfer film, and it is preferable that steps Z2 to Z5 are repeatedly performed.
• Step Z1 is a step of forming a composition layer on a substrate using a composition or a transfer film.
• the step Z1 is preferably a step of applying the composition to the substrate to form a composition layer.
• the composition application method include the method for forming the composition layer in the method for producing the transfer film described above.
• the step Z1 is preferably a step of contacting the surface of the composition layer in the transfer film opposite to the temporary support side with the substrate to bond the transfer film to the substrate.
• Examples of the bonding method of the transfer film include known transfer methods and methods using known laminators such as laminators, vacuum laminators, and autocut laminators, and a method of applying pressure and heat with a roll or the like is preferred.
• the lamination temperature is preferably 70 to 130°C.
• step Z1 is carried out after peeling the cover film from the transfer film.
• the substrate examples include a glass substrate, a glass epoxy substrate, a silicon substrate, a resin substrate, and a substrate having a conductive layer, with a substrate having a conductive layer being preferred.
• the substrate may be a light-transmitting substrate such as a glass substrate, and may be, for example, reinforced glass such as Gorilla Glass manufactured by Corning Inc. Examples of materials contained in the substrate include those described in JP-A-2010-086684, JP-A-2010-152809, and JP-A-2010-257492.
• the resin substrate is preferably a resin film having small optical distortion and/or high transparency, and specific examples thereof include polyester, polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, cycloolefin polymer, and polyimide.
• a resin substrate having a conductive layer is preferable, and a resin film having a conductive layer is more preferable, in that it can be produced by a roll-to-roll process.
• the substrate having a conductive layer may be a laminate obtained by the above-mentioned method for producing a laminate.
• the conductive layer may be, for example, a known conductive layer used for circuit wiring or touch panel wiring.
• a metal layer e.g., metal foil, etc.
• a conductive metal oxide layer e.g., graphene layer
• a carbon nanotube layer e.g., graphene layer
• a conductive polymer layer e.g., polystyrene layer
• a metal layer is more preferred
• a copper layer or a silver layer is even more preferred.
• the conductive layer may be one or more layers.
• the conductive layer may be used alone or in combination of two or more types. Examples of materials for the conductive layer include elemental metals and conductive metal oxides.
• Examples of elemental metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au.
• conductive metal oxides include ITO (indium tin oxide), IZO (indium zinc oxide) and SiO 2. Conductive means that the volume resistivity is less than 1 ⁇ 10 6 ⁇ cm, and preferably the volume resistivity is less than 1 ⁇ 10 4 ⁇ cm.
• the conductive layer may be in a pattern.
• methods for producing a patterned conductive layer include subtractive methods and additive methods such as etching.
• Examples of the etching method include the wet etching method described in paragraphs 0048 to 0054 of JP2010-152155A and known dry etching methods such as plasma etching.
• the etching method may also be a method using an etching resist.
• Step Z2 is a step of forming a pattern having vias in the composition layer.
• the pattern having vias may be formed only in the composition layer, or may be formed in both the composition layer and the substrate.
• Methods for forming a pattern having vias include, for example, methods using a drill, a laser, and plasma.
• the method for forming a pattern having vias preferably includes a step of exposing the composition layer to a pattern, a step of developing the exposed composition layer with a developer to form a pattern, and a step of etching the conductive layer in the region where the pattern is not arranged.
• the composition layer may be exposed from the side opposite to the substrate, or from the substrate side of the composition layer.
• the composition for forming the photosensitive composition layer the above-mentioned embodiment A is preferable.
• the light source used for exposure may be any light source that irradiates light in a wavelength range to which various photosensitive components in the composition layer (e.g., a resin, a polymerizable compound, a photopolymerization initiator, a photoacid generator, etc.) are sensitive (e.g., light in a wavelength range of 254 nm, 313 nm, 365 nm, 405 nm, etc.).
• various photosensitive components in the composition layer e.g., a resin, a polymerizable compound, a photopolymerization initiator, a photoacid generator, etc.
• Specific examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes).
• the exposure dose is preferably from 5 to 200 mJ/ cm2 , and more preferably from 10 to 200 mJ/ cm2 .
• step 2 exposure may be carried out after the temporary support is peeled off, or exposure may be carried out through the temporary support before the temporary support is peeled off, and then the temporary support may be peeled off.
• the pattern exposure may be exposure through a mask or direct exposure using a laser or the like.
• the mask include a quartz mask, a soda lime glass mask, and a film mask.
• the quartz mask is preferred because it has excellent dimensional accuracy, and the film mask is preferred because it can be easily made large in size.
• the material of the film mask is preferably a polyester film, more preferably a polyethylene terephthalate film, for example, XPR-7S SG (manufactured by Fujifilm Global Graphic Systems Co., Ltd.).
• the pattern having vias may be either through holes or via holes.
• the shape of the via in the pattern can be, for example, a rectangle, a trapezoid, or an inverted trapezoid in cross-sectional shape; and a circle or a rectangle in front shape (the shape of the via when observed from a direction in which the via bottom is visible).
• An inverted trapezoid is preferred as the cross-sectional shape because it increases the adhesion of plated copper to the via wall surface.
• the via size (diameter) is preferably 300 ⁇ m or less, more preferably 100 ⁇ m or less, further preferably 50 ⁇ m or less, and particularly preferably 5 ⁇ m or less.
• the lower limit is preferably 1 ⁇ m or more.
• the number of the vias may be one or more, and is preferably two or more.
• Step Z3 is a step of heating or exposing the composition layer.
• Step Z3 is preferably a step of curing the composition layer.
• the heating temperature is preferably 100 to 300° C., and the heating time is preferably 10 minutes to 10 hours.
• the exposure method may be, for example, the exposure method in step Z2.
• Step Z4 is a step of forming a circuit pattern on the pattern.
• a semi-additive process is preferred because it allows the formation of fine wiring.
• a seed layer is first formed by electroless copper plating using a palladium catalyst or the like on the via bottoms, via wall surfaces, and the entire surface of a pattern having vias.
• the seed layer is for forming a power supply layer for electrolytic copper plating, and the thickness of the seed layer is preferably 0.1 to 2.0 ⁇ m.
• the electroless copper plating process is carried out by reacting copper ions with a reducing agent to deposit metallic copper on the surface of a pattern having vias. Examples of the electroless plating process and the electrolytic plating process include known plating processes.
• the catalyst for the electroless plating process is preferably a palladium-tin mixed catalyst.
• the average primary particle size of the mixed catalyst is preferably 10 nm or less.
• the plating solution for the electroless plating process preferably contains hypophosphorous acid (reducing agent).
• Examples of electroless copper plating solutions include "MSK-DK” manufactured by Atotech Japan and “ThruCup (registered trademark) PEA ver. 4" series manufactured by Uemura Kogyo Co., Ltd.
• the method for producing the laminate may include a roughening step of roughening the pattern having the vias.
• the roughening step is preferably performed after the step Z3 and before the step Z4.
• the roughening step may be, for example, a known desmear treatment, and is preferably a treatment in which a roughening liquid is brought into contact with the surface.
• the roughening solution examples include a roughening solution containing chromium and sulfuric acid, a roughening solution containing an alkaline permanganate (such as a sodium permanganate roughening solution), and a roughening solution containing sodium fluoride, chromium, and sulfuric acid.
• a roughening solution containing chromium and sulfuric acid examples include a roughening solution containing chromium and sulfuric acid, a roughening solution containing an alkaline permanganate (such as a sodium permanganate roughening solution), and a roughening solution containing sodium fluoride, chromium, and sulfuric acid.
• the heating temperature is preferably 150 to 240° C., and the heating time is preferably 15 to 500 minutes.
• the laminate is a laminate obtained by the above-mentioned method for producing a laminate.
• the cured film may be used as an insulating film, or may be used as an organic interposer or insulating film in a so-called build-up substrate.
• the laminate is used, for example, in semiconductor devices, including various semiconductor devices such as semiconductor packages used in electrical appliances (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, aircraft, etc.).
• the cured film is a film formed by curing the above-mentioned composition.
• the curing method may be, for example, the heating method and the exposure method in step Z3.
• the composition for forming the cured film is not particularly limited as long as it is the composition described above, but it preferably contains at least one type selected from the group consisting of phenolic resins and epoxy resins.
• ⁇ resin ⁇ A-1 Phenol resin, TR4020G, manufactured by Asahi Organic Chemicals Co., Ltd.
• A-2 Epoxy resin, ZX1059 (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (1:1)), manufactured by Nippon Steel Chemical Co., Ltd.
• A-3 Polyphenylene ether resin having a branched structure, synthesized by the following method.
• 1.3 g of di- ⁇ -hydroxo-bis[(N,N,N',N'-tetramethylethylenediamine)copper(II)] chloride (Cu/TMEDA) and 1.59 mL of tetramethylethylenediamine (TMEDA) were added and thoroughly dissolved, and oxygen was supplied at 10 mL/min. 52.5 g of 2,6-dimethylphenol and 6.5 g of 2-allylphenol were dissolved in 0.75 L of toluene to prepare a raw material solution.
• A-4 Silicone resin, organopolysiloxane having 0.23 moles of vinyl groups per 100 g and a viscosity of 2,000 mPa ⁇ s, represented by the average unit formula M 2 D 3 M: (CH 2 ⁇ CH)(CH 3 )(C 6 H 5 )SiO 1/2 D: (C 6 H 5 ) 2 SiO 2/2
• ⁇ A-5 Benzocyclobutene resin, cyclotene resin XUR-JW-1148-200201415-47, manufactured by The Dow Chemical Company
• a mixture was prepared by placing 1-methoxy-2-acetoxypropane (PGMEA, 60 parts) and propylene glycol monomethyl ether (PGME, 240 parts by mass) in a 2000 mL flask. The mixture was heated to 90° C. while being stirred at a stirring speed of 250 rpm.
• PGMEA 1-methoxy-2-acetoxypropane
• PGME propylene glycol monomethyl ether
• V-601 (dimethyl 2,2'-azobis(2-methylpropionate), 9.637 parts by mass) was dissolved in PGMEA (136.56 parts by mass) to obtain the dropping liquid (2).
• the dropping liquid (1) and the dropping liquid (2) were simultaneously dropped over 3 hours into a 2000 mL flask containing the above mixed liquid heated to 90° C.
• V-601 (2.401 parts by mass) was added to the flask three times every hour. Then, the mixture was stirred at 90° C. for another 3 hours. Then, the reaction liquid obtained in the flask was diluted with PGMEA to obtain a solution containing Resin A-6 (solid concentration 36.3% by mass).
• a dropping liquid (1) methyl methacrylate (40 parts by mass), dicyclopentanyl methacrylate (40 parts by mass), and methacrylic acid (20 parts by mass) were mixed and diluted with PGMEA (60 parts) to obtain a dropping liquid (1).
• PGMEA g., 1,3-azobis(2-methylpropionate), 9.637 parts by mass
• PGMEA 136.56 parts by mass
• A-8 Liquid crystal polymer (liquid crystal polyester), synthesized by the following method.
• a 2.5L reaction vessel equipped with a stirring blade and a distillation tube 435g of p-hydroxybenzoic acid, 164g of 4,4'-dihydroxybiphenyl, 44g of hydroquinone, 146g of terephthalic acid, 78g of isophthalic acid and 684g of acetic anhydride were charged, and the mixture was reacted at 150°C for 2.5 hours while stirring under a nitrogen gas atmosphere, and then heated to 300°C in 3.5 hours. Thereafter, the polymerization temperature was maintained at 300°C, the pressure was reduced to 1.0mmHg in 1.0 hour, and the reaction was continued for another 2 hours. Next, the inside of the reaction vessel was pressurized to 0.12MPa, and Resin A-8 was discharged into a strand-like material to obtain Resin A-8.
• NHM-5N Silicon dioxide (spherical silica), surface-treated product, manufactured by Tokuyama Corporation.
• NHM-4N Silicon dioxide (spherical silica), surface-treated product, manufactured by Tokuyama Corporation.
• NHM-3N Silicon dioxide (spherical silica), surface-treated product, manufactured by Tokuyama Corporation.
• NHM-24D Silicon dioxide (spherical silica), surface-treated product, manufactured by Tokuyama Corporation.
• NP-5N Silicon dioxide (spherical silica), surface-treated product, manufactured by Tokuyama Corporation.
• NP-4N Silicon dioxide (spherical silica), surface-treated product, manufactured by Tokuyama Corporation.
• NP-3N Silicon dioxide (spherical silica), surface-treated product, manufactured by Tokuyama Corporation.
• NP-24D Silicon dioxide (spherical silica), surface-treated product, manufactured by Tokuyama Corporation.
• YA 050C-MJE silicon dioxide (spherical silica slurry), surface-treated product, MEK slurry with solid content of 50% by mass, manufactured by Admatechs Co., Ltd.
• Y50SP-AM1 silicon dioxide (spherical silica slurry), surface-treated product, manufactured by Admatechs Co., Ltd.
• Y50SZ-AM1 silicon dioxide (spherical silica slurry), surface-treated product, manufactured by Admatechs Co., Ltd.
• MEK-ST-ZL silicon dioxide (spherical silica slurry), surface-treated product, manufactured by Nissan Chemical Co., Ltd.
• MEK-ST-L silicon dioxide (spherical silica slurry), surface-treated product, manufactured by Nissan Chemical Co., Ltd.
• MEK-EC-2130Y silicon dioxide (spherical silica slurry), surface-treated product, manufactured by Nissan Chemical Co., Ltd.
• SO-C2 silicon dioxide (spherical silica), surface untreated, manufactured by Admatechs Co., Ltd.
• Pre-adjusted product A filler prepared by the following method. 10 g of silica extracted from PGM-ST (silicon dioxide (spherical silica), surface untreated, manufactured by Nissan Chemical Co., Ltd.) using centrifugation and a filter was mixed with 39 g of NMP and 1 g of 3-methacryloxypropyltrimethoxysilane and ultrasonically dispersed while stirring to prepare pre-adjusted product A.
• PGM-ST Silicon dioxide (spherical silica), untreated surface, manufactured by Nissan Chemical Industries, Ltd.
• [Polymerizable compound] SR205NS The following compound, manufactured by Sartomer Corporation SR209: The following compound, manufactured by Sartomer Corporation DPHA: Dipentaerythritol hexaacrylate, manufactured by Tokyo Chemical Industry Co., Ltd.
• S-506 Silicone-based surfactant, manufactured by DIC Corporation
• F-551A Megafac (registered trademark) F551A, fluorine-based surfactant, manufactured by DIC Corporation
• HAT 5-amino-1H-tetrazole ATA: 3-amino-1,2,4-triazole
• the structures represented by any one of formulas (a) to (e) are the same as the structures described in paragraphs 0072 to 0076 of JP 2020-026502 A.
• Platinum catalyst hydrosilylation agent, platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex diluted in polysiloxane (platinum content: 1% by mass)
• MIR-500-60T isopropylidene group-containing maleimide compound, toluene solution
• compositions of the Examples and Comparative Examples were applied onto a glass substrate and dried to form a coating film having a thickness of 4.0 ⁇ m.
• a cross section was cut out along the normal direction of the surface of the obtained coating film, and the cross section was observed under a scanning electron microscope.
• the major axes of all fillers (filler X or comparative filler) observed within an area having a length of 3 ⁇ m in the vertical direction parallel to the thickness direction of the coating film and a length of 10 ⁇ m in the horizontal direction perpendicular to the vertical direction were measured.
• the above operation was carried out at five different locations on the coating film, and the average (arithmetic mean) of the major axis lengths of all the fillers (filler X or comparative filler) measured in each operation was taken as the average particle size of the filler.
• the coating film was heated at 220° C. for 5 hours, and then the average particle diameter was measured in the same manner as described above. The average particle diameter was found to be the same as the average particle diameter before the heat treatment.
• the weight loss rate of the filler for measurement was measured three times using a TG-DTA device (TG/DTA7300) manufactured by Hitachi High-Tech Science Corporation under the condition of heating from room temperature to 1000° C. (10° C./min) in an air atmosphere, and the content of the surface modifier (value relative to the total solid content of the composition) was calculated from the arithmetic average value.
• Each composition (1 g) was dissolved in acetone and then diluted with ultrapure water to prepare an acetone:ultrapure water ratio of 1:9. The supernatant of the solution was subjected to ion chromatography to measure the Na + and Cl - contents (values relative to the total solid content of the composition).
• the analyzer was a Thermo Fisher ICS-2100, and the columns used were an IonPac AS11HC manufactured by Thermo Fisher for Cl - and an IonPac CS12 manufactured by Thermo Fisher for Na + , with the column temperature set to 35°C.
• Method X A copper-clad polyimide film (Metalloyal, manufactured by Toray Industries, Inc.) was used as a substrate, and the composition shown in the table was applied and dried on the substrate to obtain a laminate having a composition layer of 10.0 ⁇ m thickness on the substrate.
• Metalloyal manufactured by Toray Industries, Inc.
• the obtained laminate was exposed to light (high pressure mercury lamp, cumulative illuminance measured with a 365 nm wavelength illuminometer: 100 mJ/cm 2 ) from the side opposite to the substrate side of the composition layer, and then heated in an oven (220° C., 5 hours), and then immersed in 2M hydrochloric acid for 8 hours for peeling treatment, rinsed (pure water at room temperature for 1 hour), and then peeled off from the substrate to obtain a free-standing film derived from the composition layer. If the free-standing film could not be peeled off by the above peeling treatment, it was further immersed in 2M hydrochloric acid for about 1 week to peel off. The obtained free-standing film was cut into strips to obtain a measurement sample.
• Method Y A copper-clad polyimide film (Metalloyal, manufactured by Toray Industries, Inc.) was used as a substrate, and the composition shown in the table was applied and dried on the substrate to obtain a laminate having a composition layer of 10.0 ⁇ m thickness on the substrate.
• the obtained laminate was heated in an oven (220° C., 5 hours), then immersed in 2M hydrochloric acid for 8 hours for peeling treatment, rinsed (pure water at room temperature for 1 hour), and then peeled off from the substrate to obtain a free-standing film derived from the composition layer. If the free-standing film could not be peeled off by the above peeling treatment, it was further immersed in 2M hydrochloric acid for about 1 week to peel off. The obtained free-standing film was cut into strips to obtain a measurement sample.
• Dielectric loss Z is 0.0025 or less
• Dielectric loss Z is greater than 0.0025 and less than 0.0050
• C Dielectric loss Z is greater than 0.0050
• the composition contains a photopolymerization initiator
• the obtained composition layer was exposed to light using an ultra-high pressure mercury lamp.
• the integrated exposure dose measured with a 365 nm wavelength illuminometer was 100 mJ/cm 2.
• the layer was heat-treated at 220° C. for 300 minutes in a nitrogen atmosphere to prepare an evaluation sample.
• the obtained composition layer was subjected to a heat treatment at 220° C. for 300 minutes in a nitrogen atmosphere to prepare an evaluation sample.
• Ten evaluation samples were prepared, and each evaluation sample was placed in a chamber at 130°C and 85% RH (relative humidity) using a HAST (highly accelerated life test) machine to check whether migration occurred within 96 hours when a voltage of 10 V was applied. Note that in evaluation samples whose initial resistance value when first measured at room temperature (23°C) was 1 ⁇ 10 ⁇ or more, migration was deemed to have occurred when the resistance value became 1 ⁇ 10 ⁇ or less.
• A The number of measurement samples in which migration occurred was 0 or 1.
• B The number of measurement samples in which migration occurred was 2 or 3.
• C The number of measurement samples in which migration occurred was 4 or 5.
• D The number of measurement samples in which migration occurred was 6 or 7.
• E The number of measurement samples in which migration occurred was 8 to 10.
• the contents of each component and the evaluation results are shown below.
• the column “Content in solids” indicates the solids concentration (mass %) of various components relative to the total solids in the composition.
• the column “Surface modifier content” indicates the content (mass %) of the surface modifier relative to the total mass of Filler X.
• the “Na + content (ppm by mass)” column indicates the content (ppm by mass) of sodium ions relative to the total solid content in the composition.
• the column “ Cl content (ppm by mass)” indicates the content (ppm by mass) of chloride ions relative to the total solid content in the composition.
• the composition of the present invention has excellent dielectric properties and excellent migration resistance. It was confirmed that when the average particle size of the filler X is 150 nm or less, the migration resistance is superior (Examples 1 to 13, etc.). It was confirmed that when the content of the surface modifier is 2.5 mass % or less relative to the total mass of Filler X, both the dielectric properties and migration resistance are superior (Examples 1 to 14, etc.).
• a transfer film prepared by the following procedure was used to form a composition layer on a substrate, and the same evaluations as for the above composition were performed, and the same evaluation results as for the composition were obtained.
• the compositions shown in the table were applied onto a temporary support (PET film, Lumirror 16FB40, thickness 16 ⁇ m, manufactured by Toray Industries, Inc.) and dried to form a composition layer having a thickness of 10.0 ⁇ m.
• a cover film polypropylene film, FG-201, thickness 30 ⁇ m, manufactured by Oji F-Tex Co., Ltd.
• the cover film was peeled off from the transfer film obtained above, and the exposed composition layer was laminated on the substrate for various evaluations to form a composition layer.
• the lamination was performed using a vacuum laminator (manufactured by MCK Corporation) under the conditions of substrate temperature: 40°C, rubber roller temperature: 100°C, linear pressure: 3N/cm, and conveying speed: 2m/min.
• the temporary support was peeled off from the obtained sample. After that, various evaluations were performed in the same procedure as the above composition, and the same results were obtained.
• the transfer film of each example was laminated on both sides of a glass epoxy substrate (CCL-EL190T, thickness 1.0 mm, manufactured by Mitsubishi Gas Chemical Co., Ltd.) on which a circuit pattern was formed, and composition layers were formed on both sides of the glass epoxy substrate.
• a vacuum laminator was used for this. The lamination was performed using a vacuum laminator manufactured by MCK Corporation under the following conditions: substrate temperature: 40°C, rubber roller temperature: 100°C, linear pressure: 3 N/cm, and conveying speed: 2 m/min.
• a pattern having a via with a diameter of ⁇ 60 ⁇ m was formed at a predetermined position on the composition layer, and then the pattern was heated.
• the residue was removed using a sodium permanganate aqueous solution as a roughening solution, and electroless plating was performed.
• a resist pattern was formed at a predetermined position using a known dry film resist, and electrolytic plating was performed.
• the resist pattern was peeled off using a peeling solution.
• a seed layer etching process was performed, followed by a heat treatment (200° C., 1 hour) to form copper wiring on the cured film.
• the above steps from lamination to heat treatment were repeated three times, and finally a solder resist was formed as the outermost layer, and a semiconductor element was sealed and mounted to produce a semiconductor package.
• the obtained semiconductor package was mounted at a predetermined position on a printed wiring board to obtain a semiconductor package substrate. It was confirmed that the obtained semiconductor package substrate operated normally.

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