Composition, transfer film, method for producing laminate, laminate, and cured film

Abstract

The present invention addresses the problem of providing: a composition from which a film having excellent dielectric properties and excellent migration resistance can be formed; a transfer film; a method for producing a laminate; a laminate; and a cured film. A composition according to the present invention comprises a resin and a filler X that is surface-modified with a surface modifier, wherein the content of the filler X is at least 50.0 mass% with respect to the total solid content of the composition, the average particle size of the filler X is at most 300 nm, and the content of the surface modifier is at most 3.0 mass% with respect to the total mass of the filler X.

Description

Composition, transfer film, method for producing laminate, laminate, cured film

[0001] The present invention relates to a composition, a transfer film, a method for producing a laminate, a laminate, and a cured film.

[0002] In display devices (e.g., organic electroluminescence (EL) display devices and liquid crystal display devices) equipped with a touch panel such as a capacitance-type input device, conductive patterns such as an electrode pattern corresponding to a sensor in a visual recognition area, and wiring for a peripheral wiring portion and an extraction wiring portion are provided inside the touch panel. In addition, in a multilayer printed wiring board, an insulating film is provided between each layer.

[0003] As a composition for forming an insulating film, for example, Patent Document 1 discloses an epoxy resin composition having a predetermined structure.

[0004] Japanese Patent Application Laid-Open No. 2007-254709

[0005] The present inventors have found that when a film is formed using a composition having the structure described in Patent Document 1, it is difficult to obtain a film having both good dielectric properties and migration resistance.

[0006] Therefore, an object of the present invention is to provide a composition capable of forming a film having excellent dielectric properties and excellent migration resistance, as well as a transfer film, a method for producing a laminate, a laminate, and a cured film relating to the composition.

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by the following configuration, and have completed the present invention.

[0008] [1] A composition comprising a resin and a filler X surface-modified with a surface modifier, wherein the content of the filler X is 50.0% by 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, and the content of the surface modifier is 3.0% by mass or less, based on the total mass of the filler X. [2] The composition according to [1], wherein the filler X comprises at least one selected from the group consisting of silicon dioxide, boron nitride, barium sulfate, and silicates. [3] The composition according to [1] or [2], wherein the average particle size of the filler X is 150 nm or less. [4] The composition according to any one of [1] to [3], wherein the content of the filler X is 90.0% by mass or less, based on the total solid content of the composition. [5] The composition according to any one of [1] to [4], wherein the content of the surface modifier is 2.5% by mass or less, based on the total mass of the filler X. [6] The composition according to any one of [1] to [5], wherein 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, polybenzimidazole, polyphenylsulfone, polycarbonate, an acrylonitrile-butadiene-styrene resin, and polyphenylene sulfide. [7] The composition according to any one of [1] to [6], wherein the resin comprises at least one selected from the group consisting of a phenolic resin and an epoxy resin. [8] The composition according to any one of [1] to [7], further comprising no sodium ions, or, if sodium ions are contained, the content of the sodium ions is 50 ppm by mass or less based on the total solid content of the composition. [9] The composition according to any one of [1] to [8], further comprising no chloride ions, or, if it comprises chloride ions, the content of the chloride ions is 50 ppm by mass or less relative to the total solid content of the composition.

[10] The composition according to any one of [1] to [9], which satisfies at least one of the following conditions: containing the resin having an ethylenically unsaturated group; and containing a polymerizable compound having an ethylenically unsaturated group.

[11] The composition according to

[10] , which further contains a photopolymerization initiator.

[12] A transfer film having a temporary support and a composition layer formed using the composition according to any one of [1] to

[11] .

[13] A method for producing a laminate, comprising the steps of: forming a composition layer on a substrate using the composition according to any one of [1] to

[11] ; forming a pattern having vias in the composition layer; and heating or exposing the pattern.

[14] A laminate produced by the method for producing a laminate according to

[13] .

[15] A cured film obtained by curing the composition according to [7].

[0009] The present invention provides a composition capable of forming a film having excellent dielectric properties and excellent migration resistance. It also provides a transfer film, a method for producing a laminate, a laminate, and a cured film relating to the composition.

[0010] 1 is a diagram (nomograph) illustrating a method for measuring the boiling point of compound Y. FIG. 2 is a schematic diagram illustrating an example of a layer structure of a transfer film.

[0011] The present invention will be described in detail below. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In addition, in the numerical ranges described in stages in this specification, 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 stages. In addition, in the numerical ranges described in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with a value shown in the examples.

[0012] Furthermore, the term "process" in this specification does not only refer to an independent process, but also includes a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.

[0013] In this specification, unless otherwise specified, the temperature condition may be 25° C. For example, the temperature when performing each of the above steps may be 25° C. unless otherwise specified.

[0014] In this specification, "transparent" means that the average transmittance of visible light in the wavelength range 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.

[0015] In this specification, "actinic rays" or "radiation" refers to the bright line spectrum of a mercury lamp, such as g-line, h-line, and i-line, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and electron beams (EB). "Light" refers to actinic rays or radiation.

[0016] In this specification, unless otherwise specified, "exposure" includes not only exposure using far ultraviolet light typified by mercury lamps, excimer lasers, extreme ultraviolet light, X-rays, EUV light, and the like, but also exposure using particle beams such as electron beams and ion beams.

[0017] In this specification, unless otherwise specified, the refractive index is a value measured by an ellipsometer at a wavelength of 550 nm.

[0018] In this specification, unless otherwise specified, when a molecular weight distribution exists, the molecular weight is the weight average molecular weight (Mw). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values ​​determined by gel permeation chromatography (GPC) in terms of polystyrene.

[0019] In this specification, "(meth)acrylic acid" is a concept that encompasses both acrylic acid and methacrylic acid, "(meth)acryloyl group" is a concept that encompasses both acryloyl group and methacryloyl group, "(meth)acrylate" is a concept that encompasses both acrylate and methacrylate, and "(meth)acrylic resin" is a concept that encompasses both acrylic resin and methacrylic resin.

[0020] In this specification, "water-soluble" means that the solubility in 100 g of water at a liquid temperature of 22°C and a pH of 7.0 is 0.1 g or more.

[0021] The "solid content" of a composition refers to components that form a composition layer formed using the composition, and when the composition contains a solvent (e.g., an organic solvent, water, etc.), it refers to all components excluding the solvent. Furthermore, liquid components that form a composition layer are also considered to be solid content.

[0022] In this specification, unless otherwise specified, the layer thickness is the average thickness measured using a scanning electron microscope (SEM) for thicknesses of 0.5 μm or more, and the average thickness measured using a transmission electron microscope (TEM) for thicknesses of less than 0.5 μm. The average thickness is obtained by cutting a sample to be measured using an ultramicrotome, measuring the thickness at any five points, and calculating the arithmetic average of the thicknesses.

[0023] [Composition] The composition of the present invention is a composition comprising a resin and a filler X whose surface has been modified with a surface modifier, wherein the content of the filler X is 50.0 mass % or more relative to the total solid content of the composition, the average particle size of the filler X is 300 nm or less, and the content of the surface modifier is 3.0 mass % or less relative to the total mass of the filler X.

[0024] Although the detailed mechanism of action of the composition of the present invention is not clear, the inventors speculate as follows. Because the composition of the present invention contains a characteristic filler X, it is speculated that the dielectric properties and migration resistance of a film obtained using the composition of the present invention are excellent. Furthermore, because the composition of the present invention contains a resin, the above 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 is also referred to as "the effect of the present invention being superior."

[0025] The various components that may be contained in the composition of the present invention are described in detail below.

[0026] [Resin] The composition contains 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 even more preferably a (meth)acryloyl group. Unless otherwise specified, the resin may be either an unmodified product or a modified product. For example, 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.

[0027] Examples of the resin include known resins. The resin preferably contains 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, polyethersulfone, polyarylate, polyetherimide, polybenzimidazole, polyphenylsulfone, polycarbonate, an acrylonitrile-butadiene-styrene resin (ABS resin), and polyphenylene sulfide, more preferably contains 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, further preferably contains 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 (meth)acrylic resin, and a liquid crystal polymer, and particularly preferably contains at least one selected from the group consisting of a phenolic resin and an epoxy resin, in terms of ease of obtaining a cured film.

[0028] The phenolic resin is a resin having a phenolic hydroxyl group. Examples of the phenolic resin include phenol novolac resin, cresol novolac resin, biphenyl aralkyl phenolic resin, naphthol aralkyl resin, and naphthol novolac resin. Examples of the phenolic resin 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, and 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-7851-H, MEHC-7800-4S, MEH C-7800-SS, MEHC-7800-S, MEHC-7800-M and MEHC-7800-H, manufactured by Meiwa Kasei; GPH-65, GPH-103 and MEHC-7841-4S, manufactured by Nippon Kayaku; BisP-AP, B isP-MIBK, BisP-B, Bis-Z, BisP-CP, o,o'-BPF, BisP-IOTD, BisP-IBTD, BisP-DED, BisP-BA, Bis-C, Bis26X-A, BisOPP-A , BisOTBP-A, BisOCHP-A, BisOFP-A, BisOC-Z, BisOC-FL, BisOC-CP, BisOCHP-Z, MethylenebisP-CR, TM-BPF, BisOC-F, Bis3M6B-IBTD, BisOC-IST, BisP-IST, BisP-PRM, BisP-LV, BisE and BisP-TMC, manufactured by Honshu Chemical Co., Ltd.; BisA, BisF and BisP-M, manufactured by Mitsui Chemicals Fine Co., Ltd.; Examples of phenolic resins include those described in JP 2021-157174 A.

[0029] Epoxy resins are resins having epoxy groups. Examples of epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, glycidyl ester type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resins, and trimethylol type epoxy resins.

[0030] 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.

[0031] The liquid epoxy resin is preferably a bisphenol A epoxy resin, a bisphenol F epoxy resin, a phenol novolac epoxy resin, or a naphthalene epoxy resin, more preferably a bisphenol A epoxy resin, a bisphenol F epoxy resin, or a naphthalene epoxy resin. Examples of the liquid epoxy resin include HP4032, HP4032D, EXA4032SS, and HP4032SS (naphthalene epoxy resins) manufactured by DIC Corporation; jER828EL (bisphenol A epoxy resin), jER807 (bisphenol F epoxy resin), and jER152 (phenol novolac epoxy resin) manufactured by Mitsubishi Chemical Corporation; and ZX1059 (a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin) manufactured by Nippon Steel Chemical Co., Ltd. The liquid epoxy resin is preferably HP4032SS or ZX1059.

[0032] As the solid epoxy resin, a tetrafunctional naphthalene type epoxy resin, a cresol novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol epoxy resin, a naphthol novolac epoxy resin, a biphenyl type epoxy resin, or a naphthylene ether type epoxy resin is preferred, a tetrafunctional naphthalene type epoxy resin, a biphenyl type epoxy resin, or a naphthylene ether type epoxy resin is more preferred, and a biphenyl type epoxy resin is even more preferred. Examples of solid epoxy resins include HP-4700, HP-4710 (tetrafunctional naphthalene type epoxy resins), 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), and EPPN-502H (trisphenol A type epoxy resin) manufactured by DIC Corporation. Examples of suitable epoxy resins include ESN475 (naphthol novolac epoxy resin) and ESN485 (naphthol novolac epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; YX4000H, YL6121 (biphenyl epoxy resin) and YX4000HK (bixylenol epoxy resin) manufactured by Mitsubishi Chemical Corporation. Preferred solid epoxy resins include YX4000HK, NC3000L, and HP7200H.

[0033] 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. In the polyphenylene ether resin having a branched structure, it is preferable that ether bonds are directly bonded to at least three positions, i.e., the ipso position, the ortho position, and the para position, of at least one benzene ring constituting the polyphenylene ether resin.

[0034] The polyphenylene ether resin having a branched structure can be obtained, for example, by polymerizing two or more phenolic compounds. The phenolic compounds are preferably a phenolic compound having hydrogen atoms at the ortho- and para-positions and a polymerizable group, or a mixture of a phenolic compound having hydrogen atoms at the ortho- and para-positions but no polymerizable group and a phenolic compound having no hydrogen atom at the ortho-position, a hydrogen atom at the para-position, and a polymerizable group.

[0035] Examples of 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. Examples of the phenol compound 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. Of these, 2,6-dimethylphenol or 2-allylphenol is preferred as the phenol compound.

[0036] The polyphenylene ether resin also preferably has a polymerizable group. The polymerizable group is preferably an ethylenically unsaturated group, and preferably a vinylphenyl group or a (meth)acryloyl group. When the polyphenylene ether resin has a polymerizable 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. Examples of modified polyphenylene ethers include resins obtained by curing the resin composition described in WO 2022 / 102756.

[0037] Examples of 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. Examples of polyphenylene ether resins include resins described in JP 2022-157695 A.

[0038] The silicone resin is a resin having an organosiloxane structure. Examples of the silicone resin include curable silicone resins, silicone graft resins, and modified silicone resins such as alkyl-modified silicone resins, and curable silicone resins are preferred. Examples of the curable silicone resin include addition reaction silicone resins, condensation reaction silicone resins, and ultraviolet or electron beam curable silicone resins.

[0039] Examples of addition reaction silicone resins include resins obtained by reacting and curing polydimethylsiloxane having vinyl groups introduced at the end or side chain with hydrogen siloxane using a platinum catalyst. Examples of condensation reaction silicone resins include resins with a three-dimensional crosslinked structure formed by condensing polydimethylsiloxane having hydroxyl groups at the end with polydimethylsiloxane having hydrogen atoms at the end using an organotin catalyst. Examples of ultraviolet curable silicone resins include those that utilize the same radical reaction as silicone rubber crosslinking, those that introduce unsaturated groups and photocure, those that decompose onium salts with ultraviolet or electron beams to generate strong acids and cleave epoxy groups to crosslink, and those that crosslink via the addition reaction of thiol to vinyl siloxane. Specific examples include acrylate-modified polydimethylsiloxane and glycidoxy-modified polydimethylsiloxane. Examples of 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.

[0040] The silicone resin preferably has an aromatic ring, preferably an aromatic hydrocarbon ring, more preferably an aromatic hydrocarbon ring having 6 to 12 carbon atoms, and even more preferably a benzene ring.

[0041] As the silicone resin, a modified silicone resin obtained by reacting an organosilicon compound with a hydrosilylation agent is also preferred. It is preferable that the organosilicon compound further contains a polymerizable group. Examples of the polymerizable group include polymerizable groups contained in the resin. Examples of the organosilicon compound include compounds containing a silyl group, with 1,4-bis(dimethylsilyl)benzene or trivinylphenylsilane being preferred. Examples of the hydrosilylation agent include platinum-based catalysts such as platinum metal-supported carbon powder, 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.

[0042] Examples of silicone resins include resins obtained from organosiloxanes and curable compositions described in JP-A-2020-026502.

[0043] Benzocyclobutene resins are resins having a benzocyclobutene ring, such as divinylsiloxane-bisbenzocyclobutene resins (e.g., CYCLOTENE resins, manufactured by The Dow Chemical Company).

[0044] The (meth)acrylic resin is a resin having repeating units derived from a compound selected from (meth)acrylic acid and (meth)acrylic acid esters. Examples of repeating units derived from (meth)acrylic acid esters include repeating units derived from (meth)acrylic acid alkyl esters. The number of carbon atoms in the alkyl group (-COOR, the alkyl group in the R moiety) 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. Examples of (meth)acrylic acid alkyl esters include methyl (meth)acrylate. The total content of 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. The upper limit is preferably 100% by mass or less, more preferably 90% by mass or less.

[0045] 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. In other words, 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 even more preferably a benzene ring. Examples of repeating units having an aromatic ring 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 (meth)acrylates having an aromatic ring include benzyl (meth)acrylate, phenethyl (meth)acrylate, and phenoxyethyl (meth)acrylate. Examples of styrene and polymerizable styrene derivatives include styrene, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene dimer, and styrene trimer.

[0046] 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. In other words, 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 the repeating unit having an alicyclic ring is derived include dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, and cyclohexyl (meth)acrylate.

[0047] A liquid crystal polymer is a resin that exhibits liquid crystallinity. A thermotropic liquid crystal polymer is preferred as the liquid crystal polymer. A thermotropic liquid crystal polymer refers to a polymer that exhibits liquid crystallinity within a predetermined 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 an amide bond is introduced into a thermoplastic liquid crystal polyester.

[0048] 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 even more 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 compounds 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.

[0049] 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, t-butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis(4-hydroxyphenyl)propane, 4,4'-dihydroxydiphenyl ether, and chlorohydroxydiphenyl ether. aromatic diols such as hydroquinone, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxybenzophenone, and 3,4'-dihydroxybiphenyl; aliphatic and alicyclic diols such as ethylene glycol, propylene glycol, 1,4-butanediol, cyclohexanedimethanol, 1,6-hexanediol, neopentyl glycol, and 1,4-cyclohexanediol; aromatic hydroxycarboxylic acids such as 6-hydroxy-2-naphthoic acid and m-hydroxybenzoic acid; aromatic aminocarboxylic acids such as p-aminobenzoic acid and 6-amino-2-naphthoic acid; aromatic diamines such as 1,4-phenylenediamine, 4,4'-diaminobiphenyl, and 2,6-diaminonaphthalene; and aromatic hydroxylamines such as p-aminophenol.

[0050] Examples of the liquid crystal polymer include the liquid crystal polymers described in JP 2006-299254 A and WO 2015 / 064437 A.

[0051] Examples of polyethersulfone, polyarylate, polyetherimide, polybenzimidazole, polyphenylsulfone, polycarbonate, acrylonitrile-butadiene-styrene resin, and polyphenylene sulfide include known resins.

[0052] Examples of the resin include known resins other than the various resins mentioned above.

[0053] The weight average molecular weight (Mw) of the resin is preferably 2,000 to 500,000, and more preferably 5,000 to 100,000. The number average molecular weight (Mn) of the resin is preferably 800 to 250,000, and more preferably 2,000 to 50,000. The dispersity (Mw / Mn) of the resin is preferably 1.0 to 3.5, and more preferably 2.0 to 3.0.

[0054] The resin 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. The upper limit is preferably 50.0% by mass or less, more preferably 40.0% by mass or less.

[0055] [Filler X] The composition contains 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.

[0056] The content of the 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.

[0057] The average particle diameter 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 diameter of the filler X is calculated by the following particle diameter measurement method. Particle diameter measurement method: A composition is applied to a substrate to form a coating film, and a rectangular region of 3 μm × 10 μm in a cross section taken along the normal direction of the coating film surface is observed with a scanning electron microscope. The major axes of all filler X particles observed within the region are measured at five different locations 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 diameter of the filler X.

[0058] The procedure for the particle size measurement method is described in detail below. First, the composition is applied to a substrate to form a coating film. The thickness of the coating film is preferably 3 μm or more. A glass substrate is used as the substrate. When forming the coating film, a drying treatment may be performed as necessary. A cross section along the normal direction of the surface of the obtained coating film (the surface opposite the substrate side) is cut out, and a rectangular region of 3 μm x 10 μm on the cross section is observed with a scanning electron microscope, and the major diameter of all filler X observed within the region is measured. The scanning electron microscope used is an S-4800 manufactured by Hitachi High-Tech Corporation. The magnification for observation is 50,000 times. The above operation is performed at five different locations on the coating film, and the average (arithmetic mean) of the major diameters of all filler X measured in each operation is taken as the average particle size of filler X. The major diameter refers to the length of the longest line segment connecting any two points on the outline of filler X in the observed image. Furthermore, when the filler X aggregates to form an aggregate in the observed image, the major axis of each filler X constituting the aggregate is measured.

[0059] 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, relative to the total mass of Filler X. The lower limit is preferably greater than 0% by mass, more preferably 0.5% by mass or more. The content of the surface modifier refers to the total content of the surface modifier covering at least a portion of the surface of the filler constituting Filler X and 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 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 and drying the composition to a substrate so that the thickness after drying is 10 μm. The temperature during the drying is preferably 50 to 150°C, more preferably 70 to 100°C. The heating time during the drying is preferably 1 to 10 minutes, more preferably 2 to 7 minutes. Next, the obtained composition layer is dissolved in a mixed solvent of methyl ethyl ketone (MEK):N-methylpyrrolidone (NMP) = 1:1 to obtain a solution. The solution is then centrifuged and filtered using a filter to collect the filler before drying, and the filler before drying is further dried to obtain a filler for measurement. The temperature for the drying is preferably 50 to 150°C, more preferably 70 to 100°C. The heating time for the drying is preferably 1 to 120 minutes, more preferably 5 to 30 minutes. The filter can be appropriately selected depending on the average particle size of filler X. The weight loss rate of the filler for measurement is measured three times using a TG-DTA device (TG / DTA7300) manufactured by Hitachi High-Tech Science Corporation under conditions of heating from room temperature to 1000°C (10°C / min) in an air atmosphere, and the content of the surface modifier is calculated from the average value of the measured values.

[0060] The filler constituting Filler X is surface-modified with a surface modifier. The phrase "the filler constituting Filler X has been surface-treated with a surface modifier" means that at least a portion of the surface of the filler constituting Filler X is covered with a surface modifier or a component derived from the surface modifier. In other words, Filler X means that at least a portion of the surface of the filler constituting Filler X is covered with a surface modifier or a component derived from the surface modifier. When the surface modifier is a hydrolyzable compound, examples of the component derived from the surface modifier include a hydrolyzate of the surface modifier and a hydrolysis condensate thereof. It is preferable that at least a portion of the surface of the filler constituting Filler X is covered with a surface modifier or a component derived from the surface modifier via a chemical bond, and it is more preferable that at least a portion of the surface of the filler constituting Filler X is covered with a surface modifier via an "-Si-O-" bond.

[0061] Examples of surface modifiers 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. Examples of 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 a silicon atom 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. The silane coupling agent also preferably has a functional group other than the hydrolyzable group. Examples of functional groups 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 in the silane coupling agent may be 1 or 2 or more.

[0062] Examples of methods for surface-modifying the filler constituting Filler X with a surface modifier include a dry method in which the filler is surface-modified in a gas phase and a wet method in which the filler is surface-modified in a liquid phase. The dry method is preferred in terms of superior dielectric properties.

[0063] The shape of the filler X may be either spherical or non-spherical (for example, crushed or fibrous), with spherical being preferred.

[0064] Examples of the filler X include organic fillers and inorganic fillers whose surfaces are modified with a surface modifier, and inorganic fillers whose surfaces are modified with a surface modifier are preferred. Examples of the filler constituting the 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).

[0065] Examples of filler X and fillers constituting filler X include NHM-3N, NHM-4N, NHM-5N, NHM-24D, NP-3N, NP-4N, NP-5N, and NP-24D (all manufactured by Tokuyama Corporation, silicon dioxide, solid content concentration 100% by mass); YA050C-MJE, Y50SP-AM1, and Y50SZ-AM1 (all manufactured by Admatechs Co., Ltd., silicon dioxide, MEK slurry with a solid content concentration of 50% by mass); MEK-ST-ZL, MEK-ST-L, MEK- Examples of suitable surfactants include 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 Company, Ltd., silicon dioxide, solid content concentration 100% by mass), PMA-ST (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide, solid content concentration 100% by mass), and barium sulfate (manufactured by Nippon Solvay K.K., barium sulfate, solid content concentration 100% by mass).

[0066] The refractive index of the filler is preferably 0.5 to 3.0, more preferably 1.2 to 1.8. The refractive index can be measured by the method described above.

[0067] The fillers may be used alone or in combination of two or more.

[0068] [Polymerizable Compound] The composition may contain a polymerizable compound. The polymerizable compound is a compound different from the various components described above. When the composition contains a polymerizable compound (preferably a compound having an ethylenically unsaturated group), it is preferable that the composition further contains a photopolymerization initiator described below.

[0069] The polymerizable compound is a compound having one or more polymerizable groups in one molecule. As the polymerizable compound, a compound having an ethylenically unsaturated group is preferred, a compound having a (meth)acryloyl group, a vinyl group, or a styryl group is more preferred, and a compound having a (meth)acryloyl group is even more preferred.

[0070] The number of polymerizable groups in the polymerizable compound is preferably 1 or 2 or more, more preferably 2 to 10, and even more preferably 2 to 6. Examples of 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 bifunctional polymerizable compound or a trifunctional or higher functional polymerizable compound.

[0071] Examples of 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. Commercially available 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 Inc.), and SR209 (manufactured by Sartomer Inc.).

[0072] Examples of trifunctional or higher functional polymerizable compounds 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, and "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0073] Examples of the polymerizable compound 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.).

[0074] 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, and more preferably 8 or more. The upper limit is preferably 20 or less. Examples of tri- or higher functional urethane (meth)acrylates 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.).

[0075] The polymerizable compound may be used alone or in combination of two or more. The content of the polymerizable compound is preferably 30.0 mass% or less, more preferably 25.0 mass% or less, and even more preferably 20.0 mass% or less, based on the total solid content of the composition. The lower limit is preferably 1.0 mass% or more.

[0076] [Photopolymerization initiator] The composition may contain a photopolymerization initiator. The photopolymerization initiator is a compound different from the various components described above. 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.

[0077] Examples of the photopolymerization initiator include an oxime ester compound (a photopolymerization initiator having an oxime ester structure), an aminoacetophenone compound (a photopolymerization initiator having an aminoacetophenone structure), a hydroxyacetophenone compound (a photopolymerization initiator having a hydroxyacetophenone structure), an acylphosphine oxide compound (a photopolymerization initiator having an acylphosphine oxide structure), and a bistriphenylimidazole compound (a photopolymerization initiator having a bistriphenylimidazole structure). As the photopolymerization initiator, an oxime ester compound or an aminoacetophenone compound is preferred, and an oxime ester compound is more preferred.

[0078] Examples of the oxime ester compound include 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (trade name: IRGACURE OXE-01, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazol-3-yl]-[2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyloxime) (trade name: IRGACURE OXE-03, manufactured by BASF), and OXE-03, manufactured by BASF), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methylpentanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-04, manufactured by BASF and trade name: Lunar 6, manufactured by DKSH Japan Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou New Power Electronic Materials Co., Ltd.), 1,2-propanedione,3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-,2-(O-acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhou New Power Electronic Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou New Power Electronic Materials Co., Ltd.).

[0079] Examples of 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.).

[0080] Examples of the photopolymerization initiator 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 1173), 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), and H) and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819).

[0081] Examples of the photopolymerization initiator include the photopolymerization initiators described in paragraphs 0031 to 0042 of JP-A No. 2011-095716 and paragraphs 0064 to 0081 of JP-A No. 2015-014783.

[0082] The photopolymerization initiator may be used alone or in combination of two or more. The content of the photopolymerization initiator is preferably 10.0 mass% or less, more preferably 5.0 mass% or less, and even more preferably 1.0 mass% or less, based on the total solid content of the composition. The lower limit is preferably 0.1 mass% or more.

[0083] [Compound Y] The composition may contain 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. Compound Y is a compound different from the various components described above (for example, a photopolymerization initiator, etc.). When the 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 that ensures 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, making it less likely to remain in the pattern system.

[0084] The boiling point of compound Y is 300°C or higher, 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. In this specification, the boiling point of compound Y is a value determined by the following measurement method. When compound Y is distilled under normal pressure (760 mmHg), the boiling point is the gas temperature at which condensation of the evaporated gas begins (measured from 23 to 300°C, temperature rise rate 1°C / min). Distillation of compound Y is carried out using a Liebig condenser, and if distillation does not begin at 300°C under normal pressure, distillation is carried out under reduced pressure. Similar distillation was performed at pressures of 100 mmHg, 50 mmHg, and 5 mmHg in that order (measurement from 23 to 300°C, temperature increase rate 1°C / min, if distillation did not start at 300°C, distillation at the next pressure), and the boiling point at atmospheric pressure was calculated using the nomograph shown in Figure 1 (Source: Science of Petroleum, Vol. II, p. 1281 (1938)) from the temperature and pressure at which condensation of the evaporated gas began. The boiling point at atmospheric pressure was taken as the calculated boiling point. If distillation did not start at 300°C under 5 mmHg, the boiling point at atmospheric pressure was deemed to be greater than 500°C. The method of using a nomograph is well known. Specifically, a straight line was drawn between the boiling point at reduced pressure on line A and the degree of reduced pressure on line C (Procedure 1), and the value at the intersection of the line drawn in Procedure 1 and line B was read (Procedure 2), and this was deemed to be the boiling point at atmospheric pressure.

[0085] 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 1000 or less, more preferably 800 or less, and even more preferably 600 or less. When compound Y has a molecular weight distribution, the above molecular weight of compound Y refers to the weight average molecular weight.

[0086] 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 using a B-type viscometer.

[0087] Examples of compound Y include ethylphthalyl ethyl glycolate, dihexyl phthalate, tributyl o-acetylcitrate, 2-ethylhexyl benzyl 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-ethylhexanoate), tris(2-ethylhexyl) trimellitate, and bis(2-butoxyethyl) adipate.

[0088] Compound Y may be used alone or in combination of two or more. The content of compound Y is preferably 1.0 mass% or more, more preferably 3.0 mass% or more, and even more preferably 5.0 mass% or more, based on the total solid content of the composition. The upper limit is preferably less than 50.0 mass%, more preferably 35.0 mass% or less, and even more preferably 25.0 mass% or less. The total content of the polymerizable compound and compound Y is preferably less than 50.0 mass%, more preferably 30.0 mass% or less, and even more preferably 25.0 mass% or less, based on the total solid content of the composition.

[0089] [Photoacid Generator] The composition may contain a photoacid generator. The photoacid generator is a compound that generates an acid when exposed to light (for example, exposure light).

[0090] Examples of photoacid generators include ionic photoacid generators and nonionic photoacid generators. Examples of ionic photoacid generators include compounds having a sulfonium structure, onium salt compounds having a diaryliodonium or triarylsulfonium structure, and ammonium salt compounds having a quaternary ammonium structure. Examples of ionic photoacid generators include those described in paragraphs

[0114] to

[0133] of JP 2014-085643 A. Examples of nonionic photoacid generators include trichloromethyl-s-triazine and its derivatives (trichloromethyl-s-triazines 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 those described in paragraphs

[0083] to

[0088] of JP 2011-221494 A. Furthermore, examples of the oxime sulfonate compound include the compounds described in paragraphs 0084 to 0088 of WO 2018 / 179640.

[0091] The content of the photoacid generator is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 5.0% by mass, based on the total solid content of the composition.

[0092] [Surfactant] The composition may contain a surfactant. Examples of the surfactant include those described in paragraph 0017 of Japanese Patent No. 04502784 and paragraphs 0060 to 0071 of JP-A-2009-237362.

[0093] Examples of surfactants include hydrocarbon surfactants, fluorine surfactants, and silicone surfactants. From the viewpoint of improving environmental friendliness, it is preferable that the surfactant does not contain a fluorine atom. The surfactant is preferably a hydrocarbon surfactant or a silicone surfactant. Commercially available 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. MFS-579, EXP. MFS-586, EXP. MFS-587, EXP. MFS-628, EXP. MFS-631, EXP. MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K and DS-21 (all manufactured by DIC Corporation); Fluorad FC430, FC431 and FC171 (all manufactured by Sumitomo 3M Limited); Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393 and KH-40 (all manufactured by AGC); PolyFox Examples include PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA); Ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, and 683 (manufactured by NEOS Corporation); and U-120E (manufactured by Unichem).

[0094] Examples of fluorosurfactants include acrylic compounds that have a molecular structure containing a functional group having a fluorine atom, and when heated, the functional group having the fluorine atom is cleaved, causing the fluorine atom to volatilize. Examples of such fluorosurfactants include the Megafac DS series (manufactured by DIC Corporation, Chemical Daily (February 22, 2016), Nikkei Business Daily (February 23, 2016), and Megafac DS-21). Furthermore, the fluorosurfactant may be a polymer of a fluorine-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 fluorosurfactant may also 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). Further, examples of fluorine-based surfactants include fluorine-containing polymers having a group having an ethylenically unsaturated group in the side chain, such as Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0095] As the fluorine-based surfactant, from the viewpoint of improving environmental compatibility, surfactants derived from alternative materials to compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are preferred.

[0096] Examples of 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. Examples of hydrocarbon surfactants 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); 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 & Fat Co., Ltd.); Olfine E1010, Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).

[0097] Examples of silicone surfactants include linear polymers consisting of siloxane bonds, modified siloxane polymers with organic groups introduced into the side chains and / or terminals, and polymers having a repeating unit with a hydrophilic group in the side chain and a repeating unit with a group having a siloxane bond in the side chain.Preferred silicone surfactants are polymers having a repeating unit with a hydrophilic group in the side chain and a repeating unit with a group having a siloxane bond in the side chain.The polymers may be either random copolymers or block copolymers.

[0098] The repeating unit having a group having a siloxane bond in the side chain is preferably a repeating unit represented by formula (SX1) or a repeating unit represented by formula (SX2).

[0099]

[0100] In formula (SX1), each R independently represents an alkyl group having 1 to 3 carbon atoms. １ represents a hydrogen atom or a methyl group. １ represents a single bond or a divalent organic group. When a plurality of R's are present, the R's may be the same or different.

[0101]

[0102] In formula (SX2), R １ represents a hydrogen atom or a methyl group. ２ represents an alkylene group having 1 to 10 carbon atoms. ３ represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 5 to 50.

[0103] The repeating unit having a hydrophilic group in the side chain is preferably a repeating unit represented by formula (SX3).

[0104]

[0105] In formula (SX3), R ４ and R ５ each independently represents a hydrogen atom or a methyl group, n represents an integer of 1 to 4, and m represents an integer of 1 to 100.

[0106] Examples of 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, and X-22-6266 , KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KF-6001, KF-6002, KP-101KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP-124, KP-1 25, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626 and KP-652 (all manufactured by Shin-Etsu Silicone Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF-4460 and TSF-4452 (all manufactured by Momentive Perform BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378 and BYK323 (all manufactured by BYK-Chemie).

[0107] The surfactant also includes a nonionic surfactant.

[0108] The surfactant content is preferably 0.01 to 3.0 mass%, more preferably 0.01 to 1.0 mass%, and even more preferably 0.05 to 0.8 mass%, based on the total solid content of the composition.

[0109] [Curing Agent] The composition may contain a curing agent. The curing agent is not particularly limited, as long as it is, for example, a compound that promotes the curing of the various components contained in the composition. Examples of the curing agent include active ester curing agents, cyanate ester curing agents, and benzoxazine curing agents. Examples of active ester curing agents include the EPICLON series, EXB9451, EXB9460, EXB9460S, HPC8000-65T, and EXB9416-70BK (manufactured by DIC Corporation); DC808 and YLH1026 (manufactured by Mitsubishi Chemical Corporation). Examples of curing agents include those described in JP 2020-154325 A and JP 2004-277460 A.

[0110] [Other Additives] In addition to the various components described above, the composition may contain other additives. Examples of other additives include heterocyclic compounds (e.g., triazole, benzotriazole, tetrazole, and derivatives thereof, rust inhibitors), aliphatic thiol compounds, thermally crosslinkable compounds, polymerization inhibitors, hydrogen donor compounds, solvents, impurities, plasticizers, sensitizers, alkoxysilane compounds, and maleimide compounds. Examples of heterocyclic compounds, aliphatic thiol compounds, thermally crosslinkable compounds, polymerization inhibitors, and hydrogen donor compounds include the various components described in WO 2022 / 039027. Examples of plasticizers, sensitizers, and alkoxysilane compounds include paragraphs 0097 to 0119 of WO 2018 / 179640. Examples of maleimide compounds (compounds having a maleimide ring) include known maleimide compounds and the maleimide compounds described in WO 2022 / 102756.

[0111] The solvent is not particularly limited as long as it can dissolve or disperse various components that may be contained in the composition other than the solvent. Examples of 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. The solvents may be used alone or in combination. The content of the solvent is preferably 50 to 1900 parts by mass, more preferably 100 to 1200 parts by mass, and even more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solids content of the composition.

[0112] The composition may contain impurities. Examples of 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 (preferably sodium ions and chloride ions) are likely to be mixed in as impurities, so the following contents are preferred.

[0113] When the composition does not contain impurities (particularly sodium ions or chloride ions), or when the composition contains impurities, 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, still 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.

[0114] Examples of methods for adjusting the impurity content include 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 impurities from being mixed in during preparation of the composition. In particular, examples of methods for adjusting the sodium ion and chloride ion contents include a method of reducing the content of a surface modifier and a method of surface-treating the filler that constitutes Filler X with a surface modifier with low impurity contents.

[0115] The content of impurities can be quantified by known methods such as, for example, ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, ion chromatography, etc. When ion chromatography is used, for example, a Thermo Fisher ICS-2100 is used as an analyzer, and the measurement can be performed at a column temperature of 35°C using a Thermo Fisher IonPac AS11HC column when the object to be measured is an anion, or a Thermo Fisher IonPac CS12 column when the object to be measured is a cation.

[0116] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the composition is preferably low. Specifically, 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 using the same method as for the impurities described above. Furthermore, these compounds can be quantified using known measurement methods.

[0117] A preferred embodiment of the composition includes, for example, the following embodiment A. Aspect A: It is preferable that the composition satisfies at least one of the following conditions: it contains a resin having a polymerizable group (preferably an ethylenically unsaturated group) and it 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 embodiment of the resin described above.

[0118] [Transfer Film] The transfer film has a temporary support and a composition layer formed using the above-described composition.

[0119] 2 is a cross-sectional schematic diagram showing an example of an embodiment of a 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 and / or a thermoplastic resin layer, which will be described later. Each component of the transfer film will be described in detail below.

[0120] [Temporary Support] The transfer film has a temporary support, which is a member that supports the composition layer and is ultimately removed by a peeling treatment.

[0121] 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 also 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 oriented polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film, with polyethylene terephthalate film being preferred. Furthermore, the temporary support is preferably free of deformations such as wrinkles and scratches.

[0122] The temporary support preferably has high transparency in order to enable pattern exposure through the temporary support. Specifically, the transmittance at each of the wavelengths 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 each of the above wavelengths include, for example, 87%, 92%, and 98%. In terms of the pattern formability during pattern exposure through the temporary support and the transparency of the temporary support, the haze of the temporary support is preferably small. Specifically, 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. In terms of the pattern formability during pattern exposure through the temporary support and the transparency of the temporary support, the number of fine particles, foreign matter, and defects contained in the temporary support is preferably small. The number of particles, foreign matter, and defects with a diameter of 1 μm or more on the temporary support is 50 / 10 mm. ２ Preferably, 10 pieces / 10 mm or less ２ More preferably, 3 pieces / 10 mm or less ２ More preferably, 0 pieces / 10 mm or less ２ is particularly preferred.

[0123] The thickness of the temporary support is preferably 5 to 200 μm, and from the viewpoint of ease of handling and versatility, more preferably 5 to 150 μm, still more preferably 5 to 50 μm, and particularly preferably 5 to 35 μm. The thickness of the temporary support can be calculated as the average value of any five points measured by cross-sectional observation using an SEM (scanning electron microscope).

[0124] In order to improve the adhesion between the temporary support and the composition layer, the surface of the temporary support that comes into contact with the composition layer may be surface-modified by UV irradiation, corona discharge, plasma, etc. When the surface is modified by UV irradiation, the exposure dose of UV irradiation is 10 to 2000 mJ / cm. ２ is preferred, and 50 to 1000 mJ / cm ２Examples 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 output and illuminance can be adjusted as appropriate.

[0125] Examples of the temporary support include a biaxially oriented polyethylene terephthalate film having a thickness of 16 μm, a biaxially oriented polyethylene terephthalate film having a thickness of 12 μm, and a biaxially oriented polyethylene terephthalate film having a thickness of 9 μm. The temporary support may be a recycled product. Examples of the recycled product include a film obtained by cleaning and chipping used films. Examples of commercially available recycled products include the Ecouse series (manufactured by Toray Industries, Inc.).

[0126] Examples of temporary supports include those described in paragraphs 0017 to 0018 of JP-A-2014-085643, paragraphs 0019 to 0026 of JP-A-2016-027363, paragraphs 0041 to 0057 of WO 2012 / 081680, and paragraphs 0029 to 0040 of WO 2018 / 179370, the contents of which are incorporated herein by reference.

[0127] 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 μm. The thickness of the lubricant layer is preferably 0.05 to 1.0 μm. Commercially available temporary supports include 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.).

[0128] [Composition Layer] The composition layer is a layer formed using the composition. Examples of various components that can be contained in the composition layer include various components other than the solvent that can be contained in the composition. However, the preferred ranges for the content of the various components in the composition layer are the same as the preferred ranges obtained by replacing the above-mentioned "content (% by mass) of the various components relative to the total solid content of the composition" with "content (% by mass) of the various components relative to the total mass of the composition layer." Specifically, the phrase "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."

[0129] The average thickness of the composition layer is preferably 0.5 to 40 μm, more preferably 0.5 to 25 μm, and even more preferably 3 to 20 μm. When the average thickness of the composition layer is 40 μm or less, this is preferred in terms of excellent pattern resolution. When the average thickness of the composition layer is 0.5 μm or more, this is preferred in terms of excellent reliability.

[0130] [Intermediate layer and thermoplastic resin layer] The transfer film may have an intermediate layer and / or a thermoplastic resin layer. When the transfer film has an intermediate layer and / or a thermoplastic resin layer, the transfer film preferably has an intermediate layer and / or a thermoplastic resin layer between the temporary support and the composition layer. Examples of intermediate layers and thermoplastic resin layers include those described in paragraphs 0164 to 0204 of WO 2021 / 166719, the contents of which are incorporated herein by reference.

[0131] [Cover Film] The transfer film may have a cover film.

[0132] The number of fish eyes with a diameter of 80 μm or more contained in the cover film is 5 / m ２ Preferably, 0 pieces / m ２ The following are more preferred: Fisheyes are foreign matter, undissolved matter, and / or oxidized and deteriorated matter of the material that is introduced into the film when the material is thermally melted and then kneaded, extruded, and / or biaxially stretched, cast, or other methods are used to produce the film.

[0133] The number of particles with a diameter of 3 μm or more contained in the cover film is 30 / mm ２ Preferably, 10 pieces / mm or less ２ More preferably, 5 or less pieces / mm ２ More preferably, 0 pieces / mm ２ The following is particularly preferable: This can suppress defects caused by the transfer of irregularities due to particles contained in the cover film to the composition layer.

[0134] The arithmetic mean roughness Ra of the surface of the cover film is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm 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.In addition, from the viewpoint of suppressing defects during transfer, the arithmetic mean roughness Ra is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0135] Examples of the cover film include polyethylene terephthalate film, polypropylene film, polystyrene film, and polycarbonate film. Examples of the cover film include those described in paragraphs 0083 to 0087 and 0093 of JP-A No. 2006-259138.

[0136] Examples of cover films 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. Examples of recycled products include those obtained by cleaning and chipping used films and then forming the resulting material into films. Examples of commercially available recycled products include the Ecouse series (manufactured by Toray Industries, Inc.).

[0137] [Other Layers] The transfer film may have other layers in addition to the above-described layers. Examples of other layers include a high refractive index layer. Examples of high refractive index layers include those described in paragraphs 0168 to 0188 of International Publication No. 2021 / 187549, the contents of which are incorporated herein by reference.

[0138] [Method for Producing Transfer Film] The transfer film can be produced by a known production method, preferably a method in which a composition is applied to a temporary support to form a composition layer.

[0139] The method for producing a transfer film includes 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. The method for producing a transfer film preferably further includes a step of pressing a cover film onto the obtained composition layer. The obtained transfer film may also be wound up and stored in a roll form. If it is in a roll form, it can be provided in the form as it is for the lamination step with a substrate in a roll-to-roll system.

[0140] As described above, the transfer film may have an intermediate layer and / or a thermoplastic resin layer. Examples of 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.

[0141] The composition layer can be formed by a known method, for example, by applying and drying a composition. The composition is the composition of the present invention described above.

[0142] Examples of the coating method 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 may be contained in the composition, and preferred embodiments are also the same.

[0143] [Applications] The pattern (film) obtained from the composition layer formed using the composition or the transfer film can be used in various applications. For example, it can be used as an electrode protective film, an insulating film, a planarizing film, an overcoat film, a hard coat film, a passivation film, a partition wall, a spacer, a microlens, an optical filter, an anti-reflection film, an etching resist, and a plating member. More specifically, it can be used as a protective film or insulating film for a touch panel electrode, a protective film or insulating film for a printed wiring board, a protective film or insulating film for a TFT substrate, an interlayer insulating film in a build-up substrate for a semiconductor package, an organic interposer, a color filter, an overcoat film for a color filter, and an etching resist and a plating member for forming wiring.

[0144] [Method for Producing Laminate] The method for producing a laminate is not particularly limited as long as it is a method using the composition or the transfer film. Examples of methods for producing a laminate include known production methods such as methods for producing build-up substrates. A production method including steps Z1 to Z3 is preferred, and a production method including steps Z1 to Z4 is more preferred. Step Z1: Forming a composition layer on a substrate using a composition or a transfer film; Step Z2: Forming a pattern having vias in the composition layer; Step Z3: Heating or exposing the pattern; Step Z4: Forming a circuit pattern on the obtained pattern. Furthermore, the method for producing a laminate includes steps Z1 to Z4, and preferably further includes step Z5 of forming a composition layer on the laminate produced in step Z4 using a composition or a transfer film, and steps Z2 to Z5 are repeatedly performed.

[0145] <Step Z1> Step Z1 is a step of forming a composition layer on a substrate using a composition or a transfer film. When a composition is used, step Z1 is preferably a step of applying the composition to a substrate to form a composition layer. Examples of a method for applying the composition include the method for forming a composition layer in the above-mentioned method for producing a transfer film. When a transfer film is used, step Z1 is preferably a step of contacting the surface of the composition layer in the transfer film opposite the temporary support side with the substrate and laminating the transfer film and the substrate. Examples of methods for laminating the transfer film include known transfer methods and methods using known laminators such as laminators, vacuum laminators, and auto-cut laminators, and methods that involve pressure and heat using a roll or the like are preferred. The lamination temperature is preferably 70 to 130°C. Furthermore, when the transfer film has a cover film, step Z1 is preferably performed after peeling the cover film from the transfer film.

[0146] (Substrate) Examples of the substrate 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 composed of a light-transmitting substrate such as a glass substrate, or may be tempered glass such as Corning Gorilla Glass. Examples of materials contained in the substrate include materials described in JP 2010-086684 A, JP 2010-152809 A, and JP 2010-257492 A. Resin substrates are preferably resin films with low optical distortion and / or high transparency. Specific examples include polyester, polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, cycloolefin polymer, and polyimide.

[0147] The substrate having a conductive layer is preferably a resin substrate having a conductive layer, more preferably a resin film having a conductive layer, because it can be produced by a roll-to-roll process. The substrate having a conductive layer may also be a laminate obtained by the above-mentioned method for producing a laminate.

[0148] Examples of the conductive layer include known conductive layers used for circuit wiring or touch panel wiring. From the viewpoints of conductivity and fine line formability, the conductive layer is preferably one or more layers selected from the group consisting of a metal layer (e.g., metal foil, etc.), a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and even more preferably a copper layer or a silver layer. The conductive layer may also 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 simple metals and conductive metal oxides. Examples of simple metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au. Examples of conductive metal oxides include ITO (indium tin oxide), IZO (indium zinc oxide), and SiO ２ The conductivity is such that the volume resistivity is 1×10 ６ It means that the volume resistivity is less than 1×10 ４ It is preferably less than Ωcm.

[0149] The conductive layer may be patterned. Examples of methods for producing a patterned conductive layer include subtractive methods such as etching and additive methods. Examples of etching methods include wet etching methods described in paragraphs 0048 to 0054 of JP 2010-152155 A and known dry etching methods such as plasma etching. The etching method may also be a method using an etching resist.

[0150] <Step Z2> 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. Examples of methods for forming the pattern having vias include methods using a drill, a laser, and plasma.

[0151] Furthermore, when the composition layer is photosensitive, the method for forming a pattern having vias preferably includes a step of pattern-exposing the composition layer, 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. It is more preferable to include a step of curing the pattern between the step of forming the pattern and the step of etching. 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 is preferably the above-mentioned aspect A.

[0152] The light source used for exposure may be any light source that irradiates light in a wavelength range (e.g., light in a wavelength range of 254 nm, 313 nm, 365 nm, 405 nm, etc.) to which various photosensitive components in the composition layer (e.g., resin, polymerizable compound, photopolymerization initiator, photoacid generator, etc.) are sensitive. Specific examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (light-emitting diodes).

[0153] The exposure dose is 5 to 200 mJ / cm ２ is preferred, and 10 to 200 mJ / cm ２ is more preferred.

[0154] In step 2, exposure may be performed after peeling off the temporary support, or exposure may be performed through the temporary support before peeling off the temporary support, and then the temporary support may be peeled off. It is preferable to perform patternwise exposure without peeling off the temporary support in order to prevent mask contamination due to contact between the composition layer and the mask and to avoid the influence of foreign matter attached to the mask on the exposure. The patternwise exposure may be exposure through a mask or direct exposure using a laser or the like. Examples of masks include quartz masks, soda-lime glass masks, and film masks. Quartz masks are preferred because of their excellent dimensional accuracy, and film masks are preferred because they can be easily made into large sizes. As a material for the film mask, polyester film is preferred, and polyethylene terephthalate film is more preferred. As a material for the film mask, for example, XPR-7S SG (manufactured by Fujifilm Global Graphic Systems Co., Ltd.) is exemplified.

[0155] The pattern having vias may be either through holes or via holes. The shape of the vias in the pattern may be, for example, a square, trapezoid, or inverted trapezoid in cross section; or a circle or square in front view (the shape of the via when observed from the direction in which the via bottom is visible). An inverted trapezoid is preferred as the cross section because it improves the adhesion of plated copper to the via wall surface. The via size (diameter) is preferably 300 μm or less, more preferably 100 μm or less, even more preferably 50 μm or less, and particularly preferably 5 μm or less. The lower limit is preferably 1 μm or more. The number of vias may be 1 or 2 or more, and preferably 2 or more.

[0156] <Step Z3> 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. Examples of the exposure method include the exposure method in step Z2.

[0157] [Step Z4] Step Z4 is a step of forming a circuit pattern on the pattern. A semi-additive process is preferred as a method for forming a circuit pattern because it allows for the formation of fine wiring. For example, in the semi-additive process, a seed layer is first formed by electroless copper plating using a palladium catalyst or the like on the via bottoms, via walls, and the entire surface of a via-containing pattern. The seed layer is used to form a power supply layer for electrolytic copper plating, and the seed layer thickness is preferably 0.1 to 2.0 μm. A seed layer thickness of 0.1 μm or more tends to suppress a decrease in connection reliability during electrolytic copper plating. A seed layer thickness of 2.0 μm or less tends to eliminate the need for a large etching amount when flash etching the seed layer between wirings, thereby suppressing damage to the wiring during etching. Electroless copper plating is performed by depositing metallic copper on the surface of a via-containing pattern through a reaction between copper ions and a reducing agent. Examples of electroless plating methods and electrolytic plating methods include known plating methods. The catalyst for the electroless plating treatment 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 treatment preferably contains hypophosphorous acid (reducing agent). Examples of electroless copper plating solutions include "MSK-DK" manufactured by Atotech Japan and the "Sulcup (registered trademark) PEA ver. 4" series manufactured by Uemura Kogyo Co., Ltd.

[0158] The method for manufacturing a laminate may include a roughening step of roughening a pattern having vias. The roughening step is preferably performed after step Z3 and before step Z4. By performing the roughening step, the pattern surface can be roughened to improve adhesion with the circuit wiring. Smears can also be removed at the same time. Examples of the roughening step include known desmearing treatments, and treatments involving contact with a roughening liquid are preferred. Examples of the roughening liquid include a roughening liquid containing chromium and sulfuric acid, a roughening liquid containing an alkaline permanganate (e.g., a sodium permanganate roughening liquid, etc.), and a roughening liquid containing sodium fluoride, chromium, and sulfuric acid.

[0159] From the viewpoint of improving the electrical insulation reliability, curing characteristics, and adhesive strength with plated copper, it is preferable to carry out a heat treatment after forming the circuit pattern. The heating temperature is preferably 150 to 240°C, and the heating time is preferably 15 to 500 minutes.

[0160] [Laminate] The laminate is a laminate obtained by the above-mentioned laminate manufacturing method. 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. Examples of semiconductor devices include 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.).

[0161] [Cured film] The cured film is a film obtained by curing the above-described composition. Examples of the curing method include the heating method and the exposure method in step Z3. The composition that forms the cured film is not particularly limited as long as it is the above-described composition, but it preferably contains at least one resin selected from the group consisting of a phenolic resin and an epoxy resin.

[0162] The present invention will be described in further detail below based on examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the examples shown below. In the following examples and comparative examples, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

[0163] [Preparation of Composition] Various components were mixed to obtain the solid content ratios shown in the table below, and then diluted to a solid concentration of 30% by mass, a MEK (methyl ethyl ketone) concentration of 20% by mass, and a NMP (N-methylpyrrolidone) concentration of 50% by mass to prepare compositions. When the silica was not in a slurry form (when it was in a powder form), the silica was dispersed in a 50% by mass MEK solution to form a slurry, and then mixed to prepare the composition. The sodium ion and chloride ion contents in the composition were adjusted as necessary using the method for adjusting the impurity content described above.

[0164] [Resins] A-1: ​​Phenolic resin, TR4020G, manufactured by Asahi Organic Chemicals Co., Ltd. A-2: Epoxy resin, ZX1059 (a mixture (1:1) of bisphenol A epoxy resin and bisphenol F epoxy resin), manufactured by Nippon Steel Chemical Co., Ltd.

[0165] A-3: Polyphenylene ether resin having a branched structure, synthesized by the following method. 1.3 g of di-μ-hydroxo-bis[(N,N,N',N'-tetramethylethylenediamine)copper(II)] chloride (Cu / TMEDA) and 1.59 mL of tetramethylethylenediamine (TMEDA) were added to a 1500 mL two-necked recovery flask and thoroughly dissolved. 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. This raw material solution was added dropwise to the recovery flask and reacted at 45°C for 5 hours while stirring at a rotation speed of 600 rpm. After completion of the reaction, the resin was reprecipitated in a mixture of 10 L of methanol and 11 mL of concentrated hydrochloric acid, filtered, and dried at 70°C for 24 hours to obtain Resin A-3. Resin A-3 had a number average molecular weight of 25,000 and a weight average molecular weight of 66,000.

[0166] A-4: Silicone resin, 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

[0167] A-5: Benzocyclobutene resin, Cyclotene resin XUR-JW-1148-200201415-47, manufactured by The Dow Chemical Company

[0168] A-6: Acrylic resin, styrene / acrylic acid = 71% by mass / 29% by mass, synthesized by the following method. A 2000 mL flask was charged with 1-methoxy-2-acetoxypropane (PGMEA, 60 parts) and propylene glycol monomethyl ether (PGME, 240 parts by mass) to prepare a mixed solution. The resulting mixed solution was heated to 90°C while stirring at a stirring speed of 250 rpm. Dropping solution (1) was obtained by mixing styrene (71 parts by mass) and acrylic acid (29 parts by mass) and diluting with PGMEA (60 parts by mass). Dropping solution (2) was obtained by dissolving V-601 (dimethyl 2,2'-azobis(2-methylpropionate), 9.637 parts by mass) in PGMEA (136.56 parts by mass). Next, Dropping Solution (1) and Dropping Solution (2) were simultaneously added dropwise over 3 hours to a 2000 mL flask containing the mixed solution heated to 90°C. After completion of the dropwise addition, V-601 (2.401 parts by mass) was added to the flask three times every hour. The mixture was then stirred at 90°C for an additional 3 hours. The reaction solution obtained in the flask was then diluted with PGMEA to obtain a solution containing Resin A-6 (solid concentration 36.3% by mass).

[0169] A-7: Methacrylic resin, methyl methacrylate / dicyclopentanyl methacrylate / methacrylic acid = 40% by mass / 40% by mass / 20% by mass, synthesized by the following method. Resin A-7 was synthesized in the same manner as Resin A-6 described above, except that the dropping liquid (1) and dropping liquid (2) were changed, to obtain a solution containing Resin A-7 (solid content concentration 36.3% by mass). Dropping liquid (1) was obtained by mixing methyl methacrylate (40 parts by mass), dicyclopentanyl methacrylate (40 parts by mass), and methacrylic acid (20 parts by mass) and diluting with PGMEA (60 parts). Dropping liquid (2) was obtained by dissolving V-601 (dimethyl 2,2'-azobis(2-methylpropionate), 9.637 parts by mass) in PGMEA (136.56 parts by mass).

[0170] A-8: Liquid crystal polymer (liquid crystalline polyester), synthesized by the following method. A 2.5 L reaction vessel equipped with a stirring blade and a distillation tube was charged with 435 g of p-hydroxybenzoic acid, 164 g of 4,4'-dihydroxybiphenyl, 44 g of hydroquinone, 146 g of terephthalic acid, 78 g of isophthalic acid, and 684 g of acetic anhydride, and the mixture was stirred under a nitrogen gas atmosphere while reacting at 150 ° C for 2.5 hours, and then heated to 300 ° C over 3.5 hours. Thereafter, the polymerization temperature was maintained at 300 ° C, the pressure was reduced to 1.0 mmHg over 1.0 hour, and the reaction was continued for another 2 hours. Next, the reaction vessel was pressurized to 0.12 MPa, and Resin A-8 was discharged into a strand-like material, and Resin A-8 was obtained.

[0171] A-9: Vinylbenzyl-modified polyphenylene ether resin, manufactured by Mitsubishi Gas Chemical Co., Ltd., "OPE-2St 1200" toluene solution

[0172] [Filler X or comparative filler] <Filler X> 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 YA050C-MJE: Silicon dioxide (spherical silica slurry), surface-treated product, MEK slurry with a 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 Industries, Ltd. MEK-ST-L: Silicon dioxide (spherical silica slurry), surface-treated product, manufactured by Nissan Chemical Industries, Ltd. MEK-EC-2130Y: Silicon dioxide (spherical silica slurry), surface-treated product, manufactured by Nissan Chemical Industries, Ltd.

[0173] <Comparative fillers> 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 Industries, Ltd.) using centrifugation and a filter was mixed with 39 g of NMP and 1 g of 3-methacryloxypropyltrimethoxysilane, and ultrasonic dispersion was carried out while stirring to prepare pre-adjusted product A. PGM-ST: silicon dioxide (spherical silica), surface-untreated, manufactured by Nissan Chemical Industries, Ltd.

[0174] [Photopolymerization initiator] Oxe-01: Irgacure OXE-01, manufactured by BASF Irg379: Irgacure (Omnirad) 379EG, manufactured by IGM Resins B.V.

[0175] [Polymerizable compounds] 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.

[0176]

[0177] [Surfactants] S-506: Silicone surfactant, manufactured by DIC Corporation F-551A: Megafac (registered trademark) F551A, fluorine-based surfactant, manufactured by DIC Corporation

[0178] [Rust inhibitor] HAT: 5-amino-1H-tetrazole ATA: 3-amino-1,2,4-triazole

[0179] [Others] HPC8000-65T: dicyclopentadiene-type diphenol compound (polycyclopentadiene-type diphenol compound)-type active ester curing agent, toluene solution with a solids concentration of 65% by mass, manufactured by DIC Corporation. Silyl compound: synthesized by the following method. 700.0 g of 1,4-bis(dimethylsilyl)benzene (manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.36 g of 5% by mass platinum carbon powder (manufactured by N.E. Chemcat Corporation) were added to a 2 L four-neck flask equipped with a stirrer, a condenser, a dropping funnel, and a thermometer, and the mixture was heated to 90°C using an oil bath. 149 g of trivinylphenylsilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise to the mixture. After the dropwise addition, the mixture was stirred at 95°C for 4 hours. After stirring, the mixture was returned to 25°C, 8.4 g of activated carbon was added, and the mixture was stirred for 2 hours. After stirring, the mixture was filtered and concentrated under reduced pressure to obtain 500 g of a silyl compound. The silyl compound was a mixture of compounds having a structure represented by any one of formulas (a) to (e), and the ratio of each compound was (a):(b):(c):(d):(e) = 29:21:16:9:25 (mol%). Note that the structure represented by any one of formulas (a) to (e) is the same as the structure described in paragraphs 0072 to 0076 of JP 2020-026502 A.

[0180] Components (a) to (e) are shown below.

[0181]

[0182]

[0183]

[0184]

[0185] 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

[0186] [Measurement of Average Particle Diameter] Each composition of each Example and Comparative Example was applied to a glass substrate and dried to form a coating film having a thickness of 4.0 μm. A cross section of the resulting coating film was cut out along the normal direction of the surface, and the cross section was observed under a scanning electron microscope. The major axes of all fillers (filler X or comparative fillers) observed within a region having a length of 3 μm in the longitudinal direction parallel to the thickness direction of the coating film and a length of 10 μm in the transverse direction perpendicular to the longitudinal direction were measured. The above procedure was performed at five different locations on the coating film, and the average (arithmetic mean) of the major axes of all fillers (filler X or comparative fillers) measured in each procedure was taken as the average particle diameter of the filler. After measuring the average particle diameter as described above for the compositions of each Example and Comparative Example, the coating film was heated at 220° C. for 5 hours, and then the average particle diameter was measured according to the same procedure as described above. The average particle diameter was found to be the same as the average particle diameter before heat treatment.

[0187] [Surface Modifier Content] Each composition was applied to a substrate so that the dried thickness was 10 μm, and then dried (drying temperature: 100°C, drying time: 3 minutes) to form a composition layer. The resulting composition layer was then dissolved in a mixed solvent of MEK:NMP = 1:1. The resulting solution was then centrifuged and filtered using a 0.2 μm filter to separate the filler (Filler X or comparative filler). The resulting filler was dried (drying temperature: 100°C, drying time: 30 minutes) to obtain 30 mg of a filler for measurement. 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 conditions of a temperature increase (10°C / min) from room temperature to 1000°C in an air atmosphere, and the content of the surface modifier (value relative to the total solids content of the composition) was calculated from the arithmetic average value.

[0188] [Na ＋ Content and Cl － 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 analyzed by ion chromatography to determine the Na ＋ and Cl － The content (value relative to the total solid content of the composition) was measured. The analyzer was ICS-2100 manufactured by Thermo Fisher, and the column was Cl － In the case of Thermo Fisher IonPac AS11HC, Na ＋ In the case of , IonPac CS12 manufactured by ThermoFisher was used, and the column temperature was set to 35°C.

[0189] [Various Measurements and Evaluations] When the composition contained a photopolymerization initiator, a measurement sample was prepared according to the following method X. 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 to the substrate and dried to obtain a laminate having a composition layer with a thickness of 10.0 μm on the substrate. The obtained laminate was exposed to light (high-pressure mercury lamp, integrated illuminance of 100 mJ / cm2 measured with an illuminometer at a wavelength of 365 nm) from the side opposite to the substrate side of the composition layer. ２) and heat-treated in an oven (220°C, 5 hours), then immersed in 2M hydrochloric acid for 8 hours for a 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. Note that 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 be peeled off. The obtained free-standing film was cut into strips to prepare measurement samples.

[0190] When the composition did not contain a photopolymerization initiator, a measurement sample was prepared according to the following method Y. Method Y: A copper-clad polyimide film (Metalloyal, manufactured by Toray Industries, Inc.) was used as a substrate. The composition shown in the table was applied to the substrate and dried to obtain a laminate having a 10.0 μm-thick composition layer 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 a peeling treatment, rinsed (in pure water at room temperature for 1 hour), and then peeled from the substrate to obtain a free-standing film derived from the composition layer. Note that if the free-standing film could not be peeled by the above peeling treatment, it was further immersed in 2M hydrochloric acid for about 1 week to peel it off. The obtained free-standing film was cut into strips to prepare measurement samples.

[0191] [Dielectric Properties (Dielectric Loss)] The average relative permittivity and average dielectric loss tangent of the measurement samples obtained by Method X or Method Y were measured using a 28 GHz split cylinder resonator (manufactured by Kanto Electronics Application Development Co., Ltd.). Five samples were measured, and the maximum and minimum values ​​were excluded, and the arithmetic mean of the remaining three values ​​was used. Next, the dielectric loss Z was calculated using the following formula, and the specific dielectric properties were evaluated according to the following evaluation criteria. Dielectric loss Z = (Dk x Df) １／２ In the formula, Dk represents the measured average relative dielectric constant, and Df represents the measured average dielectric loss tangent.

[0192] <Evaluation criteria for dielectric properties> "A": Dielectric loss Z is 0.0025 or less "B": Dielectric loss Z is more than 0.0025 and less than 0.0050 "C": Dielectric loss Z is more than 0.0050

[0193] [Migration resistance] A copper pattern (line / space = 3 μm / 3 μm) with a thickness of 3.0 μm was formed in a comb-like wiring pattern on a silicon wafer substrate, and each composition was applied to the copper pattern so that the thickness of the composition layer on the copper pattern became 10 μm, followed by drying to form a composition layer. Next, when the composition contained a photopolymerization initiator, the obtained composition layer was exposed to light using an ultra-high pressure mercury lamp. At this time, the cumulative exposure dose measured with an illuminometer at a wavelength of 365 nm was 100 mJ / cm. ２ After the exposure, a heat treatment was carried out in a nitrogen atmosphere at 220°C for 300 minutes to prepare an evaluation sample. In addition, when the composition did not contain a photopolymerization initiator, the obtained composition layer was heat treated in a nitrogen atmosphere at 220°C for 300 minutes 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, and it was confirmed whether migration occurred within 96 hours when a voltage of 10 V was applied. Note that the initial resistance value measured at room temperature (23°C) was 1 x 10 １４ Ω or more in the evaluation sample, 1 × 10 ３ It is assumed that migration occurs when the resistance drops below Ω.

[0194] <Evaluation criteria for migration resistance> "A": Migration occurred in 0 or 1 measurement sample. "B": Migration occurred in 2 or 3 measurement samples. "C": Migration occurred in 4 or 5 measurement samples. "D": Migration occurred in 6 or 7 measurement samples. "E": Migration occurred in 8 to 10 measurement samples.

[0195] The contents of various components and the evaluation results are shown below. The "Content in solid content" column shows the solid content concentration (mass %) of various components relative to the total solid content in the composition. The "Content of surface modifier" column shows the content (mass %) of surface modifier relative to the total mass of Filler X. ＋The "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 "Content (ppm by mass)" indicates the content (ppm by mass) of chloride ions relative to the total solid content in the composition.

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203] The evaluation results shown in the table confirm that the compositions of the present invention have excellent dielectric properties and excellent migration resistance. It was confirmed that when the average particle size of Filler X is 150 nm or less, the migration resistance is even better (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 the migration resistance are even better (Examples 1 to 14, etc.). Furthermore, similar comparisons confirmed that when sodium ions are contained and the sodium ion content is 20 mass ppm or less, relative to the total solids content of the composition, and when chloride ions are contained and the chloride ion content is 20 mass ppm or less, relative to the total solids content of the composition, both the dielectric properties and the migration resistance are even better.

[0204] In each example, instead of forming a composition layer using a composition, 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. The composition shown in the table was applied to a temporary support (PET film, Lumirror 16FB40, thickness 16 μm, manufactured by Toray Industries, Inc.) and dried to form a composition layer with a thickness of 10.0 μm. A cover film (polypropylene film, FG-201, thickness 30 μm, manufactured by Oji F-Tex Co., Ltd.) was then provided on the composition layer to obtain a transfer film. The cover film was peeled from the resulting transfer film, and the exposed composition layer was laminated onto the substrate for various evaluations to form a composition layer. Lamination was performed using a vacuum laminator (manufactured by MCK Corporation) under conditions of a substrate temperature of 40°C, a rubber roller temperature of 100°C, a linear pressure of 3 N / cm, and a conveying speed of 2 m / min. The temporary support was then peeled from the resulting sample. Various evaluations were then performed using the same procedures as for the above composition, and similar results were obtained.

[0205] 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 had been formed, and composition layers were formed on both sides of the glass epoxy substrate. A vacuum laminator was used for this. Lamination was performed using a vacuum laminator manufactured by MCK Corporation under conditions of a substrate temperature of 40°C, a rubber roller temperature of 100°C, a linear pressure of 3 N / cm, and a conveying speed of 2 m / min. A pattern having vias with a diameter of 60 μm was formed at predetermined positions on the composition layer and subjected to a heat treatment. After that, residues were removed using an aqueous sodium permanganate solution as a roughening solution, and electroless plating was performed. Next, a resist pattern was formed at predetermined positions using a known dry film resist, and electrolytic plating was performed. The resist pattern was then peeled off using a stripping solution. Finally, a seed layer etching treatment was performed, followed by a heat treatment (200°C, 1 hour) to form copper wiring on the cured film. The above process from lamination to heat treatment was repeated three times. Finally, a solder resist was formed as the outermost layer, and a semiconductor element was sealed and mounted to produce a semiconductor package. The resulting semiconductor package was mounted in a predetermined position on a printed wiring board to obtain a semiconductor package substrate. The resulting semiconductor package substrate was confirmed to operate normally.

[0206] 12: Temporary support 14: Composition layer 16: Cover film 100: Transfer film

Claims

1. A composition comprising a resin and a filler X whose surface has been 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.

2. 2. The composition of claim 1, wherein the filler X comprises at least one selected from the group consisting of silicon dioxide, boron nitride, barium sulfate, and silicates.

3. 2. The composition according to claim 1, wherein the average particle size of the filler X is 150 nm or less.

4. The composition according to claim 1, wherein the content of the filler X is 90.0 mass % or less based on the total solid content of the composition.

5. The composition according to claim 1 , wherein the content of the surface modifier is 2.5 mass % or less based on the total mass of the filler X.

6. The content of the filler X is 60.0 mass% or more relative to the total solid content of the composition, The average particle size of the filler X is 150 nm or less, The composition according to claim 1 , wherein the content of the surface modifier is 2.0 mass % or less relative to the total mass of the filler X.

7. The composition described in claim 6, wherein the content of the surface modifier is 0.5 mass% or more and 1.5 mass% or less relative to the total mass of the filler X.

8. The composition described in claim 6, wherein the content of filler X is 70.0 mass% or more relative to the total solid content of the composition.

9. The composition according to claim 1, wherein 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, polybenzimidazole, polyphenylsulfone, polycarbonate, an acrylonitrile-butadiene-styrene resin, and polyphenylene sulfide.

10. The composition of claim 1 , wherein the resin comprises at least one selected from the group consisting of phenolic resins and epoxy resins.

11. Furthermore, it does not contain sodium ions or The composition according to claim 1 , wherein, when the composition contains sodium ions, the content of the sodium ions is 50 ppm by mass or less based on the total solid content of the composition.

12. Furthermore, it is chloride ion-free or The composition according to claim 1 , wherein, when the composition contains chloride ions, the content of the chloride ions is 50 ppm by mass or less based on the total solid content of the composition.

13. The composition according to claim 1 , which satisfies at least one of the following conditions: it contains the resin having an ethylenically unsaturated group; and it contains a polymerizable compound having an ethylenically unsaturated group.

14. The composition of claim 13 further comprising a photoinitiator.

15. A transfer film having a temporary support and a composition layer formed using the composition according to any one of claims 1 to 14.

16. forming a composition layer on a substrate using the composition according to any one of claims 1 to 14; forming a pattern having vias in the composition layer; and a step of heating or exposing the pattern to light.

17. A laminate produced by the method for producing a laminate according to claim 16.

18. A cured film obtained by curing the composition according to claim 10.