Resin composition

Abstract

Provided are: a resin composition which exhibits excellent adhesion to a conductor layer, suppresses the occurrence of warpage, and is capable of obtaining a cured product having low dielectric properties; and the like. A resin composition containing (A) a silicone resin having a structural unit represented by formula (A-1) and a structural unit represented by formula (A-2), (B) an epoxy resin, (C) an active ester-based curing agent, and (D) an inorganic filler. 'NUMERATION 1' # IMGABS0 #

Description

Technical Field

[0001] The present invention relates to a resin composition. Further, it relates to a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition. Background Art

[0002] As a manufacturing technique for printed wiring boards, a manufacturing method using an assembly method in which an insulating layer and a conductor layer are alternately laminated is known.

[0003] As an insulating material for a printed wiring board for such an insulating layer, for example, a resin composition is disclosed in Patent Document 1.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2013-173841 Summary of the Invention

[0007] Problems to be Solved by the Invention

[0008] In recent years, with the high functionality of printed wiring boards, for the insulating layer of printed wiring boards, high adhesion to the conductor layer and suppression of warping are required. In addition, for the insulating layer, further improvement of the dielectric loss tangent and the dielectric constant is also required. Hereinafter, the dielectric loss tangent and the relative dielectric constant may be collectively referred to as dielectric properties.

[0009] The problem of the present invention is conceived in view of the above problems, and is to provide a resin composition having excellent adhesion to a conductor layer, suppression of generation of warpage amount, and capable of obtaining a cured product having low dielectric properties; a resin sheet containing the resin composition; a printed wiring board having an insulating layer formed by using the resin composition, and a semiconductor device.

[0010] Means for Solving the Problems

[0011] The present inventors conducted intensive studies on the above problems, and as a result, found that by combinatorially containing (A) a silicone resin having specific structural units, (B) an epoxy resin, (C) an active ester-based curing agent, and (D) an inorganic filler, the above problems can be solved, and the present invention was completed.

[0012] That is, the present invention includes the following.

[0013] [1] A resin composition containing:

[0014] (A) A silicone resin having a structural unit represented by the following formula (A-1) and a structural unit represented by the following formula (A-2),

[0015] (B) Epoxy resin (except those conforming to the component (A)),

[0016] (C) Active ester-based curing agent, and

[0017] (D) Inorganic filler,

[0018] [Chemical Formula 1]

[0019]

[0020] In formula (A-1), R 1 represents a group represented by the following formula (A-1a) or a group represented by the following formula (A-1b), R 2 represents a monovalent hydrocarbon group which may have a substituent, and * represents a bonding end,

[0021] In formula (A-2), R 3 and R 4 each independently represent a monovalent hydrocarbon group which may have a substituent, and * represents a bonding end,

[0022] [Chemical Formula 2]

[0023]

[0024] In formula (A-1a), n1 represents an integer from 2 to 10, and * represents the bonding end to the silicon atom in formula (A-1),

[0025] In formula (A-1b), n2 represents an integer from 1 to 10, and * represents the bonding end to the silicon atom in formula (A-1).

[0026] [2] The resin composition according to [1], wherein n1 in formula (A-1a) represents an integer from 3 to 8.

[0027] [3] The resin composition according to [1] or [2], wherein in formula (A-1), R 2 represents an alkyl group which may have a substituent.

[0028] [4] The resin composition according to any one of [1] to [3], wherein in formula (A-2), R 3 and R 4 each independently represent an aryl group which may have a substituent.

[0029] [5] The resin composition according to any one of [1] to [4], wherein in formula (A-2), R 3 and R 4 each independently represent a phenyl group which may have a substituent.

[0030] [6] The resin composition according to any one of [1] to [5], wherein the number average molecular weight of the component (A) is 10,000 or less.

[0031] [7] The resin composition according to any one of [1] to [6], wherein the content of the component (D) exceeds 60% by mass when the non-volatile component of the resin composition is set to 100% by mass.

[0032] [8] A resin sheet, comprising: a support; and a resin composition layer provided on the support and containing the resin composition according to any one of [1] to [7].

[0033] [9] A printed wiring board, comprising an insulating layer formed of a cured product of the resin composition according to any one of [1] to [7].

[0034]

[10] A semiconductor device, comprising the printed wiring board described in [9].

[0035] Effects of the Invention

[0036] According to the present invention, it is possible to provide a resin composition having excellent adhesion to a conductor layer, suppressed generation of warpage amount, and capable of obtaining a cured product with low dielectric properties; a resin sheet containing the resin composition; a printed wiring board including an insulating layer formed using the resin composition, and a semiconductor device. Detailed Description of the Invention

[0037] Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments and illustrative examples, and can be arbitrarily modified and implemented without departing from the scope of the patent claims of the present invention and their equivalents.

[0038] [Resin Composition]

[0039] The resin composition of the present invention contains: (A) a silicone resin having a structural unit represented by formula (A-1) and a structural unit represented by formula (A-2), (B) an epoxy resin (excluding the resin corresponding to the component (A)), (C) an active ester-based curing agent, and (D) an inorganic filler. In the present invention, by containing the components (A), (B), (C), and (D) in combination, it is possible to obtain a cured product having excellent adhesion to a conductor layer, suppressed generation of warpage amount, and low dielectric properties. In addition, generally, a cured product having excellent adhesion to a copper foil after the HAST test can also be obtained.

[0040] The resin composition may further contain optional components in combination with components (A) to (D). Examples of the optional components include (E) a thermosetting resin, (F) a high molecular weight component, (G) a curing accelerator, (H) an organic filler, (I) other additives, and (J) a solvent, etc. Hereinafter, each component contained in the resin composition will be described in detail.

[0041] <(A) Silicone resin having a structural unit represented by formula (A-1) and a structural unit represented by formula (A-2)>

[0042] In the resin composition, a silicone resin having a structural unit represented by formula (A-1) and a structural unit represented by formula (A-2) is contained as component (A). By containing component (A) in the resin composition, a cured product having excellent dielectric properties and adhesion can be obtained. In addition, since component (A) has a Si-O backbone, the stress of the resin composition is alleviated. As a result, the elastic modulus of the cured product is reduced, and the warpage amount of the cured product is suppressed. Component (A) can be used alone or in combination of two or more.

[0043] [Chemical formula 3]

[0044]

[0045] In formula (A-1), R 1 represents a group represented by the following formula (A-1a) or a group represented by the following formula (A-1b), and R 2 represents a monovalent hydrocarbon group which may have a substituent. * represents a bonding end.

[0046] * represents a bonding end.

[0047] In formula (A-2), R 3 and R 4 each independently represent a monovalent hydrocarbon group which may have a substituent.

[0048] * represents a bonding end,

[0049] [Chemical formula 4]

[0050]

[0051] In formula (A-1a), n1 represents an integer of 2 to 10. * represents the bonding end to the silicon atom in formula (A-1).

[0052] In formula (A-1b), n2 represents an integer of 1 to 10. * represents the bonding end to the silicon atom in formula (A-1).

[0053] In formula (A-1), R 1represents a group represented by formula (A-1a) or a group represented by formula (A-1b).

[0054] In formula (A-1a), n1 represents an integer of 2 to 10, preferably an integer of 3 to 8, more preferably an integer of 3 to 6, still more preferably an integer of 3 to 5, and particularly preferably 3.

[0055] In formula (A-1b), n2 represents an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, still more preferably 1 or 2, and particularly preferably 1.

[0056] In formula (A-1), R 2 represents a monovalent hydrocarbon group which may have a substituent. Further, in formula (A-2), R 3 and R 4 each independently represent a monovalent hydrocarbon group which may have a substituent.

[0057] The monovalent hydrocarbon group means a group obtained by removing one hydrogen atom from a hydrocarbon compound. The monovalent hydrocarbon group may be a monovalent saturated hydrocarbon group or a monovalent unsaturated hydrocarbon group. The monovalent hydrocarbon group may have an aromatic structure or may not have an aromatic structure. The monovalent hydrocarbon group is preferably a monovalent hydrocarbon group having 1 to 20 carbon atoms, more preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, still more preferably a monovalent hydrocarbon group having 1 to 6 carbon atoms. Examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkylaryl group, etc.

[0058] The alkyl group means a straight-chain, branched-chain and / or cyclic monovalent aliphatic saturated hydrocarbon group. For the alkyl group, unless otherwise specified, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 10 carbon atoms is more preferred, an alkyl group having 1 to 6 carbon atoms is further preferred, and an alkyl group having 1 to 3 carbon atoms is particularly preferred. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, 2-methylpropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, neopentyl, tert-pentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, tert-octyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, etc., and methyl is preferred among them.

[0059] As used herein, the term "alkenyl" refers to a straight-chain, branched-chain, and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one non-aromatic carbon-carbon double bond. For alkenyl groups, unless otherwise specified, alkenyl groups having 2 to 20 carbon atoms are preferred, alkenyl groups having 2 to 10 carbon atoms are more preferred, and alkenyl groups having 2 to 6 carbon atoms are further preferred. Examples of alkenyl groups include vinyl, propenyl (allyl, 1-propenyl, isopropenyl), butenyl (1-butenyl, crotyl, methallyl, isocrotyl, etc.), pentenyl (1-pentenyl, etc.), hexenyl (1-hexenyl, etc.), heptenyl (1-heptenyl, etc.), octenyl (1-octenyl, etc.), cyclopentenyl (2-cyclopentenyl, etc.), cyclohexenyl (3-cyclohexenyl), and the like.

[0060] As used herein, the term "aryl" refers to a monovalent aromatic hydrocarbon group obtained by removing one hydrogen atom from an aromatic carbocyclic ring. For aryl groups, unless otherwise specified, aryl groups having 6 to 20 carbon atoms are preferred, aryl groups having 6 to 15 carbon atoms are more preferred, and aryl groups having 6 to 10 carbon atoms are further preferred. Examples of aryl groups include phenyl, 1-naphthyl, 2-naphthyl, etc., and phenyl is preferred.

[0061] As used herein, the term "aralkyl" refers to an alkyl group substituted with one or more (preferably one) aryl groups. For aralkyl groups, unless otherwise specified, aralkyl groups having 7 to 20 carbon atoms are preferred, aralkyl groups having 7 to 15 carbon atoms are more preferred, and aralkyl groups having 7 to 11 carbon atoms are further preferred. Examples of aralkyl groups include benzyl, phenethyl, hydrocinnamyl, α-methylbenzyl, α-cumyl, 1-naphthylmethyl, 2-naphthylmethyl, and the like.

[0062] As used herein, the term "alkylaryl" refers to an aryl group substituted with one or more (preferably one) alkyl groups. For alkylaryl groups, unless otherwise specified, alkylaryl groups having 7 to 15 carbon atoms are preferred, and alkylaryl groups having 7 to 11 carbon atoms are more preferred. Examples of alkylaryl groups include 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-ethylphenyl, 3-ethylphenyl, 2-ethylphenyl, 4-isopropylphenyl, 3-isopropylphenyl, 2-isopropylphenyl, etc., and 4-methylphenyl is preferred.

[0063] The monovalent hydrocarbon group may have substituents. Examples of substituents include halogen atoms, -OH, -O-C 1-6 alkyl, -N(C 1-10 alkyl)2, C 1-20 alkyl, C 2-30 alkenyl, C 2-30 alkynyl, C 6-10 aryl, cyano, -NH2, -CN, -C(O)O-C 1-10 alkyl, -COOH, -C(O)H, -NO2, etc. Among them, "Cp-q "(p and q are positive integers satisfying p < q.) Such a term indicates that the number of carbon atoms in the organic group described after this term is p to q. For example, "C 1-10 alkyl" such an expression indicates an alkyl group having 1 to 10 carbon atoms. These substituents may bond to each other to form a ring, and the ring structure also includes a spiro ring and a fused ring.

[0064] In formula (A-1), R 1 The monovalent hydrocarbon group which may have a substituent preferably represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and more preferably an alkyl group which may have a substituent.

[0065] In formula (A-2), R 3 and R 4 The monovalent hydrocarbon groups which may have a substituent each independently preferably represent an alkyl group which may have a substituent or an aryl group which may have a substituent, more preferably an aryl group which may have a substituent, and further preferably a phenyl group.

[0066] As specific examples of the structural unit represented by formula (A-1), the structural units represented by formulas (A-1-1) to (A-1-2) can be cited, but the present invention is not limited thereto. In the formula, * represents a bonding end.

[0067] [Chemical Formula 5]

[0068]

[0069] In component (A), the number of the structural units represented by formula (A-1) is 1 or more, preferably 100 or less, more preferably 50 or less, and further preferably 30 or less. When there are a plurality of structural units represented by formula (A-1), the structural units represented by formula (A-1) can be connected to each other as repeating units, or may not be connected to each other. When not connected to each other, for a plurality of structural units represented by formula (A-1), preferably a structural unit represented by formula (A-2) or other structural units are interposed therebetween. In addition, when there are a plurality of structural units represented by formula (A-1), R 1 and R 2 may be the same or different.

[0070] Relative to 100 mol% of the entire molecule of component (A), the amount of the structural unit represented by formula (A-1) is preferably 35 mol% or more, more preferably 40 mol% or more, further preferably 45 mol% or more, preferably 65 mol% or less, more preferably 60 mol% or less, and further preferably 55 mol% or less.

[0071] As a specific example of the structural unit represented by the formula (A-2), the structural units represented by the formulas (A-2-1) to (A-2-3) can be cited, but the present invention is not limited thereto. In the formula, * represents a bonding end.

[0072] [Chemical Formula 6]

[0073]

[0074] In the component (A), the number of the structural units represented by the formula (A-2) is 1 or more, preferably 100 or less, more preferably 50 or less, and further preferably 30 or less. When there are a plurality of structural units represented by the formula (A-2), the structural units represented by the formula (A-2) can be connected to each other as repeating units, or they may not be connected to each other. When they are not connected to each other, for a plurality of structural units represented by the formula (A-2), it is preferred that the structural unit represented by the formula (A-1) or other structural units are interposed therebetween. In addition, when there are a plurality of structural units represented by the formula (A-2), R in the formula (A-2) 3 and R 4 may be the same or different.

[0075] Relative to 100 mol% of the entire molecule of the component (A), the amount of the structural unit represented by the formula (A-2) is preferably 35 mol% or more, more preferably 40 mol% or more, further preferably 45 mol% or more, preferably 65 mol% or less, more preferably 60 mol% or less, and further preferably 55 mol% or less.

[0076] When the amount of the structural unit represented by the formula (A-1) is set to a1 and the amount of the structural unit represented by the formula (A-2) is set to b1 relative to the entire molecule of the component (A), a1 / b1 is preferably 0.8 or more, more preferably 0.9 or more, further preferably 1.0 or more, preferably 1.2 or less, more preferably 1.1 or less, and further preferably 1.05 or less.

[0077] As the component (A), a resin having the structural unit represented by the formula (A-1) and the structural unit represented by the formula (A-2) can be used. The component (A) may be a random copolymer having the structural unit represented by the formula (A-1) and the structural unit represented by the formula (A-2), a block copolymer, a graft copolymer, or an alternating copolymer.

[0078] As the terminal structure of the component (A), for example, a monovalent hydrocarbon group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an aryloxy group, or an aralkyloxy group represented by R in the formula (A-1) is preferred, an alkyl group, an aryl group, a hydroxyl group, or an alkoxy group is more preferred, an alkyl group, a hydroxyl group, an alkoxy group is further preferred, and a hydroxyl group or an alkoxy group is particularly preferred. 2 ​

[0079] The so-called alkoxy group means a monovalent group formed by bonding an alkyl group to an oxygen atom (i.e., a group represented by R A1 -O-(R A1 is an alkyl group). For the alkoxy group, unless otherwise specified, an alkoxy group having 1 to 10 carbon atoms is preferred, an alkoxy group having 1 to 6 carbon atoms is more preferred, and an alkoxy group having 1 to 3 carbon atoms is further preferred. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, and the like.

[0080] The so-called alkenyloxy group means a monovalent group formed by bonding an alkenyl group to an oxygen atom (i.e., a group represented by R A2 -O-(R A2 is an alkenyl group). For the alkenyloxy group, unless otherwise specified, an alkenyloxy group having 2 to 18 carbon atoms is preferred, an alkenyloxy group having 2 to 10 carbon atoms is more preferred, and an alkenyloxy group having 2 to 6 carbon atoms is further preferred. Examples of the alkenyloxy group include vinyloxy group, allyloxy group (allyloxy group, 1-propenyloxy group, isopropenyloxy group), and the like.

[0081] The so-called aryloxy group means a monovalent group formed by bonding an aryl group to an oxygen atom (i.e., a group represented by R A3 -O-(R A3 is an aryl group). For the aryloxy group, unless otherwise specified, an aryloxy group having 6 to 18 carbon atoms is preferred, and an aryloxy group having 6 to 10 carbon atoms is more preferred. Examples of the aryloxy group include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, and the like.

[0082] The so-called aralkyloxy group means a monovalent group formed by bonding an aralkyl group to an oxygen atom (i.e., a group represented by R A4 -O-(R A4 is an aralkyl group). For the aralkyloxy group, unless otherwise specified, an aralkyloxy group having 7 to 19 carbon atoms is preferred, and an aralkyloxy group having 7 to 11 carbon atoms is more preferred. Examples of the aralkyloxy group include benzyloxy group, α-methylbenzyloxy group, and the like.

[0083] The alkoxy group, alkenyloxy group, or aryloxy group may have a substituent. The substituent is the same as the substituent that the monovalent hydrocarbon group represented by R in the formula (A-1) may have. 2

[0084] Regarding the component (A), in addition to the structural unit represented by the formula (A-1) and the structural unit represented by the formula (A-2), other structural units may be included as long as the effects of the present invention are not hindered. Examples of the other structural units include the structural unit represented by the following formula (A-4).

[0085] ​[Chemical Formula 7]

[0086]

[0087] In formula (A-4), R 5 and R 6 each independently represent a hydrogen atom or a monovalent hydrocarbon group which may have a substituent. * represents a bonding end. However, R 5 is a group different from R 3 and R 4 in formula (A-2).

[0088] In formula (A-4), R 5 and R 6 each independently represent a hydrogen atom or a monovalent hydrocarbon group which may have a substituent. The monovalent hydrocarbon group which may have a substituent represented by R 5 and R 6 is the same as the monovalent hydrocarbon group which may have a substituent represented by R 3 , R 4 in formula (A-2).

[0089] Specific examples of the component (A) include the compounds represented by (A1) to (A6), but the present invention is not limited thereto. In the formula, * represents a bonding end.

[0090] [Chemical Formula 8]

[0091]

[0092] [Chemical Formula 9]

[0093]

[0094] There is no particular limitation on the method for synthesizing the component (A). For example, the component (A) can be synthesized by polymerizing a dialkoxysilane compound or a diaryloxysilane compound with a silanediol compound. The temperature condition is preferably 30 to 120 °C, more preferably 50 to 100 °C. The reaction time is preferably 1 hour to 7 days, more preferably 3 hours to 5 days.

[0095] The weight-average molecular weight of the component (A) is preferably 5000 or more, more preferably 6000 or more, further preferably 7000 or more, preferably 15000 or less, more preferably 14000 or less, and further preferably 13000 or less. The weight-average molecular weight of the component (A) is the weight-average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) method.

[0096] The number-average molecular weight of the component (A) is preferably 10,000 or less, more preferably 9,500 or less, still more preferably 9,000 or less, 8,500 or less, preferably 1,000 or more, more preferably 1,500 or more, still more preferably 2,000 or more, 2,500 or more. The number-average molecular weight of the component (A) is the number-average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0097] The active group equivalent of the component (A) is preferably 50 g / eq. or more, more preferably 100 g / eq. or more, still more preferably 150 g / eq. or more, 200 g / eq. or more, 250 g / eq. or more, 300 g / eq. or more, 350 g / eq. or more, preferably 1,000 g / eq. or less, more preferably 900 g / eq. or less, still more preferably 800 g / eq. or less, 700 g / eq. or less, 600 g / eq. or less, 500 g / eq. or less, 450 g / eq. or less.

[0098] Regarding the content of the component (A), when the non-volatile components in the resin composition are set to 100% by mass, it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 5% by mass or less, 3% by mass or less, 2% by mass or less.

[0099] Regarding the content of the component (A), when the resin components in the resin composition are set to 100% by mass, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, 15% by mass or less, 10% by mass or less, 8% by mass or less.

[0100] In the present invention, unless otherwise specified, the content of each component in the resin composition is the value when the non-volatile components in the resin composition are set to 100% by mass. The non-volatile components mean all the non-volatile components that do not include the following (J) solvent in the components constituting the resin composition. In addition, in the present invention, the resin components in the resin composition refer to the components that do not include the (D) inorganic filler in the non-volatile components of the resin composition.

[0101] <(B) Epoxy resin>

[0102] The resin composition contains (B) epoxy resin (excluding substances conforming to component (A)) as component (B). The (B) epoxy resin as component (B) does not contain substances conforming to component (A). By containing (B) epoxy resin in the resin composition, a cured product with good mechanical strength and insulation reliability can be obtained. The (B) epoxy resin can be used alone as one type or two or more types can be used in combination.

[0103] Examples of the (B) epoxy resin include bisxylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butylcatechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, glycidyl cyclohexane type epoxy resin, alkyl diglycidyl ether type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing a spiro ring, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthalene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, phenolphthalimide type epoxy resin, etc.

[0104] The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as component (B). From the viewpoint of significantly obtaining the desired effects of the present invention, the proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, based on 100% by mass of the (B) epoxy resin.

[0105] Among epoxy resins, there are epoxy resins that are liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter sometimes referred to as "solid epoxy resins"). Regarding the resin composition, as component (B), it may contain only liquid epoxy resin, only solid epoxy resin, or a combination of liquid epoxy resin and solid epoxy resin. Among them, from the viewpoint of significantly obtaining the effects of the present invention, it is preferred to contain a combination of liquid epoxy resin and solid epoxy resin.

[0106] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0107] As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidyl amine type epoxy resin, epoxy resin having a butadiene structure, glycidyl cyclohexane type epoxy resin, phenolphthaleimide type epoxy resin, alkyl diglycidyl ether type epoxy resin are preferred, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin are more preferred.

[0108] As specific examples of the liquid epoxy resin, “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation can be cited; “828US”, “jER828EL”, “825”, “Epicoat 828EL” (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “jER807”, “1750” (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “jER152” (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “630”, “630LSD” (glycidyl amine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “ZX1059” (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation; “Celloxide 2021P” (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation; “PB-3600” (epoxy resin having a butadiene structure) manufactured by Daicel Corporation; “ZX1658”, “ZX1658GS” (liquid 1,4-glycidyl cyclohexane type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; “YED216D” (alkyl diglycidyl ether type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. These can be used alone or in combination of two or more.

[0109] As the solid epoxy resin, a solid epoxy resin having two or more epoxy groups in one molecule is preferred, a solid epoxy resin having three or more epoxy groups in one molecule is more preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is further preferred.

[0110] As the solid epoxy resin, bisxylenol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, cresol novolak type epoxy resins, dicyclopentadiene type epoxy resins, triphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthalene ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, tetraphenylethane type epoxy resins are preferred, and naphthalene type epoxy resins and biphenyl type epoxy resins are more preferred.

[0111] Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol novolak type epoxy resin), "N-695" (cresol novolak type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000", "HP6000L" (naphthalene ether type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (triphenol type epoxy resin), "NC7000L" (naphthol novolak type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" (naphthalene type epoxy resin), "ESN485" (naphthol novolak type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bisxylenol type epoxy resin), "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" (bisphenol AF type epoxy resin), "YL7800" (fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "WHR-991S" (phenolphthaleimide type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. etc. These can be used alone, or two or more of them can be used in combination.

[0112] When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (B), their quantitative ratio (liquid epoxy resin:solid epoxy resin) is expressed as a mass ratio, preferably 1:0.1 to 1:20, more preferably 1:0.15 to 1:10, and particularly preferably 1:0.2 to 1:5. By setting the quantitative ratio of the liquid epoxy resin and the solid epoxy resin within this range, the desired effects of the present invention can be significantly obtained.

[0113] The epoxy equivalent of the component (B) is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., further preferably 80 g / eq. to 2000 g / eq., and even more preferably 110 g / eq. to 1000 g / eq. By being within this range, a cured body with a sufficient crosslinking density of the cured product of the resin composition can be achieved. The epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured in accordance with JIS K7236.

[0114] The weight average molecular weight (Mw) of the component (B) is preferably 100 to 5000, more preferably 150 to 3000, and further preferably 200 to 1500. The weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene measured by the gel permeation chromatography (GPC) method.

[0115] Regarding the content of the component (B), when the non-volatile components in the resin composition are set to 100% by mass, it is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less.

[0116] Regarding the content of the component (B), when the resin components in the resin composition are set to 100% by mass, it is preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 55% by mass or less, and further preferably 50% by mass or less, 45% by mass or less, 40% by mass or less.

[0117] <(C) Active ester curing agent>

[0118] The resin composition contains a (C) active ester-based curing agent as the component (C). In the (C) active ester-based curing agent as the component (C), substances corresponding to the above-mentioned components (A) to (B) are not contained. The (C) active ester-based curing agent usually forms a bond through reaction with the (B) epoxy resin, and can cure the resin composition. In addition, by combining the component (A) and the component (C) and containing them in the resin composition, a cured product with excellent adhesiveness and a low elastic modulus can be obtained. The component (C) can be used alone as one kind, or two or more kinds can be used in combination.

[0119] As the (C) active ester-based curing agent, compounds having two or more highly reactive ester groups in one molecule, such as phenolic esters, thiophenolic esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc., are generally preferably used. The active ester-based curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadiene-type diphenol compound, phenol novolac, etc. Among them, the so-called "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

[0120] Specifically, examples of the component (C) include dicyclopentadiene type active ester curing agents, naphthalene type active ester curing agents containing a naphthalene structure, active ester curing agents containing an acetylated product of phenol novolac, active ester curing agents containing a benzoylated product of phenol novolac, active ester curing agents which are acetylated products of phenol novolac, phosphorus-containing active esters, active ester curing agents containing a styryl group and a naphthalene structure, etc. Any one of a dicyclopentadiene type active ester curing agent, a naphthalene type active ester curing agent containing a naphthalene structure, and an active ester curing agent containing a styryl group and a naphthalene structure is preferred, and any one of a dicyclopentadiene type active ester curing agent and a naphthalene type active ester curing agent containing a naphthalene structure is more preferred. As the dicyclopentadiene type active ester curing agent, an active ester curing agent containing a dicyclopentadiene type diphenol structure is preferred. The so-called "dicyclopentadiene type diphenol structure" means a divalent structural unit composed of phenylene - dicyclopenteneylene - phenylene.

[0121] Examples of commercially available products of the component (C) include, as the active ester curing agent containing a dicyclopentadiene type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000L-65TM", "HPC-8000-65T", "EXB-8000H", "EXB-8000L-65TM" (manufactured by DIC Corporation); as the active ester curing agent containing a naphthalene structure, "EXB-9416-70BK", "EXB-8100L-65T", "HPC-8150-62T", "EXB-8150L-65T", "EXB-8100L-65T", "EXB-8" (manufactured by DIC Corporation); as the phosphorus-containing active ester curing agent, "EXB9401" (manufactured by DIC Corporation), as the active ester curing agent containing an acetylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation); as the active ester curing agent containing a benzoylated product of phenol novolac, "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation), "EXB-8500-65T" (manufactured by DIC Corporation); as the active ester curing agent containing a styryl group and a naphthalene structure, "PC1300-02-65T", "PC1300-02-65MA" (manufactured by Air Water Inc.), etc.

[0122] Regarding the active ester group equivalent of component (C), from the viewpoint of being able to reduce the dielectric loss tangent and simultaneously obtaining a cured product with excellent peel strength, it is preferably 50 g / eq. to 500 g / eq., more preferably 50 g / eq. to 400 g / eq., and still more preferably 100 g / eq. to 300 g / eq. The active ester group equivalent is the mass of the active ester-based curing agent containing 1 equivalent of the active ester group.

[0123] Regarding the quantitative ratio of component (B) epoxy resin to component (C) active ester-based curing agent, in terms of the ratio of [total number of active groups of the active ester-based curing agent] / [total number of epoxy groups of the epoxy resin], it is preferably 0.01 or more, more preferably 0.3 or more, still more preferably 0.5 or more, preferably 5 or less, more preferably 4 or less, and still more preferably 3 or less. Herein, the so-called "number of epoxy groups of the epoxy resin" is the total value obtained by summing up the values obtained by dividing the mass of the non-volatile component of the epoxy resin present in the resin composition by the epoxy equivalent. In addition, the so-called "number of active groups of the active ester-based curing agent" is the total value obtained by summing up the values obtained by dividing the mass of the non-volatile component of the active ester-based curing agent present in the resin composition by the active ester group equivalent. By making the quantitative ratio of the epoxy resin to the active ester-based curing agent within this range, the effects of the present invention can be significantly obtained.

[0124] Regarding the content of component (C), when the non-volatile component in the resin composition is set to 100% by mass, it is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more. In addition, the upper limit is preferably 35% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, 20% by mass or less, and 15% by mass or less.

[0125] Regarding the content of component (C), when the resin component in the resin composition is set to 100% by mass, it is preferably 30% by mass or more, more preferably 35% by mass or more, and still more preferably 40% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 65% by mass or less, and particularly preferably 60% by mass or less.

[0126] Regarding the total content of component (A), component (B), and component (C), when the non-volatile component in the resin composition is set to 100% by mass, it is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more, preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less.

[0127] <(D) Inorganic filler>

[0128] The resin composition contains (D) an inorganic filler as component (D). By containing (D) the inorganic filler in the resin composition, a cured product with low dielectric properties can be obtained. (D) The inorganic filler is usually contained in the resin composition in the form of particles. Component (D) can be used alone as one kind, or two or more kinds can be used in combination.

[0129] As the material of (D) the inorganic filler, an inorganic compound is used. As the material of (D) the inorganic filler, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium phosphotungstate, etc. can be cited. Among these, silica is particularly preferred. As silica, for example, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. can be cited. In addition, as silica, spherical silica is preferred.

[0130] As commercially available products of (D) the inorganic filler, for example, "SP60-05", "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Admatechs Co., Ltd.; "UFP-30", "DAW-03", "FB-105FD" manufactured by Denka Co., Ltd.; "Silfill NSS-3N", "Silfill NSS-4N", "Silfill NSS-5N" manufactured by Tokuyama Corporation; "Celsfiers MGH-005" manufactured by Taiheiyo Cement Corporation, etc. can be cited.

[0131] (D) The average particle diameter of the inorganic filler is preferably 0.01 μm or more, more preferably 0.1 μm or more, further preferably 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, preferably 10 μm or less, more preferably 5 μm or less, and further preferably 3 μm or less.

[0132] (D) The average particle diameter of the inorganic filler can be measured by the laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be produced on a volume basis by a laser diffraction / scattering type particle size distribution measuring device, and the median diameter thereof can be measured as the average particle diameter. Regarding the measurement sample, a product obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial (glass bottle) and subjecting the mixture to ultrasonic dispersion for 10 minutes can be used. For the measurement sample, a laser diffraction type particle size distribution measuring device is used, and the particle size distribution of the inorganic filler on a volume basis is measured in a flow cell manner using light source wavelengths of blue and red, and the average particle diameter can be calculated as the median diameter from the obtained particle size distribution. As the laser diffraction type particle size distribution measuring device, for example, "LA-960" manufactured by Horiba, Ltd. can be cited.

[0133] (D) The BET specific surface area of the inorganic filler is preferably 0.1 m 2 / g or more, more preferably 0.5 m 2 / g or more, still more preferably 1 m 2 / g or more, preferably 100 m 2 / g or less, more preferably 70 m 2 / g or less, still more preferably 40 m 2 / g or less.

[0134] (D) The specific surface area of the inorganic filler can be measured by adsorbing nitrogen on the surface of the sample in accordance with the BET method using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) and calculating the specific surface area using the BET multipoint method.

[0135] Regarding the (D) inorganic filler, from the viewpoints of improving moisture resistance and dispersibility, it is preferably treated with a surface treatment agent. As the surface treatment agent, for example, fluorosilane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, etc. can be cited. The surface treatment agent can be used alone as one kind, or two or more kinds can be arbitrarily combined and used.

[0136] Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane), "KBM803" (3-mercaptopropyltrimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane), "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), "SZ-31" (hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane), "KBM-4803" (long-chain epoxy type silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), etc., all manufactured by Shin-Etsu Chemical Co., Ltd.

[0137] Regarding the degree of surface treatment with the surface treatment agent, from the viewpoint of improving the dispersibility of the inorganic filler, it is preferably within a specific range. Specifically, it is preferable that 100% by mass of the inorganic filler is surface-treated with 0.2% to 5% by mass of the surface treatment agent, more preferably with 0.2% to 3% by mass of the surface treatment agent, and still more preferably with 0.3% to 2% by mass of the surface treatment agent.

[0138] Regarding the degree of surface treatment with the surface treatment agent, it can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Regarding the amount of carbon per unit surface area of the inorganic filler, from the viewpoint of improving the dispersibility of the inorganic filler, it is preferably 0.02 mg / m 2 or more, more preferably 0.1 mg / m 2 or more, and still more preferably 0.2 mg / m 2 or more. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition, it is preferably 1.0 mg / m 2 or less, more preferably 0.8 mg / m 2 or less, and still more preferably 0.5 mg / m 2 or less.

[0139] (D) The amount of carbon per unit surface area of the inorganic filler can be measured after cleaning the surface-treated inorganic filler with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, an adequate amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid component, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd., etc. can be used.

[0140] In addition, regarding the degree of surface treatment using the surface treatment agent, the carbon amount per unit mass of the inorganic filler can be used for evaluation. The carbon amount per unit mass of the inorganic filler is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more. In addition, it is preferably 1.0% by mass or less, more preferably 0.8% by mass or less, still more preferably 0.5% by mass or less. (D) The carbon amount per unit mass of the inorganic filler can be measured using a carbon analyzer in the same manner as the carbon amount per unit surface area of the (D) inorganic filler.

[0141] (D) When the non-volatile components in the resin composition are set to 100% by mass, the content of the inorganic filler is preferably more than 60% by mass, more preferably 65% by mass or more, still more preferably 68% by mass or more, 70% by mass or more, preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less.

[0142] <(E) Thermosetting resin>

[0143] As an optional component, the resin composition may further contain (E) a thermosetting resin as the (E) component. The (E) thermosetting resin as the (E) component does not contain substances corresponding to the (A) to (D) components. Regarding the (E) thermosetting resin, as long as it can be cured by heat, its type is not particularly limited. The (E) thermosetting resin can be used alone as 1 type, or 2 or more types can be used in combination.

[0144] Examples of the (E) thermosetting resin include radical polymerizable resins, phenolic resins, cyanate ester resins, carbodiimide resins, acid anhydride resins, amine resins, benzoxazine resins, and thiol resins. Hereinafter, phenolic resins, cyanate ester resins, carbodiimide resins, acid anhydride resins, amine resins, benzoxazine resins, and thiol resins may be collectively referred to as "curing agents".

[0145] Regarding the radical polymerizable resin as the (E) component, as long as it has 1 or more (preferably 2 or more) radical polymerizable unsaturated groups in 1 molecule, its type is not particularly limited. As the radical polymerizable resin, for example, resins having 1 or more selected from maleimide groups, vinyl groups, allyl groups, styryl groups, vinylphenyl groups, acryloyl groups, methacryloyl groups, fumaroyl groups, and maleoyl groups as radical polymerizable unsaturated groups can be cited. Among them, the radical polymerizable resin is preferably a maleimide resin, a (meth)acrylic resin, or a styrene resin.

[0146] As a maleimide resin, as long as it has one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl) in one molecule, there is no particular limitation on its type. Examples of the maleimide resin include (1) maleimide resins containing an aliphatic skeleton (preferably an aliphatic skeleton having 36 carbon atoms derived from a dimer diamine) such as "BMI-3000J", "BMI-5000", "BMI-1400", "BMI-1500", "BMI-1700", "BMI-689" (all manufactured by Designer Molecules Inc.), "SLK6895-T90" (manufactured by Shin-Etsu Chemical Co., Ltd.); (2) maleimide resins containing an indane skeleton as described in the Invention Association's publicly disclosed technical report public technology serial number 2020-500211; (3) maleimide resins containing an aromatic ring skeleton directly bonded to the nitrogen atom of the maleimide group such as "MIR-3000-70MT" (manufactured by Nippon Kayaku Co., Ltd.), "BMI-4000" (manufactured by Daiwa Kasei Co., Ltd.), "BMI-80" (manufactured by KAI CHEMICAL CO., LTD.).

[0147] As a (meth)acrylic resin, as long as it has one or more (preferably two or more) (meth)acryloyl groups in one molecule, there is no particular limitation on its type, and it can be a monomer or an oligomer. Among them, the term "(meth)acryloyl group" is a general term for acryloyl group and methacryloyl group. Examples of the methacrylic resin include, in addition to (meth)acrylate monomers, (meth)acrylic resins such as "A-DOG" (manufactured by Shin-Nakamura Chemical Co., Ltd.), "DCP-A" (manufactured by Kyoeisha Chemical Co., Ltd.), "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", "SA9000" (manufactured by SABIC), "DPHA" (all manufactured by Nippon Kayaku Co., Ltd.).

[0148] Regarding styrene resins, for example, they are compounds having one or more, preferably two or more vinyl groups directly bonded to aromatic carbon atoms. As styrene resins, for example, divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'-divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, bis(4-vinylphenyl) ether and other low-molecular-weight (molecular weight less than 1000) styrene-based compounds can be cited; vinylbenzyl-modified polyphenylene ether resins, styrene-divinylbenzene copolymers and other high-molecular-weight (molecular weight 1000 or more) styrene resins, etc. As commercially available products of styrene resins, for example, "ODV-XET(X03)", "ODV-XET(X04)", "ODV-XET(X05)" (styrene-divinylbenzene copolymer) manufactured by Nippon Steel Chemical & Material Co., Ltd., "OPE-2St 1200", "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resin) manufactured by Mitsubishi Gas Chemical Company can be cited.

[0149] Regarding the content of the free-radical polymerizable resin as the (E) thermosetting resin, when the non-volatile components in the resin composition are set to 100% by mass, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less.

[0150] Regarding the content of the free-radical polymerizable resin as the (E) thermosetting resin, when the resin components in the resin composition are set to 100% by mass, it is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less.

[0151] As the phenolic resin, a compound having one or more, preferably two or more hydroxyl groups bonded to an aromatic ring such as a benzene ring or a naphthalene ring in one molecule can be used. When the phenolic resin is combined with an epoxy resin, it can react with the epoxy resin to cure the resin composition, and thus is sometimes referred to as a "phenolic curing agent". Regarding the phenolic resin, from the viewpoint of significantly obtaining the effects of the present invention, a phenolic resin having a novolak structure is preferred. In addition, from the viewpoint of adhesion, a nitrogen-containing phenolic resin is preferred, and a phenolic resin containing a triazine skeleton is more preferred. Among them, from the viewpoint of significantly obtaining the effects of the present invention, a phenol novolak resin containing a triazine skeleton is preferred. As specific examples of the phenolic resin, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiko Kasei Co., Ltd., "NHN", "CBN", "GPH" manufactured by Nippon Kayaku Co., Ltd., "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395" manufactured by Nippon Steel Chemical & Material Co., Ltd., "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", "TD-2090-60M", "KA-1163" manufactured by DIC Corporation, etc. can be cited.

[0152] As the cyanate resin, a compound having one or more, preferably two or more cyanate groups in one molecule can be used. When the cyanate resin is combined with an epoxy resin, it can react with the epoxy resin to cure the resin composition, and thus is sometimes referred to as a "cyanate curing agent". As the cyanate resin, for example, bisphenol A dicyanate, polyphenol cyanate (oligomeric (3-methylidene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanatephenyl)propane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl) sulfide, and bis(4-cyanatephenyl) ether and other bifunctional cyanate resins, polyfunctional cyanate resins derived from phenol novolak and cresol novolak, and prepolymers obtained by partial triazine formation of these cyanate resins can be cited. As specific examples of the cyanate resin, "PT30" and "PT60" (both are phenol novolak type polyfunctional cyanate resins), "BA230", "BA230S75" (a prepolymer obtained by triazine formation of a part or all of bisphenol A dicyanate to form a trimer) manufactured by arxada company, etc. can be cited.

[0153] As the carbodiimide resin (excluding substances conforming to the component (A)), a compound having one or more, preferably two or more carbodiimide structures in one molecule and not having a radically polymerizable group can be used. In the case of the carbodiimide resin, when combined with an epoxy resin, it can react with the epoxy resin to cure the resin composition, and thus is sometimes referred to as a "carbodiimide-based curing agent".

[0154] Specific examples of the carbodiimide resin include aliphatic biscarbodiimides such as tetramethylene-bis(tert-butylcarbodiimide) and cyclohexane bis(methylene-tert-butylcarbodiimide); biscarbodiimides such as phenylenebis(xylenylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylene carbodiimide, polytrimethylhexamethylene carbodiimide, polycyclohexylene carbodiimide, poly(methylenebiscyclohexylene carbodiimide), and poly(isophorone carbodiimide); and aromatic polycarbodiimides such as poly(phenylene carbodiimide), poly(naphthylene carbodiimide), poly(m-tolylene carbodiimide), poly(methyldiisopropylphenylene carbodiimide), poly(triethylphenylene carbodiimide), poly(diethylphenylene carbodiimide), poly(triisopropylphenylene carbodiimide), poly(diisopropylphenylene carbodiimide), poly(xylenylcarbodiimide), poly(tetramethylxylenylcarbodiimide), poly(methylenediphenylene carbodiimide), and poly[methylenebis(m-methylphenyl)]carbodiimide.

[0155] Commercially available products of the carbodiimide resin include, for example, "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07", and "Carbodilite V-09" manufactured by Nisshinbo Chemical Inc.; "Stabaxol P", "Stabaxol P100", "Stabaxol P400", "Highcadyl 510", etc. manufactured by LANXESS Corporation.

[0156] As the acid anhydride resin, a compound having one or more, preferably two or more acid anhydride groups in one molecule can be used. When combined with an epoxy group, the acid anhydride resin can react with the epoxy resin to cure the resin composition, and thus is sometimes referred to as an "acid anhydride-based curing agent". Specific examples of the acid anhydride resin include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride), polymer-type acid anhydrides such as styrene-maleic acid resin obtained by copolymerizing styrene and maleic acid, etc. Commercially available products of the acid anhydride resin include, for example, "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by Shin Nippon Rika Co., Ltd.; "YH-306", "YH-307" manufactured by Mitsubishi Chemical Corporation; "HN-2200", "HN-5500" manufactured by Resonac Co., Ltd.; "EF-30", "EF-40", "EF-60", "EF-80" manufactured by Cray Valley Co., Ltd., etc.

[0157] As the amine resin, a compound having one or more, preferably two or more amino groups in one molecule can be used. When combined with an epoxy group, the amine resin can react with the epoxy resin to cure the resin composition, and thus is sometimes referred to as an "amine-based curing agent". Examples of the amine resin include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc., among which aromatic amines are preferred. The amine resin is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine resin include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. Commercially available products of the amine resin include, for example, "SEIKACURE-S" manufactured by SEIKA Corporation; "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD A-A", "KAYAHARD A-B", "KAYAHARD A-S" manufactured by Nippon Kayaku Co., Ltd.; "EPICURE W" manufactured by Mitsubishi Chemical Corporation; "DTDA" manufactured by Sumitomo Seika Chemicals Co., Ltd., etc.

[0158] When combined with an epoxy resin, the benzoxazine resin can react with the epoxy resin to cure the resin composition, and thus is sometimes referred to as a "benzoxazine-based curing agent". Specific examples of the benzoxazine resin include "JBZ-OP100D", "ODA-BOZ" manufactured by JFE Chemical Corporation; "HFB2006M" manufactured by Showa Highpolymer Co., Ltd.; "P-d", "F-a" manufactured by Shikoku Kasei Kogyo Co., Ltd., etc.

[0159] When combined with an epoxy resin, the thiol resin can react with the epoxy resin to cure the resin composition, and thus is sometimes referred to as a "thiol-based curing agent". Examples of the thiol resin include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), tris(3-mercaptopropyl)isocyanurate, etc.

[0160] The equivalent weight of the active groups of the curing agent is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., still more preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The equivalent weight of the active groups is the mass of the curing agent per 1 equivalent of the active groups.

[0161] The weight-average molecular weight (Mw) of the curing agent is preferably 100 to 5000, more preferably 250 to 3000, still more preferably 400 to 1500. The weight-average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a value in terms of polystyrene conversion.

[0162] When the number of epoxy groups of the (B) epoxy resin is 1, the number of active groups of the curing agent is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, preferably 5 or less, more preferably 3 or less, and particularly preferably 2 or less. The so-called "number of epoxy groups of the epoxy resin" means the total value obtained by dividing the mass of the non-volatile components of the epoxy resin present in the resin composition by the epoxy equivalent. In addition, the so-called "number of active groups of the curing agent" means the total value obtained by dividing the mass of the non-volatile components of the curing agent present in the resin composition by the equivalent weight of the active groups.

[0163] When the non-volatile components in the resin composition are set to 100% by mass, the content of the curing agent for the (E) thermosetting resin is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less.

[0164] When the resin components in the resin composition are set to 100% by mass, the content of the curing agent for the (E) thermosetting resin is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, preferably 35% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less.

[0165] (E) When the non-volatile components in the resin composition are set to 100% by mass, the content of the thermosetting resin is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less.

[0166] (E) When the resin components in the resin composition are set to 100% by mass, the content of the thermosetting resin is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, preferably 35% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less.

[0167] <(F) Polymer Component>

[0168] In the case of the resin composition, as an optional component, (F) polymer component may be further contained as the (F) component. The (F) polymer component as the (F) component does not contain substances corresponding to the (A) -

[0169] (E) component. By containing the (F) component in the resin composition, the stress of the resin composition is alleviated, and as a result, a cured product with a low elastic modulus can be obtained. The (F) component can be used alone or in combination of two or more.

[0170] (F) component can use components with a high molecular weight in terms of weight average molecular weight. As such components, for example, polyimide resin, phenoxy resin, polyimide resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester resin, etc. can be cited.

[0171] (F) The weight average molecular weight (Mw) of the component is preferably greater than 5000, more preferably 8000 or more, still more preferably 10000 or more, particularly preferably 20000 or more, preferably 100000 or less, more preferably 70000 or less, still more preferably 60000 or less, and particularly preferably 50000 or less.

[0172] Polyimide resin refers to a resin containing repeating units containing imide bonds. Generally, polyimide resin contains repeating units having a structure obtained by reacting a diamine compound with an acid anhydride (imide-forming reaction).

[0173] As the diamine compound, for example, aliphatic diamine compounds and aromatic diamine compounds can be cited. Among them, aromatic diamine compounds are preferred. As the aromatic diamine compound, for example, benzene diamine compounds, naphthalene diamine compounds, diphenylamine compounds, etc. can be cited, and diphenylamine compounds are preferred among them.

[0174] The so-called diphenylamine compound refers to a compound containing two aniline structures in the molecule. The benzene rings in the aniline structure may each optionally have 1 - 3 substituents. The two aniline structures in the diphenylamine compound are directly bonded or may be bonded via a linking structure having 1 - 100 backbone atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms.

[0175] As specific examples of the "linking structure" in the diphenylamine compound, -NHCO-, -CONH-, -OCO-, -COO-, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH(CH3)-, -C(CH3)2-, -C(CF3)2-, -CH=CH-, -O-, -S-, -CO-, -SO2-, -NH-, -Ph-, -Ph-Ph-, -C(CH3)2-Ph-C(CH3)2-, -O-Ph-O-, -O-Ph-Ph-O-, -O-Ph-SO2-Ph-O-, -O-Ph-C(CH3)2-Ph-O-, -Ph-CO-O-Ph-, -C(CH3)2-Ph-C(CH3)2-, the group represented by the following formula (I), the group represented by (II), and the group composed of their combinations can be cited. In this specification, as for "Ph", unless otherwise specified, it represents 1,4-phenylene, 1,3-phenylene or 1,2-phenylene. In the following formulas (I) and (II), "*" represents a bonding end.

[0176]

Chemical formula 10

[0177]

[0178] As the diphenylamine compound, for example, 4,4'-diamino-2,2'-bis(trifluoromethyl)-1,1'-biphenyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4-aminophenyl 4-aminobenzoate, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)propane, 4,4'-(hexafluoroisopropylidene)diphenylamine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, α,α-bis[4-(4-aminophenoxy)phenyl]-1,3-diisopropylbenzene, α,α-bis[4-(4-aminophenoxy)phenyl]-1,4-diisopropylbenzene, 4,4'-(9-fluorenylidene)diphenylamine, 2,2-bis(3-methyl-4-aminophenyl)propane, 2,2-bis(3-methyl-4-aminophenyl)benzene, 4,4'-diamino-3,3'-dimethyl-1,1'-biphenyl, 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis(3-methyl-4-aminophenyl)fluorene, 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane, etc. can be cited. The diamine compound can be used alone or in combination of two or more.

[0179] As the acid anhydride, generally, acid dianhydride can be used, and aromatic tetracarboxylic dianhydride is preferred. As the aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, naphthalenetetracarboxylic dianhydride, anthracenetetracarboxylic dianhydride, diphthalic dianhydride, etc. can be cited, and diphthalic dianhydride is preferred.

[0180] The so-called diphthalic dianhydride means a compound containing two phthalic anhydride structures in the molecule. The benzene rings in the phthalic anhydride structure can each optionally have 1 to 3 substituents. The two phthalic anhydride structures in the diphthalic dianhydride can be directly bonded or bonded via a linking structure having 1 to 100 backbone atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms.

[0181] As an example of the "linking structure" in the diphthalic dianhydride, a divalent group represented by -[R e -Ph] me -R e -[Ph-R e ne - can be cited. In this formula, R e ​Each independently represents a single bond, -(substituted or unsubstituted alkylene)-, -O-, -S-, -CO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-; me and ne each independently represent an integer from 0 to 2 (preferably 0 or 1). Specific examples of the linking structure include -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH(CH3)-, -C(CH3)2-, -O-, -CO-, -SO2-, -Ph-, -O-Ph-O-, -O-Ph-SO2-Ph-O-, -O-Ph-C(CH3)2-Ph-O-, etc.

[0182] Examples of the dianhydride of diphthalic acid include 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl sulfone tetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl) sulfone dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylene-4,4'-diphthalic dianhydride, 2,2-propylene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic dianhydride, etc. The acid anhydride can be used alone or in combination of two or more.

[0183] The polyimide resin can be manufactured by known methods. For example, the polyimide resin can be manufactured by a method including heating a mixture of a diamine compound, an acid anhydride, and a solvent to cause a reaction. In addition, as the polyimide resin, commercially available products can be used. Specific examples of commercially available polyimide resins include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., "Rika Coat SN20" and "Rika Coat PN20" manufactured by Nippon Rika Kako Co., Ltd., and the like.

[0184] As the phenoxy resin, for example, phenoxy resins having one or more skeletons selected from a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolak skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton can be cited. The terminal of the phenoxy resin can be any functional group such as a phenolic hydroxyl group or an epoxy group. Specific examples of the phenoxy resin include "1256" and "4250" (both are phenoxy resins containing a bisphenol A skeleton) manufactured by Mitsubishi Chemical Corporation; "YX8100" (a phenoxy resin containing a bisphenol S skeleton) manufactured by Mitsubishi Chemical Corporation; "YX6954" (a phenoxy resin containing a bisphenol acetophenone skeleton) manufactured by Mitsubishi Chemical Corporation; "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482", and "YL7891BH30" manufactured by Mitsubishi Chemical Corporation, and the like.

[0185] As the polyvinyl acetal resin, for example, polyvinyl formal resins and polyvinyl butyral resins can be cited, and polyvinyl butyral resins are preferred. Specific examples of the polyvinyl acetal resin include the ESREC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, BM series, etc. manufactured by Sekisui Chemical Co., Ltd.

[0186] As the polyolefin resin, for example, ethylene-based copolymer resins such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; polyolefin-based polymers such as polypropylene and ethylene-propylene block copolymer can be cited.

[0187] As the polybutadiene resin, for example, resins containing a hydrogenated polybutadiene backbone, polybutadiene resins containing a hydroxyl group, polybutadiene resins containing a phenolic hydroxyl group, polybutadiene resins containing a carboxyl group, polybutadiene resins containing an acid anhydride group, polybutadiene resins containing an epoxy group, polybutadiene resins containing an isocyanate group, polybutadiene resins containing a urethane group, polyphenylene ether-polybutadiene resins, etc. can be cited.

[0188] As specific examples of the polyamideimide resin, "VYRMAX HR11NN" and "VYRMAX HR16NN" manufactured by Toyobo Co., Ltd. can be cited. As other specific examples of the polyamideimide resin, modified polyamideimides such as "KS9100" and "KS9300" (polyamideimide containing a polysiloxane backbone) manufactured by Resona Co., Ltd. can be cited.

[0189] As a specific example of the polyethersulfone resin, "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. can be cited.

[0190] As specific examples of the polysulfone resin, polysulfones "P1700", "P3500", etc. manufactured by Solvay Advanced Polymers can be cited.

[0191] As a specific example of the polyphenylene ether resin, "NORYL SA90" manufactured by SABIC can be cited. As a specific example of the polyetherimide resin, "ULTEM" manufactured by GE can be cited.

[0192] As the polycarbonate resin, for example, carbonate resins containing a hydroxyl group, carbonate resins containing a phenolic hydroxyl group, carbonate resins containing a carboxyl group, carbonate resins containing an acid anhydride group, carbonate resins containing an isocyanate group, carbonate resins containing a urethane group, etc. can be cited. As specific examples of the polycarbonate resin, "FPC0220" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002", "T6001" (polycarbonate diol) manufactured by Asahi Kasei Corporation, "C-1090", "C-2090", "C-3090" (polycarbonate diol) manufactured by Kuraray Co., Ltd., etc. can be cited. As a specific example of the polyetheretherketone resin, "Sumipro EK" manufactured by Sumitomo Chemical Co., Ltd. can be cited.

[0193] As the polyester resin, for example, polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polypropylene terephthalate resin, polypropylene naphthalate resin, polycyclohexanedimethanol terephthalate resin, etc. can be cited.

[0194] Regarding the content of the (F) polymer component, when the non-volatile components in the resin composition are set to 100% by mass, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 0.8% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less, and still more preferably 1.5% by mass or less.

[0195] Regarding the content of the (F) polymer component, when the resin components in the resin composition are set to 100% by mass, it is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 8% by mass or less.

[0196] <(G) Curing Accelerator>

[0197] Regarding the resin composition, as an optional component, (G) curing accelerator can be further contained as the (G) component. Among the (G) curing accelerators as the (G) component, substances conforming to the above (A) to (F) components are not contained. By containing the (G) component, the curing of the (B) component can be further promoted. The (G) component can be used alone as one kind, or two or more kinds can be used in combination.

[0198] As the (G) component, for example, phosphorous curing accelerators, urea curing accelerators, guanidine curing accelerators, imidazole curing accelerators, metal curing accelerators, amine curing accelerators, etc. can be cited. Among them, curing accelerators selected from amine curing accelerators and metal curing accelerators are preferred, and amine curing accelerators are particularly preferred.

[0199] As the phosphorus-based curing accelerator, for example, aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyl dimethylphosphonium tetraphenylborate, etc.; aromatic phosphonium salts such as methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetrakis(p-tolyl)borate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetrakis(p-tolyl)borate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc.; aromatic phosphine·borane complexes such as triphenylphosphine·triphenylborane; aromatic phosphine·quinone addition reactants such as triphenylphosphine·p-benzoquinone addition reactant; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, tricyclohexylphosphine, etc.; aromatic phosphines such as dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, 2,2'-bis(diphenylphosphino)diphenyl ether, etc.

[0200] As the urea-based curing accelerator, for example, 1,1-dimethylurea can be cited; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3-cyclooctyl-1,1-dimethylurea; aromatic dimethylureas such as 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea], etc.

[0201] As the guanidine-based curing accelerator, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc. can be cited.

[0202] As imidazole-based curing accelerators, examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate or ester, 1-cyanoethyl-2-phenylimidazolium trimellitate or ester, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds and adducts of imidazole compounds and epoxy resins.

[0203] As imidazole-based curing accelerators, commercially available products can be used. For example, "1B2PZ", "C11Z", "2P4MZ", "2MZA-PW", "2PHZ-PW", "C11Z-A" manufactured by Shikoku Kasei Kogyo Co., Ltd., "P200-H50" manufactured by Mitsubishi Chemical Corporation, etc. can be cited.

[0204] As metal-based curing accelerators, for example, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, tin, etc. can be cited. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate, cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, organomanganese complexes such as manganese(II) acetylacetonate, etc. As organometallic salts, for example, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, etc. can be cited.

[0205] As amine-based curing accelerators, for example, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc. can be cited.

[0206] As the amine-based curing accelerator, commercially available products can be used. For example, “MY-25” manufactured by Ajinomoto Fine-Techno Co., Inc. etc. can be cited.

[0207] Regarding the content of the component (G), when the non-volatile components in the resin composition are set to 100% by mass, it is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, further preferably 0.05% by mass or more, preferably 3% by mass or less, more preferably 1% by mass or less, and further preferably 0.8% by mass or less.

[0208] Regarding the content of the component (G), when the resin components in the resin composition are set to 100% by mass, it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1.5% by mass or less.

[0209] <(H) Organic filler>

[0210] Regarding the resin composition, as an optional component, (H) organic filler can be further contained as the component (H). In the (H) organic filler as the component (H), substances corresponding to the above components (A) to (G) are not contained. The component (H) can be used alone as one kind, or two or more kinds can be used in combination.

[0211] The component (H) exists in the resin composition in a particulate form. As the component (H), for example, rubber particles, polyamide fine particles, silicone particles, core-shell type particles, etc. can be cited. In the present invention, from the viewpoint of significantly obtaining the desired effects of the present invention, either rubber particles or core-shell type particles are preferably used, and rubber particles are more preferably used.

[0212] Examples of the rubber component contained in the rubber particles include olefin-based thermoplastic elastomers such as polybutadiene, polyisoprene, polychloroprene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isobutene copolymer, acrylonitrile-butadiene copolymer, isoprene-isobutene copolymer, isobutene-butadiene copolymer, ethylene-propylene-diene terpolymer, and ethylene-propylene-butene terpolymer; and thermoplastic elastomers such as acrylic-based thermoplastic elastomers like poly(propyl) (meth)acrylate, poly(butyl) (meth)acrylate, poly(cyclohexyl) (meth)acrylate, and poly(octyl) (meth)acrylate. Olefin-based thermoplastic elastomers are preferred, and styrene-butadiene copolymer is more preferred. Furthermore, silicone-based rubbers such as polyorganosiloxane rubber can be mixed in the rubber component. The glass transition temperature of the rubber component contained in the rubber particles is, for example, 0°C or lower, preferably -10°C or lower, more preferably -20°C or lower, and further preferably -30°C or lower.

[0213] As the rubber particles, commercially available products can be used. For example, "EXL2655" manufactured by Dow Chemical Japan Co., Ltd., "AC3401N" and "AC3816N" manufactured by Aika Industries Co., Ltd., etc. can be cited.

[0214] The so-called core-shell particles are particulate organic filler materials composed of core particles containing the above-listed rubber components and one or more shell portions covering them. Furthermore, the core-shell particles are preferably core-shell graft copolymer particles composed of core particles containing the above-listed rubber components and a shell portion formed by graft copolymerizing a monomer component copolymerizable with the rubber component contained in the core particles. The so-called core-shell type here does not necessarily mean only the type in which the core particles and the shell portion can be clearly distinguished, but also includes the type in which the boundary between the core particles and the shell portion is unclear, and the core particles may not be completely covered by the shell portion.

[0215] In the core-shell graft copolymer particles, the rubber component preferably contains 40% by mass or more, more preferably 50% by mass or more, and further preferably 60% by mass or more. There is no particular limitation on the upper limit of the content of the rubber component in the core-shell graft copolymer particles. From the viewpoint of sufficiently covering the core particles with the shell portion, for example, it is preferably 95% by mass or less, 90% by mass.

[0216] Examples of the monomer component for forming the shell of the core-shell graft copolymer particles include (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, and glycidyl (meth)acrylate; (meth)acrylic acid; N-substituted maleimides such as N-methylmaleimide and N-phenylmaleimide; maleimide; α,β-unsaturated carboxylic acids such as maleic acid and itaconic acid; aromatic vinyl compounds such as styrene, 4-vinyltoluene, and α-methylstyrene; (meth)acrylonitrile, etc. (meth)acrylic acid esters are preferred, and methyl (meth)acrylate is more preferred.

[0217] Examples of commercially available core-shell graft copolymer particles include "CHT" manufactured by Samsung SDI Co., Ltd.; "B602" manufactured by Techno UMG Co., Ltd.; "Paraloid EXL2602", "Paraloid EXL2603", "Paraloid EXL2655", "Paraloid EXL2311", "Paraloid EXL2313", "Paraloid EXL2315", "Paraloid KM330", "Paraloid KM336P", "Paraloid KCZ201" manufactured by Dow Chemical Japan Co., Ltd.; "Metablen C-223A", "Metablen E-901", "Metablen S-2001", "Metablen W-450A", "Metablen SRK-200" manufactured by Mitsubishi Rayon Co., Ltd.; "Kanekaes M-511", "Kanekaes M-600", "Kanekaes M-400", "Kanekaes M-580", "Kanekaes MR-01" manufactured by Kaneka Corporation, etc. These can be used alone or in combination of two or more.

[0218] There is no particular limitation on the average particle diameter (average primary particle diameter) of the core-shell graft copolymer particles. It is preferably 20 nm or more, more preferably 50 nm or more, further preferably 80 nm or more, particularly preferably 100 nm or more, preferably 5000 nm or less, more preferably 2000 nm or less, further preferably 1000 nm or less, and particularly preferably 500 nm or less. The average particle diameter (average primary particle diameter) of the core-shell graft copolymer particles can be measured using a ζ-potential particle size distribution measuring device or the like.

[0219] When the non-volatile content in the resin composition is set to 100% by mass, the content of the component (H) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, preferably 3% by mass or less, more preferably 1% by mass or less, and further preferably 0.5% by mass or less.

[0220] When the resin component in the resin composition is 100% by mass, the content of the (H) component is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, preferably 8% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less.

[0221] <(I) Other Additives>

[0222] In the case of the resin composition, in addition to the above components, other additives may be further included as optional components. Examples of the (I) other additives include polymerization initiators; organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentonite and montmorillonite; antifoaming agents such as silicone-based antifoaming agents, acrylic-based antifoaming agents, fluorine-based antifoaming agents, and vinyl resin-based antifoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as ureasilanes; adhesion improvers such as triazole-based adhesion improvers, tetrazole-based adhesion improvers, and triazine-based adhesion improvers; antioxidants such as hindered phenol-based antioxidants; optical brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate ester-based stabilizers, titanate ester-based stabilizers, aluminate ester-based stabilizers, zirconate ester-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers; photoinitiator assistants such as tertiary amines; and photosensitizers such as pyrarizone-based compounds, anthracene-based compounds, coumarin-based compounds, xanthenone-based compounds, and thioxanthenone-based compounds. The (I) other additives may be used alone or in combination of two or more.

[0223] <(J) Solvent>

[0224] Regarding the resin composition, in addition to the above-mentioned non-volatile components, as volatile components, any solvent can be further contained. As the (J) solvent, known solvents can be appropriately used, and there is no particular limitation on its type, and an organic solvent is preferred. As the (J) solvent, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone can be listed; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diethylene glycol acetate, γ-butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. The (J) solvent can be used alone or two or more kinds can be used in combination at any ratio.

[0225] The resin composition preferably contains 0.5% by mass or more and 3% by mass or less of the (J) solvent based on 100% by mass of all the components of the resin composition. Specifically, the (J) solvent is preferably 3% by mass or less, more preferably 2% by mass or less, further preferably 1.5% by mass or less, preferably 0.5% by mass or more, more preferably 0.8% by mass or more, and further preferably 1% by mass or more based on 100% by mass of all the components of the resin composition.

[0226] There is no particular limitation on the method for preparing the resin composition of the present invention. For example, a method of adding compounding components, solvents as required, and using a rotary mixer to perform mixing and dispersion can be listed.

[0227] <Physical Properties and Uses of Resin Composition>

[0228] Since the resin composition contains components (A) to (D) in combination, the adhesion between the resin composition and the conductor layer is excellent, the generation of warpage amount is suppressed, and a cured product with low dielectric properties can be obtained. In addition, a cured product with excellent adhesion to copper foil after the HAST test can usually be obtained.

[0229] Regarding the cured product obtained by thermally curing the resin composition at 200°C for 90 minutes, it exhibits excellent adhesion to the copper foil before the accelerated environmental test (HAST). Therefore, the above-mentioned cured product provides an insulating layer with excellent adhesion (peel strength) to the copper foil before the HAST test. The peel strength is preferably 0.4 kgf / cm or more, more preferably 0.5 kgf / cm or more, and further preferably 0.6 kgf / cm or more. The upper limit of the peel strength can be 10 kgf / cm or less, etc. Regarding the measurement of the peel strength, it can be measured according to the method described in the examples below.

[0230] Regarding the cured product obtained by thermally curing the resin composition at 200°C for 90 minutes, it generally exhibits excellent adhesion to the copper foil after the accelerated environmental test (HAST). Therefore, the above-mentioned cured product provides an insulating layer with excellent adhesion (peel strength) to the copper foil after the HAST test. The peel strength after the HAST test is preferably 0.3 kgf / cm or more, more preferably 0.4 kgf / cm or more, and further preferably 0.5 kgf / cm or more. The upper limit of the peel strength after the HAST test can be 10 kgf / cm or less, etc. Regarding the measurement of the peel strength, it can be measured according to the method described in the examples below.

[0231] Regarding the cured product obtained by thermally curing the resin composition at 190°C for 90 minutes, it exhibits a low dielectric loss tangent. Therefore, the above-mentioned cured product provides an insulating layer with a low dielectric loss tangent. The dielectric loss tangent is preferably 0.005 or less, more preferably 0.0045 or less, and further preferably 0.004 or less. The lower limit value of the dielectric loss tangent can be 0.0001 or more, etc. Regarding the measurement of the dielectric loss tangent, it can be measured according to the method described in the examples below.

[0232] Regarding the cured product obtained by thermally curing the resin composition at 190°C for 90 minutes, it exhibits a low dielectric constant (relative dielectric constant). Therefore, the above-mentioned cured product provides an insulating layer with a low relative dielectric constant. The relative dielectric constant is preferably 5 or less, more preferably 4 or less, and further preferably 3.5 or less, 3.3 or less. The lower limit value of the relative dielectric constant can be 1 or more, etc. Regarding the measurement of the relative dielectric constant, it can be measured according to the method described in the examples below.

[0233] Regarding the cured product obtained by thermally curing the resin composition at 190°C for 90 minutes, since it exhibits the property of having a low elastic modulus at 23°C, it also exhibits the property that the generation of warpage amount is suppressed. Therefore, the above-mentioned cured product provides an insulating layer in which the generation of warpage amount is suppressed. The elastic modulus at 23°C is preferably 20 GPa or less, more preferably 15 GPa or less, and further preferably 13 GPa or less. The lower limit can be 0.1 GPa or more, etc. Regarding the measurement of the elastic modulus, it can be measured according to the method described in the following examples.

[0234] Regarding the resin composition of the present invention, the adhesion to the conductor layer is excellent, the generation of warpage amount is suppressed, and a cured product with low dielectric properties can be obtained. Furthermore, a cured product with excellent adhesion after the HAST test can generally be obtained. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulating purposes. Specifically, it can be suitably used as a resin composition for forming the insulating layer (resin composition for forming the insulating layer for the conductor layer) for forming the conductor layer (including the rewiring layer) formed on the insulating layer.

[0235] In addition, in the multilayer printed wiring board described later, it can be suitably used as a resin composition for forming the insulating layer of the multilayer printed wiring board (resin composition for forming the insulating layer of the multilayer printed wiring board) and a resin composition for forming the interlayer insulating layer of the printed wiring board (resin composition for forming the interlayer insulating layer of the printed wiring board).

[0236] In addition, for example, when manufacturing a semiconductor chip package through the following steps (1) to (6), the resin composition of the present invention can also be suitably used as a resin composition for forming the rewiring formation layer for the insulating layer for forming the rewiring layer (resin composition for forming the rewiring formation layer) and a resin composition for sealing the semiconductor chip (resin composition for sealing the semiconductor chip). When manufacturing a semiconductor chip package, a rewiring layer can be further formed on the sealing layer.

[0237] (1) A step of laminating a temporary fixing film on a substrate,

[0238] (2) A step of temporarily fixing a semiconductor chip on the temporary fixing film,

[0239] (3) A step of forming a sealing layer on the semiconductor chip,

[0240] (4) A step of peeling the substrate and the temporary fixing film from the semiconductor chip,

[0241] (5) A step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been peeled, and

[0242] (6) A step of forming a rewiring layer as a conductor layer on a rewiring formation layer

[0243] [Resin sheet]

[0244] The resin sheet of the present invention includes a support and a resin composition layer provided on the support and formed of the resin composition of the present invention.

[0245] Regarding the thickness of the resin composition layer, from the viewpoints of thinning of the printed wiring board and providing a cured product with excellent insulation even if the cured product of the resin composition is a thin film, it is preferably 100 μm or less, more preferably 80 μm or less, and further preferably 50 μm or less. There is no particular limitation on the lower limit of the thickness of the resin composition layer, and it can usually be 5 μm or more, etc.

[0246] Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferred.

[0247] When using a film made of a plastic material as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes simply referred to as "PET"), polyethylene naphthalate (hereinafter sometimes simply referred to as "PEN"), polycarbonate (hereinafter sometimes simply referred to as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyethersulfone (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and polyethylene terephthalate with a low price is particularly preferred.

[0248] When using a metal foil as the support, examples of the metal foil include a copper foil and an aluminum foil, and a copper foil is preferred. As the copper foil, a foil made of single metal of copper or a foil made of an alloy of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used.

[0249] Regarding the support, the surface joined to the resin composition layer can be subjected to matting treatment, corona treatment, or antistatic treatment.

[0250] In addition, as the support, a support with a release layer having a release layer on the surface joined to the resin composition layer can be used. As the release agent used in the release layer of the support with a release layer, for example, one or more release agents selected from alkyd resins, polyolefin resins, urethane resins, and silicone resins can be cited. Commercially available products can be used as the support with a release layer. For example, "SK-1", "AL-5", "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, "Unipile" manufactured by Unitika Ltd., etc., which are PET films having a release layer mainly composed of an alkyd resin-based release agent, can be cited.

[0251] The thickness of the support is not particularly limited, and the range of 5 μm to 75 μm is preferred, and the range of 10 μm to 60 μm is more preferred. It should be noted that when using a support with a release layer, it is preferred that the overall thickness of the support with a release layer is within the above range.

[0252] In one embodiment, the resin sheet may further contain other layers as needed. As such other layers, for example, a protective film based on the support provided on the surface of the resin composition layer that is not joined to the support (i.e., the surface opposite to the support) can be cited. The thickness of the protective film is not particularly limited, for example, it is 1 μm to 40 μm. By laminating the protective film, the attachment of garbage, etc. and scratches on the surface of the resin composition layer can be suppressed.

[0253] For the resin sheet, for example, it can be manufactured by preparing a resin varnish in which the resin composition is dissolved in a solvent, coating the resin varnish on the support using a die coater, etc., and then drying it to form a resin composition layer. For the solvent, as described above.

[0254] Drying can be carried out by using known methods such as heating and jetting hot air. The drying conditions are not particularly limited, and it is dried so that the content of the solvent in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. It also varies depending on the boiling point of the solvent in the resin varnish. For example, when using a resin varnish containing 30% to 60% by mass of the solvent, by drying at 50°C to 150°C for 3 minutes to 10 minutes, a resin composition layer can be formed.

[0255] The resin sheet can be wound into a roll for storage. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0256] [Printed Wiring Board]

[0257] The printed wiring board of the present invention includes an insulating layer formed by a cured product of the resin composition of the present invention.

[0258] A printed wiring board can be manufactured, for example, by using the above resin sheet and by a method including the following steps (I) and (II).

[0259] (I) A step of laminating the resin composition layer of the resin sheet on the inner layer substrate in a manner of bonding to the inner layer substrate

[0260] (II) A step of thermally curing the resin composition layer to form an insulating layer

[0261] The "inner layer substrate" used in step (I) is a member that becomes the substrate of the printed wiring board. For example, glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc. can be cited. In addition, the substrate may have a conductor layer on one or both sides thereof, and the conductor layer can be pattern-processed. Sometimes the inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate is called an "inner layer circuit substrate". In addition, in the manufacture of a printed wiring board, an intermediate product on which an insulating layer and / or a conductor layer should be further formed is also included in the "inner layer substrate" in the present invention. In the case where the printed wiring board is a board with components built-in, an inner layer substrate with components built-in can be used.

[0262] The lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. As a member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member"), for example, a heated metal plate (such as a SUS mirror plate) or a metal roll (SUS roll) can be cited. It should be noted that it is preferable to apply pressure to the surface unevenness of the inner layer substrate in such a way that the resin sheet sufficiently follows via an elastic material such as heat-resistant rubber, rather than directly applying pressure to the resin sheet with the thermocompression bonding member.

[0263] The lamination of the inner layer substrate and the resin sheet can be carried out by a vacuum lamination method. In the vacuum lamination method, the thermocompression bonding temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the thermocompression bonding pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa, and the thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably carried out under a reduced pressure condition of 26.7 hPa or less.

[0264] The lamination can be carried out by a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum pressure type laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum booster manufactured by Nippon Materials Co., Ltd., an intermittent vacuum pressure laminator, etc. can be cited.

[0265] After lamination, a smoothing process of the laminated resin sheet can be performed by pressing the heating and bonding member from the support side under normal pressure (atmospheric pressure). The pressing conditions for the smoothing process can be set to the same conditions as the heating and bonding conditions for the above lamination. The smoothing process can be carried out using a commercially available laminator. It should be noted that lamination and the smoothing process can be continuously performed using the above-mentioned commercially available vacuum laminator.

[0266] The support can be removed between process (I) and process (II), or can be removed after process (II).

[0267] In process (II), the resin composition layer is thermally cured to form an insulating layer. There are no particular limitations on the thermal curing conditions of the resin composition layer, and the conditions commonly used when forming the insulating layer of a printed wiring board can be used.

[0268] For example, the thermal curing conditions of the resin composition layer vary depending on the type of resin composition, etc. The curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and further preferably 170°C to 210°C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and further preferably 15 minutes to 100 minutes.

[0269] Before thermally curing the resin composition layer, the resin composition layer can be preheated at a temperature lower than the curing temperature. For example, before thermally curing the resin composition layer, the resin composition layer can be preheated at a temperature of 50°C or higher and less than 120°C (preferably 60°C or higher and 115°C or lower, more preferably 70°C or higher and 110°C or lower) for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and further preferably 15 minutes to 100 minutes).

[0270] When manufacturing a printed wiring board, processes (III) of drilling holes in the insulating layer, (IV) of roughening the insulating layer, and (V) of forming a conductor layer can be further implemented. For these processes (III) to (V), they can be implemented according to various methods well-known to those skilled in the art for the manufacture of printed wiring boards. It should be noted that in the case of removing the support after process (II), the removal of the support can be implemented between process (II) and process (III), between process (III) and process (IV), or between process (IV) and process (V). In addition, if necessary, the formation of the insulating layer and the conductor layer in processes (II) to (V) can be repeatedly implemented to form a multilayer wiring board.

[0271] Process (III) is a process of drilling holes in the insulating layer, whereby holes such as vias and through-holes can be formed in the insulating layer. Process (III) can be carried out using, for example, a drill bit, a laser, or a plasma, depending on the composition of the resin composition used in the formation of the insulating layer, etc. The size and shape of the holes can be appropriately determined according to the design of the printed wiring board.

[0272] Process (IV) is a process of roughening the insulating layer. Generally, in this process (IV), stains are also removed. There are no particular limitations on the steps and conditions of the roughening treatment, and known steps and conditions commonly used in the formation of the insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by successively performing a swelling treatment using a swelling liquid, a roughening treatment using an oxidizing agent, and a neutralization treatment using a neutralizing liquid. There are no particular limitations on the swelling liquid used for the roughening treatment, and examples include an alkali solution and a surfactant solution. An alkali solution is preferred, and as this alkali solution, sodium hydroxide solution and potassium hydroxide solution are more preferred. As commercially available swelling liquids, for example, "Swelling Dip Security Gun P", "Swelling Dip Security Gun SBU", and "Swelling Dip Security Gun P" manufactured by Atotech Japan Co., Ltd. can be cited. There are no particular limitations on the swelling treatment using the swelling liquid. For example, it can be carried out by immersing the insulating layer in the swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferred to immerse the insulating layer in the swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes. There are no particular limitations on the oxidizing agent used for the roughening treatment. For example, an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide can be cited. The roughening treatment using an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the insulating layer in the oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. In addition, the concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. As commercially available oxidizing agents, for example, alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution Security Gun P" manufactured by Atotech Japan Co., Ltd. can be cited. In addition, as the neutralizing liquid used for the roughening treatment, an acidic aqueous solution is preferred. As a commercially available product, for example, "Reduction Solution Security Gun P" manufactured by Atotech Japan Co., Ltd. can be cited. Regarding the treatment using the neutralizing liquid, it can be carried out by immersing the treated surface that has undergone the roughening treatment using the oxidizing agent in the neutralizing liquid at 30°C to 80°C for 1 minute to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object that has undergone the roughening treatment using the oxidizing agent in the neutralizing liquid at 40°C to 70°C for 5 minutes to 20 minutes is preferred.

[0273] In one embodiment, the arithmetic mean roughness (Ra) of the surface of the roughened insulating layer is preferably 300 nm or less, more preferably 250 nm or less, and still more preferably 200 nm or less. There is no particular limitation on the lower limit, and it is preferably 30 nm or more, more preferably 40 nm or more, and still more preferably 50 nm or more. The arithmetic mean roughness (Ra) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

[0274] Process (V) is a process of forming a conductor layer, and a conductor layer is formed on the insulating layer. There is no particular limitation on the conductor material used in the conductor layer. In a preferred embodiment, the conductor layer contains one or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer can be a single-metal layer or an alloy layer. As the alloy layer, for example, a layer formed of an alloy of two or more metals selected from the above group (such as nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy) can be cited. Among them, from the viewpoints of the versatility of forming the conductor layer, cost, ease of patterning, etc., a single-metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy is preferred, a single-metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy is more preferred, and a single-metal layer of copper is still more preferred.

[0275] The conductor layer can have a single-layer structure, or can be a multilayer structure in which two or more single-metal layers or alloy layers composed of different kinds of metals or alloys are laminated. In the case where the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single-metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0276] The thickness of the conductor layer depends on the design of the desired printed wiring board and is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0277] In one embodiment, the conductor layer can be formed by plating. For example, by plating on the surface of the insulating layer using a conventionally known technique such as semi-additive method or full-additive method, a conductor layer having a desired wiring pattern can be formed. From the viewpoint of manufacturing simplicity, it is preferably formed by the semi-additive method. Hereinafter, an example of forming a conductor layer by the semi-additive method is shown.

[0278] First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Secondly, on the formed plating seed layer, a mask pattern that exposes a part of the plating seed layer is formed according to the desired wiring pattern. After a metal layer is formed by electroplating on the exposed plating seed layer, the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

[0279] [Semiconductor device]

[0280] The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

[0281] Examples of the semiconductor device include various semiconductor devices for electrical products (such as computers, mobile phones, digital cameras, and televisions, etc.) and transportation means (such as motorcycles, automobiles, trams, ships, and aircraft, etc.).

[0282] The semiconductor device of the present invention can be manufactured by mounting components (semiconductor chips) on the conductive portions of the printed wiring board. The so-called "conductive portion" is "the portion in the printed wiring board that transmits electrical signals", and its location can be on the surface or an embedded portion. In addition, the semiconductor chip is not particularly limited as long as it is a circuit element made of semiconductor.

[0283] Regarding the method of mounting the semiconductor chip when manufacturing the semiconductor device, as long as the semiconductor chip functions effectively, it is not particularly limited. Specifically, examples include wire bonding mounting methods, flip chip mounting methods, mounting methods using a bump-less build-up layer (BBUL), mounting methods using an anisotropic conductive film (ACF), mounting methods using a non-conductive film (NCF), etc. Among them, the so-called "mounting method using a bump-less build-up layer (BBUL)" refers to "a mounting method in which the semiconductor chip is directly embedded in the recess of the printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board".

[0284] Examples

[0285] Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. It should be noted that in the following description, unless otherwise specified, "parts" and "%" mean "parts by mass" and "mass%", respectively.

[0286] The conditions of the GPC used in the measurement of the number average molecular weight and the like are as follows.

[0287] Measurement device: "HLC-8420GPC" manufactured by Tosoh Corporation

[0288] Column: Guard column "HXL-L" manufactured by Tosoh Corporation + "TSK-GEL SuperHZ2000" manufactured by Tosoh Corporation + "TSK-GEL SuperHZ2000" manufactured by Tosoh Corporation + "TSK-GEL SuperHZ3000" manufactured by Tosoh Corporation + "TSK-GELSuperHZ4000" manufactured by Tosoh Corporation

[0289] Detector: RI (differential refractometer)

[0290] Data processing: "GPC Workstation Eco SEC-Work Station" manufactured by Tosoh Corporation

[0291] Column temperature: 40 °C

[0292] Developing solvent: Tetrahydrofuran

[0293] Flow rate: 0.35 mL / min

[0294] Method for measuring molecular weight: According to the measurement manual of the above-mentioned "GPC Workstation Eco SEC-Work Station", the molecular weight uses the following known monodisperse polystyrene.

[0295] TSKgel F-10, F-4, F-1, A-5000, A-1000, A-500 (manufactured by Tosoh Corporation)

[0296] Sample: The product obtained by filtering a tetrahydrofuran solution containing 0.2% by mass of resin solid content with a microfilter (10 μL)

[0297] <Synthesis Example 1: Synthesis of Organosilicon Resin 1>

[0298] In a eggplant-shaped flask equipped with a Dean-Stark apparatus, 2.95 g of diphenylsilanediol, 3.00 g of 3-glycidoxypropyl(dimethoxy)methylsilane, and 128 mg of barium hydroxide monohydrate were added, and the mixture was stirred at 85 °C for 6 hours under an argon atmosphere. After cooling to room temperature, toluene was added, and the unnecessary substances were filtered off. By concentration under reduced pressure, 6 g of a colorless transparent oily organosilicon resin 1 was obtained. It was dissolved in toluene to obtain the target organosilicon epoxy resin 1 with a solid content concentration of 50% by mass (number average molecular weight 3468, active group equivalent about 385 g / eq., non-volatile component rate 50%). For the organosilicon epoxy resin 1, an NMR apparatus (nuclear magnetic resonance apparatus: Bruker AVANCE 400 (400 MHz)) was used for identification, and it was confirmed that it had a structural unit represented by the following formula (A-1-1) and a structural unit represented by the formula (A-2-1) (where * represents the bonding end).

[0299] 1 H-NMR (400 MHz, chloroform-d) δ 7.67 - 7.01 (m, 10H), 3.76 - 2.84 (m, 5H), 2.82 - 2.62 (m, 1H), 2.61 - 2.41 (m, 1H), 1.67 - 1.03 (m, 2H), 0.64 - 0.17 (m, 2H), 0.16 - 0.35 (m, 3H)

[0300]

Chemical Formula 11

[0301]

[0302] <Synthesis Example 2: Synthesis of Silicone Resin 2>

[0303] 4.91 g of diphenylsilanediol, 5.00 g of 3-glycidoxypropyl(dimethoxy)methylsilane, and 215 mg of barium hydroxide monohydrate were added to a eggplant-shaped flask equipped with a Dean-Stark apparatus, and stirred at 85 °C for 3 days under an argon atmosphere. After cooling to room temperature, toluene was added, and unnecessary substances were filtered off. By concentration under reduced pressure, 10 g of a colorless transparent oily silicone-based epoxy resin 2 was obtained. It was dissolved in toluene to obtain the target silicone resin 2 having a solid content concentration of 50% by mass (number average molecular weight 7869, active group equivalent about 393 g / eq., non-volatile component ratio 50%). The silicone-based epoxy resin 2 was identified using an NMR apparatus (Bruker AVANCE 400 (400 MHz)), and it was confirmed to have a structural unit represented by the following formula (A-1-1) and a structural unit represented by formula (A-2-1) (where * represents a bonding end in the formula).

[0304] 1 H-NMR (400 MHz, chloroform-d) δ 7.68 - 7.02 (m, 10H), 3.75 - 2.85 (m, 5H), 2.81 - 2.60 (m, 1H), 2.59 - 2.41 (m, 1H), 1.66 - 1.02 (m, 2H), 0.65 - 0.18 (m, 2H), 0.17 - 0.33 (m, 3H)

[0305] [Chemical Formula 12]

[0306]

[0307] <Synthesis Example 3: Synthesis of Maleimide A>

[0308] A MEK solution of maleimide A (non-volatile component 62% by mass, t” = 1.47 (mainly 1, 2 or 3), Mw / Mn = 1.81) synthesized by the method described in Synthesis Example 1 of Publication No. 2020 - 500211 of the Technical Bulletin of the Japan Institute of Invention was prepared. This maleimide A has a structure represented by the following formula (1).

[0309] [Chemical Formula 13]

[0310]

[0311] <Synthesis Example 4: Synthesis of Polyimide B>

[0312] Prepare a 500 mL separable flask equipped with a moisture quantifying receiver connected to a reflux condenser, a nitrogen inlet tube, and a stirrer. Add 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 29.6 g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane to the flask, and stir at 45 °C for 2 hours under a nitrogen stream to carry out the reaction. Next, heat up the reaction solution, and while maintaining at about 160 °C, azeotropically remove the condensed water together with toluene under a nitrogen stream. Confirmation: A specified amount of water accumulates in the moisture quantifying receiver and no water outflow is seen. After confirmation, further heat up the reaction solution and stir at 200 °C for 1 hour. Then, cool to obtain a polyimide solution (nonvolatile content: 20% by mass) containing a polyimide resin having a 1,1,3-trimethylindane skeleton. The obtained polyimide resin has a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). In addition, the weight average molecular weight of the above polyimide resin is 12,000.

[0313] [Chemical 14]

[0314]

[0315] <Manufacture of Resin Varnish>

[0316] Weigh each component in the mass parts described in the table, and further mix 15 parts of MEK and 2 parts of cyclohexanone, and disperse uniformly using a high-speed rotary mixer to obtain a resin varnish.

[0317]

[0318] Details of each component described in the table are as follows.

[0319] (Component (A))

[0320] · Silicone resin 1: The product synthesized and prepared in Synthesis Example 1

[0321] · Silicone resin 2: The product synthesized and prepared in Synthesis Example 2

[0322] (Component (B))

[0323] · HP-4032-SS: Naphthalene type epoxy resin (functional group equivalent: 144 g / eq., manufactured by DIC Corporation)

[0324] · NC-3000-L: Biphenyl type epoxy resin (functional group equivalent: 269 g / eq., manufactured by Nippon Kayaku Co., Ltd.)

[0325] · ZX-1059: A 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent 169 g / eq.)

[0326] · ESN-475V: Naphthalene type epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent 332 g / eq.)

[0327] · 828EL: Bisphenol A type liquid epoxy resin, functional group equivalent 189 g / eq., manufactured by Mitsubishi Chemical Corporation

[0328]

Chemical Formula 15

[0329]

[0330] · X-40-2669: Silicone resin represented by the following structural formula, functional group equivalent 200 g / eq., manufactured by Shin-Etsu Chemical Co., Ltd.

[0331]

Chemical Formula 16

[0332]

[0333] (C) Component

[0334] · HPC-8150-62T: Active ester type curing agent (active ester resin with a naphthalene structure, functional group equivalent 223 g / eq., manufactured by DIC Corporation)

[0335] · HPC-8000L-65TM: Active ester type curing agent (active ester resin containing a dicyclopentadiene type diphenol structure, functional group equivalent 229 g / eq., manufactured by DIC Corporation)

[0336] · PC1300-02-65MA: Active ester type curing agent (active ester resin with a naphthalene structure, functional group equivalent 199 g / eq., manufactured by Air Water Incorporated)

[0337] (D) Component

[0338] · SO-C2: Spherical silica surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), average particle diameter 0.5 μm, specific surface area 5.8 m 2 / g, manufactured by Admatechs Co., Ltd.

[0339] · UFP-30: Spherical silica surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), average particle diameter 0.3 μm, specific surface area 30.7 m 2 / g, manufactured by Denka Company Limited

[0340] (E) component

[0341] · Maleimide A: The product synthesized in Synthesis Example 3, a maleimide-based free-radical polymerizable compound

[0342] · ODV-XET-X04: A styrene-based free-radical polymerizable compound, manufactured by Nippon Steel Chemical & Material Co., Ltd.

[0343] · LA-3018-50P: A 1-methoxy-2-propanol solution with a functional group equivalent of 151 g / eq. and a non-volatile content of 50% by mass, manufactured by DIC Corporation

[0344] · V–03: A toluene solution with a functional group equivalent of 216 g / eq. and a non-volatile content of 50% by mass, manufactured by Nisshinbo Chemical Inc.

[0345] · BA230S75: A prepolymer of bisphenol A dicyanate, with a functional group equivalent of 232 g / eq., manufactured by arxada

[0346] (F) component

[0347] · YX7553BH30: A phenoxy resin, a 1:1 solution of MEK and cyclohexanone with a non-volatile content of 30% by mass, manufactured by Mitsubishi Chemical Corporation

[0348] · Polyimide B: The product synthesized in Synthesis Example 4

[0349] (G) component

[0350] · 1B2PZ: An imidazole-based reaction accelerator, manufactured by Shikoku Kasei Kogyo Co., Ltd.

[0351] · DMAP: An amine-based curing accelerator, manufactured by Tokyo Chemical Industry Co., Ltd.

[0352] · Co(III): A metal-based curing accelerator, manufactured by Tokyo Chemical Industry Co., Ltd.

[0353] (H) component

[0354] · EXL2655: Core-shell graft copolymer rubber particles, manufactured by The Dow Chemical Company

[0355] <Measurement of dielectric constant, dielectric loss tangent, and elastic modulus>

[0356] (1) Preparation of resin sheet A with a resin composition layer thickness of 40 μm

[0357] As a support, a polyethylene terephthalate film with a release layer (Lintec Corporation's "AL5", thickness 38 μm) was prepared. On the release layer of this support, the resin varnishes obtained in the examples and comparative examples were uniformly coated so that the thickness of the dried resin composition layer became 40 μm. Then, the resin composition was dried at 80°C to 100°C (average 90°C) for 2 minutes to obtain a resin sheet A comprising the support and the resin composition layer.

[0358] (2) Preparation of the cured product of the resin composition layer

[0359] The resin sheet A obtained in the examples and comparative examples was cured in an oven at 190°C for 90 minutes. The support was peeled off from the resin sheet A taken out of the oven, whereby a cured product of the resin composition layer was obtained.

[0360] (3) Measurement of dielectric constant and dielectric loss tangent (dielectric properties)

[0361] The cured product was cut into 80 mm in length and 2 mm in width, and using "HP8362B" manufactured by Agilent Technologies, the values of dielectric constant and dielectric loss tangent (Dk value and Df value) were measured at a measurement frequency of 5.8 GHz, measurement temperatures of 23°C and 90°C by the cavity resonance perturbation method (hollow resonance perturbation method). The measurement was carried out using 2 test pieces, and the average was calculated.

[0362] (4) Measurement of elastic modulus

[0363] A tensile strength measurement was carried out using a tensile testing machine "RTC-1250A" manufactured by Orientec to measure the elastic modulus at 23°C. The measurement was carried out in accordance with JIS K7127. The measurement was carried out 5 times, and the average of the first 3 points was calculated.

[0364] <Evaluation of adhesion>

[0365] (1) Substrate treatment of copper foil

[0366] The shiny surface of the electrolytic copper foil (Mitsui Mining & Smelting Co., Ltd.'s "3EC-III", thickness 35 μm) was etched by 1 μm using a micro-etchant ("CZ8101" manufactured by Meck Co., Ltd.) for roughening the copper surface, and then, an anti-rust treatment (CL8300) was carried out. Hereinafter, the copper foil whose surface has been etched with the above micro-etchant may sometimes be referred to as "CZ copper foil". Further, this copper foil was heat-treated in an oven at 130°C for 30 minutes to obtain a copper foil I having a treated surface on which a roughening treatment has been carried out.

[0367] (2) Preparation of inner layer substrate

[0368] Prepare a glass cloth substrate epoxy resin double-sided copper-clad laminate with copper foil on the surface and an inner layer circuit formed (copper foil thickness 18 μm, substrate thickness 0.4 mm, "R1515A" manufactured by Panasonic Corporation). Etch both sides of this glass cloth substrate epoxy resin double-sided copper-clad laminate with a micro-etchant ("CZ8101" manufactured by Meck Corporation) by 1 μm to perform roughening treatment on the copper foil surface. Thus, an inner layer substrate with CZ copper foil having a treated surface on the surface is obtained.

[0369] (3) Lamination of the resin composition layer

[0370] Laminate the resin sheets produced in the examples and comparative examples on both sides of the inner layer substrate. For this laminate, use a batch-type vacuum pressure laminator ("CVP700", a two-stage assembled laminator manufactured by Niko Materials Co., Ltd.) in such a way that the resin composition layer is in contact with the above-mentioned inner layer substrate. In addition, evacuate the above laminate for 30 seconds, adjust the air pressure to 13 hPa or less, and then press-bond at 120 °C and a pressure of 0.74 MPa for 30 seconds to implement this. Next, perform hot pressing on the laminated resin sheets at 100 °C and a pressure of 0.5 MPa for 60 seconds. Then, peel off the support to expose the resin composition layer.

[0371] (4) Lamination of copper foil and curing of the resin composition layer

[0372] On the exposed resin composition layer, laminate the treated surface of copper foil I under the same conditions as in the above-mentioned "(3) Lamination of the resin composition layer". Then, cure the resin composition layer under curing conditions of 200 °C for 90 minutes to form an insulating layer containing a cured product of the resin composition. Through the above operations, an evaluation substrate C with CZ copper foil laminated on both sides of the insulating layer is obtained. This evaluation substrate C has a layer structure of copper foil I / insulating layer / inner layer substrate / insulating layer / copper foil I.

[0373] (5) Measurement of the adhesion (peel strength) to copper foil before the HAST test

[0374] Cut the evaluation substrate C into small pieces of 150 mm × 30 mm. In the copper foil I of the small pieces, use a cutting knife to form a cut mark surrounding a portion with a width of 10 mm and a length of 100 mm. Peel off one end of this portion and clamp it with a fixture of a tensile testing machine ("AC-50C-SL", an autocom universal testing machine manufactured by T.S.E.). At room temperature (25 °C), stretch it vertically at a speed of 50 mm / minute, and measure the load [kgf / cm] when 35 mm is peeled off as the copper foil peel strength. The measurement is carried out in accordance with Japanese Industrial Standard JIS C6481.

[0375] (6) Measurement of the copper foil peel strength after the accelerated environmental test (HAST)

[0376] For the evaluation substrate C, using a highly accelerated life test device ("PM422" manufactured by Kusumoto Chemical Co., Ltd.), an accelerated environmental test was conducted for 100 hours under the conditions of 130°C and 85% RH. Then, in the same manner as the measurement of adhesion 1, one end of the copper foil was peeled off, clamped with a jig (manufactured by T.S.E., Auto Com type testing machine, "AC-50C-SL"), and using an Instron universal testing machine, the load when peeling 35 mm in the vertical direction at a speed of 50 mm / minute at room temperature was measured according to JIS C6481.

[0377]

Claims

1. A resin composition comprising: (A) a silicone resin having a structural unit represented by the following formula (A-1) and a structural unit represented by the following formula (A-2); (B) Epoxy resins, other than those meeting the requirements of (A); (C) an active ester curing agent; and (D) Inorganic filling materials, In formula (A-1), R 1 represents a group represented by the following formula (A-1a) or a group represented by the following formula (A-1b), R 2 represents a monovalent hydrocarbon group which may have a substituent, * represents a bonding end, In formula (A-2), R 3 and R 4 Each independently represents a monovalent hydrocarbon group which may have a substituent, * represents a bonding end, In formula (A-1a), n1 represents an integer of 2 to 10, * represents a bonding end to the silicon atom in formula (A-1), In the formula (A-1b), n2 represents an integer of 1 to 10, and * represents a bonding end to the silicon atom in the formula (A-1).

2. The resin composition according to claim 1, wherein In the formula (A-1a), n1 represents an integer of 3-8.

3. The resin composition according to claim 1, wherein In formula (A-1), R 2 It represents an alkyl group which may have a substituent.

4. The resin composition according to claim 1, wherein In formula (A-2), R 3 and R 4 Each independently represents an aryl group which may have a substituent.

5. The resin composition according to claim 1, wherein In formula (A-2), R 3 and R 4 Each independently represents a phenyl group which may have a substituent.

6. The resin composition according to claim 1, wherein The number average molecular weight of the component (A) is 10,000 or less.

7. The resin composition according to claim 1, wherein The content of the component (D) exceeds 60% by mass when the nonvolatile matter of the resin composition is 100% by mass. 8 . A resin sheet comprising: a support; and a resin composition layer provided on the support and comprising the resin composition according to claim 1 . 9 . A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to claim 1 . 10 . A semiconductor device comprising the printed wiring board according to claim 9 .

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