Resin composition

Abstract

To provide a resin composition that can yield a cured product with superior crack resistance.SOLUTION: A resin composition includes (A) an epoxy resin, (B) a curing agent, and (C) a thermoplastic resin with a hyperbranched structure.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] As a manufacturing technique for printed wiring boards, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately stacked is known.

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

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Disclosure of the Invention

Problems to be Solved by the Invention

[0005] By the way, in recent years, for example, an insulating layer used for a wiring board having an embedded wiring layer is required to be excellent in crack resistance (suppression of crack generation) in order to improve the yield.

[0006] An object of the present invention is to provide a resin composition capable of obtaining a cured product excellent in crack resistance; a resin sheet containing the resin composition; a printed wiring board provided with an insulating layer formed using the resin composition, and a semiconductor device.

Means for Solving the Problems

[0007] As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by incorporating a combination of an epoxy resin, a curing agent, and a thermoplastic resin having a hyperbranched structure, and have completed the present invention.

[0008] That is, the present invention includes the following contents. [1] A resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) a thermoplastic resin having a hyperbranched structure. [2] The resin composition according to [1], wherein the component (C) has a cyclic structure. [3] The resin composition according to [1] or [2], wherein the component (C) has a phenylene ether skeleton. [4] The resin composition according to any one of [1] to [3], wherein the component (C) has a siloxane structure. [5] The resin composition according to any one of [1] to [4], wherein the component (C) has a triazine ring. [6] The resin composition according to any one of [1] to [5], wherein the weight average molecular weight of the component (C) is 1000 or more and 40000 or less. [7] The resin composition according to any one of [1] to [6], wherein the component (C) has a multi-branched structure in which structures derived from trifunctional or higher functional compounds and structures derived from bifunctional compounds are alternately bonded, and the terminal has a structure derived from a monofunctional compound. [8] The resin composition according to any one of [1] to [7], wherein the component (C) is a resin having a glass transition temperature of 50°C or higher and 150°C or lower. [9] The resin composition according to any one of [1] to [8], wherein the terminal of the component (C) contains either an alkoxysilyl group or an arylalkoxy group.

[10] The resin composition according to any one of [1] to [9], further comprising (D) an inorganic filler.

[11] The resin composition according to

[10] , wherein the content of the component (D) is 50% by mass or more when the resin components in the resin composition are 100% by mass.

[12] The resin composition according to any one of [1] to

[11] , wherein the component (B) contains an active ester-based curing agent.

[13] 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

[12] .

[14] A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of [1] to

[12] .

[15] A semiconductor device comprising the printed wiring board according to

[14] . [Advantages of the Invention]

[0009] According to the present invention, it is possible to provide a resin composition capable of obtaining a cured product excellent in crack resistance; a resin sheet containing the resin composition; a printed wiring board provided with an insulating layer formed using the resin composition; and a semiconductor device. [Embodiments for Carrying Out the Invention]

[0010] Hereinafter, the present invention will be described in detail with reference to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified and implemented without departing from the scope of the claims of the present invention and its equivalent scope. In the present invention, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass unless otherwise specified.

[0011] [Resin Composition] The resin composition of the present invention contains (A) an epoxy resin, (B) a curing agent, and (C) a thermoplastic resin having a hyperbranched structure. In the present invention, by combining the components (A) to (C) and containing them in the resin composition, a cured product excellent in crack resistance can be obtained. Further, according to the cured product of the resin composition of the present invention, a cured product excellent in dielectric loss tangent and plating adhesion can usually be obtained.

[0012] The resin composition may further contain optional components in combination with components (A) to (C). Examples of the optional components include (D) inorganic fillers, (E) radically polymerizable compounds, (F) curing accelerators, (G) thermoplastic resins, and (H) other additives, etc. Hereinafter, each component contained in the resin composition will be described in detail.

[0013] <(A) Epoxy resin> The resin composition contains (A) epoxy resin as component (A). Examples of the (A) epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, and trimethylol type epoxy resin, etc. The (A) epoxy resin may be used alone or in combination of two or more.

[0014] The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. 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 with respect to 100% by mass of the non-volatile components of the epoxy resin.

[0015] Epoxy resins are classified into liquid epoxy resins (hereinafter referred to as "liquid epoxy resins") that are liquid at a temperature of 20°C and solid epoxy resins (hereinafter referred to as "solid epoxy resins") that are solid at a temperature of 20°C. The resin composition may contain only a liquid epoxy resin or only a solid epoxy resin as the epoxy resin, but from the viewpoint of significantly obtaining the effects of the present invention, it is preferable to contain a combination of a liquid epoxy resin and a solid epoxy resin.

[0016] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

[0017] Preferable liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, glycidyl amine type epoxy resins, and epoxy resins having a butadiene structure. Bisphenol A type epoxy resins and bisphenol F type epoxy resins are more preferable.

[0018] Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "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" (glycidylamine-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "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-glycidylcyclohexane-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd., and the like. These may be used alone or in combination of two or more.

[0019] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferred.

[0020] As the solid epoxy resin, a bixylenol-type epoxy resin, a naphthalene-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a novolac-type epoxy resin, a cresol novolac-type epoxy resin, a dicyclopentadiene-type epoxy resin, a trisphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, a naphthylene ether-type epoxy resin, an anthracene-type epoxy resin, a bisphenol A-type epoxy resin, a bisphenol AF-type epoxy resin, a tetraphenylethane-type epoxy resin is preferred, and a biphenyl-type epoxy resin is more preferred.

[0021] Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (tetrafunctional naphthalene-type 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" (naphthylene ether-type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (trisphenol-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" (bixylenol-type epoxy resin), "YX8800" (anthracene-type epoxy resin), "157S70" (novolak-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YX7760" (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, etc. These may be used alone or in combination of two or more kinds.

[0022] When a solid epoxy resin and a liquid epoxy resin are used in combination as the epoxy resin, their mass ratio (solid epoxy resin: liquid epoxy resin) is preferably 1:0.01 to 1:50, more preferably 1:0.05 to 1:20, and particularly preferably 1:0.1 to 1:10. By setting the amount ratio of the liquid epoxy resin and the solid epoxy resin within such a range, 1) appropriate adhesiveness is brought about when used in the form of a resin sheet, 2) sufficient flexibility is obtained when used in the form of a resin sheet, and the handleability is improved, and 3) effects such as being able to obtain a cured product having sufficient breaking strength can be obtained.

[0023] The epoxy equivalent of the epoxy resin is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., still more 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 product of a resin composition having a sufficient crosslink density can be obtained. The epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0024] From the viewpoint of significantly obtaining the desired effects of the present invention, the weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 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.

[0025] From the viewpoint of obtaining a cured product showing good mechanical strength and insulation reliability, when the non-volatile components in the resin composition are taken as 100% by mass, the content of the epoxy resin is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more. The upper limit of the content of the epoxy resin is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less from the viewpoint of significantly obtaining the desired effects of the present invention.

[0026] <(B) Hardening Agent> The resin composition contains a (B) hardening agent as the (B) component. The (B) hardening agent as this (B) component does not include those corresponding to the above-mentioned (A) component. The (B) hardening agent has a function of curing the (A) epoxy resin. The (B) hardening agent may be used alone or in combination of two or more.

[0027] The (B) hardening agent is not particularly limited as long as it has a function of curing the (A) epoxy resin. For example, active ester-based hardening agents, phenol-based hardening agents, naphthol-based hardening agents, benzoxazine-based hardening agents, cyanate ester-based hardening agents, and carbodiimide-based hardening agents can be mentioned. Among them, from the viewpoint of remarkably obtaining the effects of the present invention, it is preferable to contain one or more selected from phenol-based hardening agents, active ester-based hardening agents, and carbodiimide-based hardening agents, and it is more preferable to contain an active ester-based hardening agent.

[0028] As the phenol-based hardening agent and naphthol-based hardening agent, from the viewpoints of heat resistance and water resistance, a phenol-based hardening agent having a novolak structure or a naphthol-based hardening agent having a novolak structure is preferable. Also, from the viewpoint of the adhesion strength with the conductor layer, a nitrogen-containing phenol-based hardening agent or a nitrogen-containing naphthol-based hardening agent is preferable, and a phenol-based hardening agent containing a triazine skeleton or a naphthol-based hardening agent containing a triazine skeleton is more preferable. Among them, from the viewpoint of highly satisfying heat resistance, water resistance, and the adhesion strength with the conductor layer, a phenol novolak resin containing a triazine skeleton is preferable. These may be used alone or in combination of two or more.

[0029] As the active ester curing agent, there is no particular limitation, but generally, 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 preferably used. The active ester compound 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. Particularly from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester compound 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, phloroglucin, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolak, etc. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

[0030] As the active ester curing agent, specifically, dicyclopentadiene-type active ester compounds, naphthalene-type active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated product of phenol novolak, and active ester compounds containing a benzoylated product of phenol novolak are preferred. Among them, it is more preferred that it is at least one selected from dicyclopentadiene-type active ester compounds and naphthalene-type active ester compounds. As the dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferred.

[0031] Commercially available products of the active ester curing agent include, as the active ester compound containing a dicyclopentadiene-type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000L-65TM", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM" (manufactured by DIC Corporation); as the active ester compound containing a naphthalene structure, "HP-B-8151-62T", "EXB-8100L-65T", "EXB-9416-70BK", "HPC-8150-62T", "EXB-8" (manufactured by DIC Corporation); as the phosphorus-containing active ester compound, "EXB9401" (manufactured by DIC Corporation), as the active ester compound which is an acetylated product of phenol novolak, "DC808" (manufactured by Mitsubishi Chemical Corporation), as the active ester compound which is a benzoylated product of phenol novolak, "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation), as the active ester compound containing a styryl group and a naphthalene structure, "PC1300-02-65MA" (manufactured by Air Water Inc.), etc.

[0032] Specific examples of phenolic hardeners and naphthol-based hardeners include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN", "CBN", "GPH" manufactured by Nippon Kayaku Co., Ltd., "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", "SN395" manufactured by Nippon Steel Chemical & Material Co., Ltd., "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" manufactured by DIC Corporation, and the like.

[0033] Specific examples of benzoxazine-based hardeners include "HFB2006M" manufactured by Showa Highpolymer Co., Ltd., "P-d" and "F-a" manufactured by Shikoku Kasei Kogyo Co., Ltd.

[0034] Examples of cyanate ester-based hardeners include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins derived from phenol novolac and cresol novolac, and prepolymers in which some of these cyanate resins are partially triazinized. Specific examples of cyanate ester-based hardeners include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resins), "ULL-950S" (polyfunctional cyanate ester resin), "BA230", "BA230S75" (prepolymer in which part or all of bisphenol A dicyanate is triazinized to form a trimer) manufactured by Lonza Japan Co., Ltd., and the like.

[0035] The carbodiimide-based curing agent is a compound having one or more carbodiimide groups (-N = C = N-) in one molecule, and the carbodiimide-based curing agent is preferably a compound having two or more carbodiimide groups in one molecule.

[0036] Specific examples of the carbodiimide-based curing agent include commercially available carbodiimide-based curing agents such as Carbodilite V-03 (carbodiimide group equivalent: 216), V-05 (carbodiimide group equivalent: 262), V-07 (carbodiimide group equivalent: 200); V-09 (carbodiimide group equivalent: 200) manufactured by Nisshinbo Chemical Co., Ltd.; and Stabaxol P (carbodiimide group equivalent: 302) manufactured by Rhein Chemie.

[0037] The quantitative ratio of the epoxy resin to the curing agent is in the ratio of [total number of epoxy groups of the epoxy resin]:[total number of active groups of the curing agent], and the range of 1:0.01 to 1:10 is preferable, 1:0.3 to 1:5 is more preferable, and 1:0.5 to 1:3 is even more preferable. Here, the "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. Also, the "number of active groups of the curing agent" is the total value obtained by summing up the values obtained by dividing the mass of the non-volatile component of the curing agent present in the resin composition by the active group equivalent. By setting the quantitative ratio with the epoxy resin as the curing agent within such a range, the effects of the present invention can be remarkably obtained.

[0038] From the viewpoint of remarkably obtaining the desired effects of the present invention, when the non-volatile component in the resin composition is 100% by mass, the content of the curing agent is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less.

[0039] <(C) Thermoplastic resin having a hyperbranched structure> The resin composition contains, as component (C), a thermoplastic resin having a (C) hyperbranched structure. By including component (C) in the resin composition, it becomes possible to obtain a cured product with excellent crack resistance. Component (C) may be used alone or in combination of two or more.

[0040] (A) The thermoplastic resin having a hyperbranched structure refers to a thermoplastic resin having a multi-branched structure with a plurality of branches. The thermoplastic resin having a hyperbranched structure preferably has 2 or more, more preferably 3 or more, still more preferably 4 or more, 5 or more, 6 or more, 8 or more branched chains. (C) The thermoplastic resin having a hyperbranched structure preferably refers to a resin having a multi-branched structure in which structures derived from trifunctional or higher-functional compounds and structures derived from bifunctional compounds are alternately bonded, and having a structure derived from a monofunctional compound at the terminal.

[0041] The thermoplastic resin having such a preferable hyperbranched structure can be obtained by reacting a trifunctional or higher-functional compound, a bifunctional compound, which are at the center of the molecular structure, and a monofunctional compound at the terminal of the molecule. Since the thermoplastic resin having a hyperbranched structure has a multi-branched structure, it may have free space around the branched portion. By having free space, it is considered that even when the resin composition is cured, it is difficult to shrink and stress is hardly generated, and as a result, the occurrence of cracks is suppressed.

[0042] From the viewpoint of improving crack resistance, the terminal of component (C) is preferably a group having no ethylenic unsaturated bond such as a vinyl (-CH=CH2) group. That is, when the terminal of component (C) has an ethylenic unsaturated bond, it is excluded. Since the case where the terminal of component (C) has an ethylenic unsaturated bond is excluded, component (C) functions as a thermoplastic resin. It is considered that the stress of the cured product of the resin composition containing component (C) is relaxed, thereby improving crack resistance. As the terminal of component (C), it is preferably either an alkoxysilyl group or an aryloxy group, and more preferably all terminals are alkoxysilyl groups.

[0043] Examples of the alkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, a dimethoxymethylsilyl group, a methoxydimethylsilyl group, a diethoxymethylsilyl group, an ethoxydimethylsilyl group, a dimethoxyphenylsilyl group, a diethoxyphenylsilyl group, and the like.

[0044] Examples of the aryloxy group include a phenoxy group, a naphthyloxy group, an anthracenyloxy group, and the like.

[0045] From the viewpoint of remarkably obtaining the effects of the present invention, the component (C) preferably contains a cyclic structure, and the cyclic structure preferably contains an aromatic structure. The aromatic structure is a chemical structure generally defined as an aromatic, and also includes a polycyclic aromatic and an aromatic heterocycle.

[0046] Examples of the cyclic structure include a heterocyclic skeleton, a bisphenol skeleton, a phenylene ether skeleton, a phenylene skeleton, a naphthylene skeleton, a dimethylmethylenebiscyclohexylene skeleton, an anthracene skeleton, and the like. A heterocyclic skeleton and a bisphenol skeleton are preferable. Examples of the heterocyclic skeleton include a heterocyclic skeleton containing a nitrogen atom such as a triazine ring and a pyridine ring, and a triazine ring is preferable. Examples of the bisphenol skeleton include a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol AP skeleton, a bisphenol AF skeleton, a bisphenol B skeleton, a bisphenol BP skeleton, a bisphenol S skeleton, a bisphenol Z skeleton, a bisphenol C skeleton, a bisphenol TMC skeleton, a bisphenol AF skeleton, a bisphenol E skeleton, a bisphenol G skeleton, a bisphenol M skeleton, a bisphenol PH skeleton, and the like. A bisphenol TMC and a bisphenol AF skeleton are preferable. Among them, the component (C) preferably contains either a heterocyclic skeleton or a phenylene ether skeleton, more preferably contains either a triazine ring or a phenylene ether skeleton, and even more preferably has two cyclic structures of a triazine ring and a phenylene ether skeleton.

[0047] The cyclic structure is preferably included in any of the structures derived from a trifunctional or higher-functional compound, the structure derived from a bifunctional compound, and the structure derived from a monofunctional compound, and more preferably included in the structures derived from a trifunctional or higher-functional compound and the structure derived from a bifunctional compound.

[0048] The ring in the cyclic structure may have a substituent. Examples of such substituents include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an arylalkyl group having 7 to 12 carbon atoms, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group, an oxo group, and the like.

[0049] From the viewpoint of remarkably obtaining the effects of the present invention, the component (C) preferably has a siloxane structure (-Si-O-Si-). The siloxane structure is preferably included in any of the structures derived from a trifunctional or higher-functional compound, the structure derived from a bifunctional compound, and the structure derived from a monofunctional compound, and more preferably included in the structures derived from a bifunctional compound and the structure derived from a monofunctional compound. The structure derived from a bifunctional compound preferably contains, in one molecule, the structure derived from a bifunctional compound having a siloxane structure and the structure derived from a bifunctional compound not having a siloxane structure.

[0050] From the viewpoint of remarkably obtaining the effects of the present invention, the content ratio (the structure derived from a bifunctional compound having a siloxane structure / the structure derived from a bifunctional compound not having a siloxane structure) of the structure derived from a bifunctional compound having a siloxane structure and the structure derived from a bifunctional compound not having a siloxane structure in one molecule of the component (C) is preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0.2 or more, preferably 2 or less, still more preferably 1.5 or less, and more preferably 1 or less. The content ratio is a value calculated from the molar ratio of the charged amounts of the reaction raw materials.

[0051] The compound having three or more functional groups is a compound that can have a structure derived from a compound having three or more functional groups and can serve as the core of a hyperbranched structure. In addition, the compound having three or more functional groups has a functional group that can react with a bifunctional compound and a monofunctional compound. The compound having three or more functional groups becomes a structure derived from the compound having three or more functional groups in the hyperbranched structure. The compound having three or more functional groups is preferably a trifunctional compound or a tetrafunctional compound, and more preferably a trifunctional compound.

[0052] Examples of the functional group of the compound having three or more functional groups include halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; OH group (including phenolic hydroxyl group); amino group; epoxy group; glycidyl ether group, etc. Among them, halogen atoms are preferred.

[0053] From the viewpoint of significantly obtaining the effects of the present invention, the compound having three or more functional groups preferably contains a cyclic structure. The cyclic structure preferably contains an aromatic structure, preferably contains a heterocyclic skeleton, more preferably contains an aromatic heterocycle, even more preferably contains an aromatic heterocycle containing a nitrogen atom, and particularly preferably contains a triazine ring. The nitrogen atom contained in the aromatic heterocycle containing a nitrogen atom is preferably one or more, more preferably two or more, preferably six or less, more preferably five or less, and particularly preferably three.

[0054] Specific examples of the compound having three or more functional groups include, for example, cyanuric chloride, 2,4,6-trichloropyrimidine, 2,4,6-trichloropyridine, etc. Among them, cyanuric chloride is preferred as the compound having three or more functional groups.

[0055] The bifunctional compound is a compound that can bind to either the functional group of the compound having three or more functional groups or the functional group of the monofunctional compound, and has a functional group that can react with the functional group of the compound having three or more functional groups and the functional group of the monofunctional compound. The bifunctional compound becomes a structure derived from the bifunctional compound in the hyperbranched structure.

[0056] Examples of the functional groups of the bifunctional compound include, for example, an OH group (including a phenolic hydroxyl group), an epoxy group, a glycidyl ether group, an amino group, etc., and either an OH group or an amino group is preferable.

[0057] From the viewpoint of improving crack resistance, the bifunctional compound preferably contains a combination of a bifunctional compound containing a siloxane structure (-Si-O-Si-) and a bifunctional compound not containing a siloxane structure. The content ratio in one molecule of the bifunctional compound containing a siloxane structure and the bifunctional compound not containing a siloxane structure is the same as the content ratio of the structure derived from the bifunctional compound having a siloxane structure and the structure derived from the bifunctional compound not having a siloxane structure.

[0058] From the viewpoint of significantly obtaining the effects of the present invention, the bifunctional compound may contain a cyclic structure, and the cyclic structure preferably contains an aromatic structure, more preferably contains a phenylene skeleton or a phenylene ether skeleton, and even more preferably contains a phenylene ether skeleton. From the viewpoint of significantly obtaining the effects of the present invention, the phenylene ether skeleton is preferably contained in the bifunctional compound not containing a siloxane structure.

[0059] Specific examples of the bifunctional compound include, for example, compounds represented by the following formulas (1) to (50). In formula (32), X represents a phenyl group and Y represents a methyl group. In formulas (33) to (38), n represents an integer from 1 to 300, and in formulas (37) to (42), m represents an integer from 1 to 300. In formula (38), Y represents an oxygen atom, a methylene group, or a dimethylmethylene group. In formulas (39) to (42), R represents a methylene group or a phenylene group. In formula (40), R a represents a methyl group or a phenyl group.

[0060]

Chemical formula

Chemical formula

Chemical formula

Chem.

Chem.

Chem.

[0061] As the bifunctional compound, a compound obtained by reacting a trifunctional compound with a monofunctional compound described later may be used. Examples of such a bifunctional compound include compounds represented by the following formulas (43) to (50). In formula (43), R represents an isopropyl group.

Chem.

[0062] Among them, as the bifunctional compound, compounds represented by formulas (24), (25), (38) to (42) are preferable.

[0063] Commercially available products may be used as the bifunctional compound. Examples of commercially available products include "KF-2201" and "KF-8010" manufactured by Shin-Etsu Silicone Co., Ltd., "KF-8010", "X-22-9409", "KF-2201" manufactured by Shin-Etsu Chemical Co., Ltd., "SA90" manufactured by SABIC Innovative Plastics, etc.

[0064] The monofunctional compound is a compound that can bind to either the functional group of a trifunctional or higher-functional compound or the functional group of a bifunctional compound, and has a functional group that can react with either the functional group of a trifunctional or higher-functional compound or the functional group of a bifunctional compound. Further, as the structure derived from the monofunctional compound, the monofunctional compound can be at the end of the component (C).

[0065] Examples of the functional group of the monofunctional compound include, for example, an amino group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; an OH group (including a phenolic hydroxyl group); a thiol group; an amino group; an epoxy group; a glycidyl ether group, etc., and an amino group, a thiol group, and an OH group are preferable.

[0066] From the viewpoint of significantly obtaining the effects of the present invention, the monofunctional compound preferably contains a siloxane bond (-Si-O-), and more preferably is an alkoxysilane compound having the above functional group.

[0067] Specific examples of the monofunctional compound include, for example, compounds represented by the following formulas (1-1) to (1-24). In the following formulas, R represents an isopropyl group. In formulas (1-13) to (1-16), n represents an integer of 1 to 300.

Chemical formula

Chemical formula

Chemical formula

[0068] Among them, as the monofunctional compound, a compound represented by formula (1-10), a compound represented by formula (1-22), a compound represented by formula (1-23), and a compound represented by formula (1-24) are preferable.

[0069] Commercially available products may be used as the monofunctional compound. Examples of commercially available products include "X-22-170BX" and "X-22-170DX" manufactured by Shin-Etsu Silicone Co., Ltd., and "KBM903", "KBE903", "KBM603", "KBM573", "KBM802", etc. manufactured by Shin-Etsu Chemical Co., Ltd.

[0070] (C) The thermoplastic resin having a hyperbranched structure can be prepared by reacting a compound having a functionality of 3 or more, a bifunctional compound, and a monofunctional compound. Further, the bifunctional compound is preferably prepared by combining a bifunctional compound having a siloxane structure and a bifunctional compound not having a siloxane structure.

[0071] The reaction temperature is preferably 10°C or higher, more preferably 30°C or higher, still more preferably 40°C or higher, and preferably 100°C or lower, more preferably 80°C or lower, still more preferably 60°C or lower. Particularly preferably, it is 50°C.

[0072] The reaction time is preferably 1 hour or longer, more preferably 5 hours or longer, still more preferably 10 hours or longer, and preferably 50 hours or shorter, more preferably 24 hours or shorter, still more preferably 15 hours or shorter. Particularly preferably, it is overnight (12 hours).

[0073] Specific examples of the (C) thermoplastic resin having a hyperbranched structure include the following, but the present invention is not limited thereto. In the following formula, the broken line means that a multi-branched structure in which structures derived from a compound having a functionality of 3 or more and a structure derived from a bifunctional compound are alternately bonded is further bonded. R represents a methylene group or a phenylene group.

Chemical formula

[0074] Regarding the weight average molecular weight of the (C) component, from the viewpoint of remarkably obtaining the effects of the present invention, it is preferably 1000 or more, more preferably 1200 or more, still more preferably 1400 or more, and preferably 40000 or less, more preferably 30000 or less, still more preferably 20000 or less, 10000 or less, 6000 or less. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by the gel permeation chromatography (GPC) method.

[0075] The glass transition temperature (Tg) of component (C) is preferably 50°C or higher, more preferably 60°C or higher, still more preferably 70°C or higher, and preferably 150°C or lower, more preferably 140°C or lower, still more preferably 130°C or lower, from the viewpoint of significantly obtaining the effects of the present invention. The glass transition temperature can be measured by differential scanning calorimetry (DSC). Component (C) may have a plurality of glass transition temperatures. In that case, the plurality of glass transition temperatures are preferably within such a range.

[0076] The content of component (C) 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, and preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less, 5% by mass or less, 3% by mass or less, when the non-volatile components in the resin composition are 100% by mass, from the viewpoint of obtaining a cured product having excellent crack resistance.

[0077] <(D) Inorganic filler> The resin composition may contain an optional (D) inorganic filler as component (D). By including the (D) inorganic filler in the resin composition, it becomes possible to obtain a cured product having a low dielectric tangent.

[0078] As the material of the inorganic filler, an inorganic compound is used. Examples of the material of the inorganic filler include 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 tungstate phosphate, etc. Among these, silica is particularly preferable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. Also, as silica, spherical silica is preferable. (D) The inorganic filler may be used alone or in combination of two or more kinds.

[0079] (D) Examples of commercially available products of the inorganic filler include, for example, "UFP-30" manufactured by Denka Chemical Industry Co., Ltd.; "SP60-05", "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatechs Co., Ltd.; "UFP-30" manufactured by Denka Co., Ltd.; "Silfill NSS-3N", "Silfill NSS-4N", "Silfill NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", "SC2050-SXF" manufactured by Admatechs Co., Ltd.; and the like.

[0080] (D) From the viewpoint of significantly obtaining the desired effects of the present invention, the average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, and preferably 5 μm or less, more preferably 2 μm or less, still more preferably 1 μm or less.

[0081] (D) The average particle size 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 is created on a volume basis using a laser diffraction / scattering type particle size distribution measuring device, and the median diameter is used as the average particle size for measurement. As the measurement sample, 100 mg of the inorganic filler, 10 g of methyl ethyl ketone, and 0.1 g of a dispersant ("SN9228" manufactured by Sannopco) can be weighed into a vial and dispersed by ultrasonic waves for 10 minutes for use. The measurement sample is measured for the volume-based particle size distribution of the inorganic filler using a laser diffraction type particle size distribution measuring device with the light source wavelengths of blue and red, and the average particle size is calculated as the median diameter from the obtained particle size distribution. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba, Ltd. and "SALD-2200" manufactured by Shimadzu Corporation.

[0082] (D) From the viewpoint of significantly obtaining the desired effects of the present invention, the specific surface area of the inorganic filler is preferably 1 m 2 / g or more, more preferably 2 m 2 / g or more, and particularly preferably 3 m 2 / g or more. There is no particular limitation on the upper limit, but it is preferably 60 m 2 / g or less, 50 m 2 / g or less, or 40 m 2 / g or less. The specific surface area can be obtained by measuring the specific surface area of the inorganic filler by adsorbing nitrogen gas on the sample surface using a BET fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) and calculating the specific surface area using the BET multi-point method.

[0083] (D) From the viewpoint of enhancing moisture resistance and dispersibility, the inorganic filler is preferably treated with a surface treatment agent. Examples of the surface treatment agent include fluorine-containing silane coupling agents such as 3,3,3-trifluoropropyltrimethoxysilane; aminosilane-based coupling agents such as 3-aminopropyltriethoxysilane, N-phenyl-8-aminooctyl-trimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; epoxy silane-based coupling agents such as 3-glycidoxypropyltrimethoxysilane; mercapto silane-based coupling agents such as 3-mercaptopropyltrimethoxysilane; silane-based coupling agents; alkoxysilanes such as phenyltrimethoxysilane; organosilazane compounds such as hexamethyldisilazane; titanate-based coupling agents, and the like. Further, the surface treatment agent may be used alone or in any combination of two or more kinds.

[0084] Examples of commercially available products of the surface treatment agent include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

[0085] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent preferably falls within a predetermined range. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 to 5 parts by mass of the surface treatment agent, preferably surface-treated with 0.2 to 3 parts by mass, and preferably surface-treated with 0.3 to 2 parts by mass.

[0086] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg / m 2 or more from the viewpoint of improving the dispersibility of the inorganic filler, 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 suppressing the increase in the melt viscosity of the resin varnish and the melt viscosity in the sheet form, it is preferably 1 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.

[0087] (D) The amount of carbon per unit surface area of the inorganic filler can be measured after washing the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient 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 content, 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. can be used.

[0088] (D) As the content of the inorganic filler, from the viewpoint of obtaining a cured product with a low dielectric loss tangent, when the non-volatile components in the resin composition are 100% by mass, it is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less.

[0089] <(E) Radical polymerizable compound> The resin composition may further contain, as an optional component, (E) a radically polymerizable compound in combination with the above-described components (A) to (C). The (E) radically polymerizable compound as this (E) component does not include those corresponding to the above-described components (A) to (D). The (E) radically polymerizable compound may be used alone or in combination of two or more kinds.

[0090] (E) The radically polymerizable compound may have an ethylenically unsaturated bond. The (E) radically polymerizable compound may have, for example, an unsaturated hydrocarbon group such as an allyl group, 3-cyclohexenyl group, 3-cyclopentenyl group, p-vinylphenyl group, m-vinylphenyl group, o-vinylphenyl group; an α,β-unsaturated carbonyl group such as an acryloyl group, methacryloyl group, maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group); and the like. The (E) radically polymerizable compound preferably has two or more radically polymerizable groups.

[0091] Examples of the (E) radically polymerizable compound include (meth)acrylic radically polymerizable compounds, styrenic radically polymerizable compounds, allylic radically polymerizable compounds, maleimide-based radically polymerizable compounds, and the like.

[0092] (Meth)acrylic radical polymerizable compounds are, for example, compounds having one or more, preferably two or more acryloyl groups and / or methacryloyl groups. Examples of (meth)acrylic radical polymerizable compounds include low molecular weight (molecular weight less than 1000) aliphatic (meth)acrylate compounds such as cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate; low molecular weight (molecular weight less than 1000) ether-containing (meth)acrylate compounds such as dioxane glycol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di(meth)acrylate, 3,6,9-trioxaundecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate; low molecular weight (molecular weight less than 1000) isocyanurate-containing (meth)acrylate compounds such as tris(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate; high molecular weight (molecular weight 1000 or more) acrylate compounds such as (meth)acrylic-modified polyphenylene ether resin, and the like.Examples of commercially available (meth)acrylic radical polymerizable compounds include, for example, "A-DOG" (dioxane glycol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" (tricyclodecane dimethanol diacrylate), "DCP" (tricyclodecane dimethanol dimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd., "KAYARAD R-684" (tricyclodecane dimethanol diacrylate), "KAYARAD R-604" (dioxane glycol diacrylate) of Nippon Kayaku Co., Ltd., "SA-9000", "SA-9000-111" (methacryl-modified polyphenylene ether) manufactured by SABIC Innovative Plastics, etc.

[0093] Styrene-based radical polymerizable compounds are, for example, compounds having one or more, preferably two or more vinyl groups directly bonded to aromatic carbon atoms. Examples of styrene-based radical polymerizable compounds include low molecular weight (molecular weight less than 1000) styrene-based compounds such as 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; high molecular weight (molecular weight 1000 or more) styrene-based compounds such as vinylbenzyl-modified polyphenylene ether resin, styrene-divinylbenzene copolymer, etc. Examples of commercially available styrene-based radical polymerizable compounds include, 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, Inc.

[0094] An allyl radical polymerizable compound is, for example, a compound having one or more, preferably two or more allyl groups. Examples of the allyl radical polymerizable compound include aromatic carboxylic acid allyl ester compounds such as diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, diallyl 2,3-naphthalenedicarboxylate; allyl ester compounds of isocyanuric acid such as 1,3,5-triallyl isocyanurate, 1,3-diallyl-5-glycidyl isocyanurate; epoxy-containing aromatic allyl compounds such as 2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane; benzoxazine-containing aromatic allyl compounds such as bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane; ether-containing aromatic allyl compounds such as 1,3,5-triallyl ether benzene; allyl silane compounds such as diallyl diphenyl silane and the like. Examples of commercially available allyl radical polymerizable compounds include "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Kasei Co., Ltd., "DAD" (diallyl diphenate) manufactured by Nittsu Techno Fine Chemical Co., Ltd., "TRIAM-705" (triallyl trimellitate) manufactured by Wako Pure Chemical Industries, Ltd., the product name "DAND" (diallyl 2,3-naphthalenedicarboxylate) manufactured by Nippon Distillation Industry Co., Ltd., "ALP-d" (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane) manufactured by Shikoku Kasei Kogyo Co., Ltd., "RE-810NM" (2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane) manufactured by Nippon Kayaku Co., Ltd., "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Kasei Co., Ltd. and the like.

[0095] The maleimide-based radically polymerizable compound is, for example, a compound having one or more, preferably two or more maleimide groups. The maleimide-based radically polymerizable compound may be an aliphatic maleimide compound containing an aliphatic amine skeleton or an aromatic maleimide compound containing an aromatic amine skeleton. Examples of commercially available maleimide-based radically polymerizable compounds include "SLK-2600" manufactured by Shin-Etsu Chemical Co., Ltd., "BMI-1500", "BMI-1700", "BMI-3000J", "BMI-689", "BMI-2500" (maleimide compound containing a dimer diamine structure) manufactured by Designer Molecules, Inc., "BMI-6100" (aromatic maleimide compound) manufactured by Designer Molecules, Inc., "MIR-5000-60T", "MIR-3000-70MT" (biphenyl aralkyl type maleimide compound) manufactured by Nippon Kayaku Co., Ltd., "BMI-70", "BMI-80" manufactured by K.I. Kasei Co., Ltd., "BMI-2300", "BMI-TMH" manufactured by Daiwa Kasei Kogyo Co., Ltd., and the like. Further, as the maleimide-based radically polymerizable compound, a maleimide resin (maleimide compound containing an indane ring skeleton) disclosed in Invention Association Public Technical Report Publication No. 2020-500211 may be used.

[0096] (E) The ethylene unsaturated bond equivalent of the radically polymerizable compound is preferably 20 g / eq. to 3000 g / eq., more preferably 50 g / eq. to 2500 g / eq., still more preferably 70 g / eq. to 2000 g / eq., and particularly preferably 90 g / eq. to 1500 g / eq. The ethylene unsaturated bond equivalent represents the mass of the radically polymerizable compound per equivalent of the ethylene unsaturated bond.

[0097] (E) The weight average molecular weight (Mw) of the radically polymerizable compound is preferably 40000 or less, more preferably 10000 or less, still more preferably 5000 or less, and particularly preferably 3000 or less. The lower limit is not particularly limited, but may be, for example, 150 or more.

[0098] (E) The content of the radically polymerizable compound may be 0% by mass, preferably 0.01% 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 10% by mass or less, and particularly preferably 5% by mass or less, when the nonvolatile components in the resin composition are taken as 100% by mass.

[0099] <(F) Curing accelerator> The resin composition may further contain, as an optional component, (F) a curing accelerator in combination with the above-mentioned components (A) to (D). The (F) curing accelerator as the (F) component does not include those corresponding to the above-mentioned components (A) to (E). The (F) curing accelerator has a function as a curing catalyst for promoting the curing of the (A) epoxy resin.

[0100] As the (F) curing accelerator, a compound that promotes the effect of the (A) epoxy resin can be used. Examples of such (F) curing accelerators include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators, etc. The (F) curing accelerator may be used alone or in combination of two or more.

[0101] Examples of phosphorus-based hardening accelerators include 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-butyldimethylphosphonium tetraphenylborate; aromatic phosphonium salts such as methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate; 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;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)diphenylether, etc. are mentioned.;

[0102] Examples of urea-based curing accelerators include, for example, 1,1-dimethylurea; 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.

[0103] Examples of guanidine-based curing accelerators include, 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.

[0104] Examples of imidazole-based curing accelerators include imidazole compounds such as 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 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, 1-cyanoethyl-2-phenylimidazolium trimellitate, 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 adducts of imidazole compounds and epoxy resins. Commercially available products of imidazole-based curing accelerators include, for example, "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", "2MA-OK-PW", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", "C11Z-A" manufactured by Shikoku Kasei Kogyo Co., Ltd.; "P200-H50" manufactured by Mitsubishi Chemical Corporation, etc.

[0105] Examples of the metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, tin, etc. Specific examples of the organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and 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, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of the organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, etc.

[0106] Examples of the amine-based hardening accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc. As the amine-based hardening accelerator, commercially available products may be used, and examples thereof include "MY-25" manufactured by Ajinomoto Fine-Techno Co., Inc.

[0107] (F) When the non-volatile components in the resin composition are 100% by mass, the content of the hardening accelerator 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, and preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.3% by mass or less.

[0108] <(G) Thermoplastic resin> The resin composition may further contain, as an optional component, (G) a thermoplastic resin (however, those corresponding to the component (C) are excluded) in combination with the above-described components (A) to (C). The (G) thermoplastic resin as the component (G) does not include those corresponding to the above-described components (A) to (F).

[0109] (G) Examples of the thermoplastic resin include, for example, 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, and the like. (G) The thermoplastic resin may be used alone or in combination of two or more.

[0110] Examples of the phenoxy resin include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Specific examples of the phenoxy resin include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both are bisphenol A skeleton-containing phenoxy resins); "YX8100" manufactured by Mitsubishi Chemical Corporation (bisphenol S skeleton-containing phenoxy resin); "YX6954" manufactured by Mitsubishi Chemical Corporation (bisphenol acetophenone skeleton-containing phenoxy resin); "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.

[0111] Specific examples of the polyimide resin include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., "Ricacote SN20" and "Ricacote PN20" manufactured by Nippon Rika Kasei Co., Ltd., and the like.

[0112] Examples of the polyvinyl acetal resin include, for example, polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin include "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", "Denka Butyral 6000-EP" manufactured by Denki Kagaku Kogyo Co., Ltd.; ESREC BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, BM series manufactured by Sekisui Chemical Co., Ltd.; and the like.

[0113] Examples of the polyolefin resin include ethylene-based copolymer resins such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer; and polyolefin polymers such as polypropylene, ethylene-propylene block copolymer.

[0114] Examples of the polybutadiene resin include, for example, resins containing a hydrogenated polybutadiene skeleton, hydroxyl group-containing polybutadiene resin, phenolic hydroxyl group-containing polybutadiene resin, carboxy group-containing polybutadiene resin, acid anhydride group-containing polybutadiene resin, epoxy group-containing polybutadiene resin, isocyanate group-containing polybutadiene resin, urethane group-containing polybutadiene resin, polyphenylene ether-polybutadiene resin, and the like.

[0115] Specific examples of the polyamideimide resin include "Vironmax HR11NN" and "Vironmax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin also include modified polyamideimides such as "KS9100" and "KS9300" (polyamideimide containing a polysiloxane skeleton) manufactured by Hitachi Chemical Co., Ltd.

[0116] Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0117] Specific examples of the polysulfone resin include polysulfones "P1700", "P3500", etc. manufactured by Solvay Advanced Polymers.

[0118] Specific examples of the polyphenylene ether resin include "NORYL SA90" manufactured by SABIC. Specific examples of the polyetherimide resin include "ULTEM" manufactured by GE.

[0119] Examples of the polycarbonate resin include a hydroxy group-containing carbonate resin, a phenolic hydroxyl group-containing carbonate resin, a carboxy group-containing carbonate resin, an acid anhydride group-containing carbonate resin, an isocyanate group-containing carbonate resin, a urethane group-containing carbonate resin, etc. Specific examples of the polycarbonate resin include "FPC0220" manufactured by Mitsubishi Gas Chemical Company, "T6002", "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals Corporation, "C-1090", "C-2090", "C-3090" (polycarbonate diol) manufactured by Kuraray Co., Ltd. Specific examples of the polyetheretherketone resin include "Sumipro EK" manufactured by Sumitomo Chemical Company.

[0120] Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexanedimethylene terephthalate resin, etc.

[0121] (G) The weight average molecular weight (Mw) of the thermoplastic resin is preferably greater than 5,000, more preferably 8,000 or more, still more preferably 10,000 or more, particularly preferably 20,000 or more, and preferably 100,000 or less, more preferably 70,000 or less, still more preferably 60,000 or less, particularly preferably 50,000 or less.

[0122] (G) When the content of the thermoplastic resin is based on 100% by mass of the non-volatile components in the resin composition, it may be 0% by mass, may be greater than 0% by mass, preferably 0.01% by mass or more, more preferably 0.10% by mass or more, still more preferably 0.2% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 2% by mass or less.

[0123] <(H) Optional Additives> The resin composition may further contain, as an optional non-volatile component in combination with the above-described components (A) to (C), (H) an optional additive. Examples of the (H) optional additive include a polymerization initiator; an organometallic compound such as an organic copper compound, an organic zinc compound, or an organic cobalt compound; a colorant such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, or carbon black; a polymerization inhibitor such as hydroquinone, catechol, pyrogallol, or phenothiazine; a leveling agent such as a silicone-based leveling agent or an acrylic polymer-based leveling agent; a thickener such as benton or montmorillonite; an antifoaming agent such as a silicone-based antifoaming agent, an acrylic-based antifoaming agent, a fluorine-based antifoaming agent, or a vinyl resin-based antifoaming agent; an ultraviolet absorber such as a benzotriazole-based ultraviolet absorber; an adhesion improver such as urea silane; an adhesion promoter such as a triazole-based adhesion promoter, a tetrazole-based adhesion promoter, or a triazine-based adhesion promoter; an antioxidant such as a hindered phenol-based antioxidant; a fluorescent brightener such as a stilbene derivative; a surfactant such as a fluorine-based surfactant or a silicone-based surfactant; a flame retardant such as a phosphorus-based flame retardant (e.g., a phosphate ester compound, a phosphazene compound, a phosphinic acid compound, or red phosphorus), a nitrogen-based flame retardant (e.g., melamine sulfate), a halogen-based flame retardant, or an inorganic flame retardant (e.g., antimony trioxide); a dispersant such as a phosphate ester-based dispersant, a polyoxyalkylene-based dispersant, an acetylene-based dispersant, a silicone-based dispersant, an anionic dispersant, or a cationic dispersant; a stabilizer such as a borate-based stabilizer, a titanate-based stabilizer, an aluminate-based stabilizer, a zirconate-based stabilizer, an isocyanate-based stabilizer, a carboxylic acid-based stabilizer, or a carboxylic anhydride-based stabilizer; a photoinitiator coagent such as a tertiary amine; a photosensitizer such as a pyralizone, an anthracene, a coumarin, a xanthone, or a thioxanthone. The (H) optional additive may be used alone or in combination of two or more.

[0124] The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method of adding a solvent or the like as necessary to the compounding components and mixing and dispersing them using a rotary mixer or the like.

[0125] <Physical properties and uses of the resin composition> Since the resin composition contains a combination of components (A) to (C), the occurrence of cracks is suppressed, and usually, a cured product excellent in dielectric tangent and plating adhesion can be obtained.

[0126] The cured product obtained by thermally curing the resin composition at 130°C for 30 minutes and then at 180°C for 30 minutes exhibits the characteristic that the occurrence of cracks is suppressed. Therefore, the cured product provides an insulating layer excellent in crack resistance. Specifically, a resin composition is laminated on an inner layer substrate having circuit conductors on both sides to obtain a resin composition layer. The inner layer substrate laminated with the resin composition layer is thermally cured at 130°C for 30 minutes and then at 180°C for 30 minutes to obtain a cured substrate. A desmear treatment is performed on the cured substrate to obtain a sample, and the surface of the insulating layer after the desmear treatment of the sample is observed. Among 100 samples, the ratio of samples with cracks is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more, 80% or more. The upper limit is not particularly limited, but can be 100% or less, 95% or less, etc. The details of crack measurement can be measured according to the method described in the examples below.

[0127] The cured product obtained by thermally curing the resin composition at 130°C for 30 minutes and then at 180°C for 30 minutes usually exhibits the characteristic of excellent adhesion to plating. Therefore, the cured product provides an insulating layer excellent in adhesion to the plated conductor layer. The plating adhesion (peel strength) is preferably 0.30 kgf / cm or more, more preferably 0.35 kgf / cm or more, still more preferably 0.40 kgf / cm or more. The upper limit value of the plating adhesion can be 10 kgf / cm or less, etc. The measurement of the plating adhesion can be measured according to the method described in the examples below.

[0128] The cured product obtained by thermosetting the resin composition at 200°C for 90 minutes usually exhibits the property of having 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 0.004 or less, more preferably 0.0035 or less, and even more preferably 0.003 or less. On the other hand, the lower limit value of the dielectric loss tangent can be 0.0001 or more, etc. The measurement of the dielectric loss tangent can be carried out according to the method described in the examples below.

[0129] The resin composition can obtain a cured product with excellent crack resistance. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulating applications. Specifically, it can be suitably used as a resin composition for forming the insulating layer (including the 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.

[0130] Also, in the multilayer printed wiring board described below, 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).

[0131] Also, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can also be suitably used as a resin composition for the rewiring formation layer as an insulating layer for forming the rewiring layer (resin composition for forming the rewiring formation layer), and a resin composition for encapsulating the semiconductor chip (resin composition for encapsulating the semiconductor chip). When manufacturing the semiconductor chip package, a further rewiring layer may be formed on the encapsulation layer. (1) Step of laminating a temporary fixing film on a substrate, (2) Step of temporarily fixing a semiconductor chip on the temporary fixing film, (3) Step of forming an encapsulation layer on the semiconductor chip, (4) Step of peeling the substrate and the temporary fixing film from the semiconductor chip, (5) Forming a redistribution layer as an insulating layer on the surface from which the substrate of the semiconductor chip and the temporary fixing film have been peeled, and (6) Forming a redistribution layer as a conductor layer on the redistribution layer forming layer

[0132] [Resin sheet] The resin sheet of the present invention includes a support and a resin composition layer formed of the resin composition of the present invention provided on the support.

[0133] From the viewpoints of thinning the printed wiring board and providing a cured product having excellent insulation even if the cured product of the resin composition is a thin film, the thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, and still more preferably 30 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more, etc.

[0134] 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 preferable.

[0135] 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 abbreviated as "PET"), polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyethersulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

[0136] When using a metal foil as the support, examples of the metal foil include copper foil, aluminum foil, etc., and copper foil is preferred. As the copper foil, a foil made of single metal copper may be used, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may also be used.

[0137] The support may be subjected to matting treatment, corona treatment, or antistatic treatment on the surface that joins the resin composition layer.

[0138] Also, as the support, a support with a release layer having a release layer on the surface that joins the resin composition layer may be used. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. As the support with a release layer, a commercially available product may be used. For example, "SK-1", "AL-5", "AL-7" manufactured by Lintec Corporation, which are PET films having a release layer mainly composed of an alkyd resin-based release agent, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, "Unipile" manufactured by Unitika Ltd., etc.

[0139] The thickness of the support is not particularly limited, but a range of 5 μm to 75 μm is preferred, and a range of 10 μm to 60 μm is more preferred. When using a support with a release layer, it is preferable that the total thickness of the support with a release layer is within the above range.

[0140] In one embodiment, the resin sheet may further contain other layers as needed. Examples of such other layers include a protective film similar to the support provided on the surface of the resin composition layer that is not joined to the support (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion of dust or the like and scratches on the surface of the resin composition layer.

[0141] The resin sheet can be manufactured, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying this resin varnish onto a support using a die coater or the like, and further drying it to form a resin composition layer.

[0142] Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

[0143] Drying may be carried out by known methods such as heating and hot air blowing. The drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% to 60% by mass of the organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0144] The resin sheet can be wound into a roll and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0145] [Printed Wiring Board] The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention.

[0146] The printed wiring board can be manufactured, for example, by a method including the following steps (I) and (II) using the above resin sheet. (I) A step of laminating on an inner layer substrate such that the resin composition layer of the resin sheet is joined to the inner layer substrate (II) A step of thermally curing the resin composition layer to form an insulating layer

[0147] The "inner layer substrate" used in step (I) is a member serving as a substrate of a printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. Further, the substrate may have a conductor layer on one or both sides thereof, and this conductor layer may be pattern-processed. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate may be referred to as an "inner layer circuit board". In addition, when manufacturing a printed wiring board, an intermediate product on which an insulating layer and / or a conductor layer is to be further formed is also included in the "inner layer substrate" referred to in the present invention. When the printed wiring board is a component-built circuit board, an inner layer substrate incorporating components can be used.

[0148] 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. Examples of a member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as a "thermocompression bonding member") include a heated metal plate (such as a SUS mirror plate) or a metal roll (SUS roll). Note that it is preferable to press through an elastic material such as a heat-resistant rubber so that the resin sheet sufficiently follows the surface unevenness of the inner layer substrate, rather than directly pressing the thermocompression bonding member against the resin sheet.

[0149] The lamination of the inner layer substrate and the resin sheet may 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 a pressure of 26.7 hPa or less.

[0150] Lamination can be carried out using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include, for example, the vacuum pressure type laminator manufactured by Meiki Seisakusho Co., Ltd., the vacuum applicator manufactured by Nichioh Materials Co., Ltd., the batch type vacuum pressure laminator, and the like.

[0151] After lamination, under normal pressure (atmospheric pressure), for example, by pressing a heat-bonding member from the support side, a smoothing treatment of the laminated resin sheet may be performed. The pressing conditions for the smoothing treatment can be the same as the heat-bonding conditions for the above lamination. The smoothing treatment can be carried out using a commercially available laminator. In addition, lamination and smoothing treatment may be continuously carried out using the above-mentioned commercially available vacuum laminator.

[0152] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0153] In step (II), the resin composition layer is thermally cured to form an insulating layer. The thermal curing conditions of the resin composition layer are not particularly limited, and the conditions usually adopted when forming an insulating layer of a printed wiring board may be used.

[0154] For example, the thermal curing conditions of the resin composition layer vary depending on the type of the resin composition and the like, but the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and still more preferably 170°C to 210°C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and still more preferably 15 minutes to 100 minutes.

[0155] Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, at a temperature of 50°C or higher and lower than 120°C (preferably 60°C or higher and 115°C or lower, more preferably 70°C or higher and 110°C or lower), the resin composition layer may be preheated for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and still more preferably 15 minutes to 100 minutes).

[0156] When manufacturing a printed wiring board, the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer may be further performed. These steps (III) to (V) may be performed according to various methods known to those skilled in the art used for manufacturing a printed wiring board. When removing the support after step (II), the removal of the support may be performed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). Further, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board.

[0157] Step (III) is a step of drilling holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be performed using, for example, a drill, a laser, a plasma, etc., according to the composition of the resin composition used for forming the insulating layer. The dimensions and shapes of the holes may be appropriately determined according to the design of the printed wiring board.

[0158] Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), smears are also removed. The procedures and conditions for the roughening treatment are not particularly limited, and known procedures and conditions commonly used when forming the insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. The swelling liquid used for the roughening treatment is not particularly limited, and examples include an alkaline solution and a surfactant solution, preferably an alkaline solution. As the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Commercially available swelling liquids include, for example, "Swelling Dip Security Gun P", "Swelling Dip Security SBU", and "Swelling Dip Security Agent P" manufactured by Atotech Japan Co., Ltd. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in a 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 preferable to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes. The oxidizing agent used for the roughening treatment is not particularly limited, and examples include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. Also, the concentration of the permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Commercially available oxidizing agents include, for example, alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security Gun P" manufactured by Atotech Japan Co., Ltd. Further, the neutralizing liquid used for the roughening treatment is preferably an acidic aqueous solution, and commercially available products include, for example, "Reduction Solution Security Agent P" manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing liquid can be performed by immersing the treated surface that has been roughened with the oxidizing agent in a 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 an object that has been roughened with an oxidizing agent in a neutralizing solution at 40°C to 70°C for 5 minutes to 20 minutes is preferable.

[0159] In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment 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, but 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 type surface roughness meter.

[0160] Step (V) is a step of forming a conductor layer, and a conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include a layer formed from an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among them, from the viewpoints of versatility, cost, ease of patterning, etc. of conductor layer formation, 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 preferable, 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 preferable, and a single metal layer of copper is still more preferable.

[0161] The conductor layer may have a single-layer structure or a multi-layer structure in which a single metal layer or an alloy layer made of different types of metals or alloys is laminated in two or more layers. When the conductor layer has a multi-layer 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.

[0162] The thickness of the conductor layer depends on the design of the desired printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0163] In one embodiment, the conductor layer may be formed by plating. For example, by a conventionally known technique such as a semi-additive method or a full-additive method, plating is performed on the surface of the insulating layer to form a conductor layer having a desired wiring pattern. From the viewpoint of manufacturing simplicity, it is preferable to form the conductor layer by the semi-additive method. Hereinafter, an example of forming the conductor layer by the semi-additive method will be shown.

[0164] First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to the desired wiring pattern. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

[0165] [Semiconductor device] 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.

[0166] Examples of the semiconductor device include various semiconductor devices used in electric products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, airplanes, etc.).

[0167] The semiconductor device of the present invention can be manufactured by mounting components (semiconductor chips) at the conductive portions of the printed wiring board. The "conductive portion" is "a portion that transmits an electrical signal in the printed wiring board", and the location may be either on the surface or an embedded portion. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

[0168] The method for mounting a semiconductor chip in manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. Specifically, examples include a wire bonding mounting method, a flip chip mounting method, a mounting method using a bump-less build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), and the like. Here, the "mounting method using a bump-less build-up layer (BBUL)" refers to "a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip is connected to wiring on the printed wiring board."

Example

[0169] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following description, unless otherwise specified, "parts" and "%" mean "parts by mass" and "mass%", respectively.

[0170] <Synthesis Example 1: Synthesis of Thermoplastic Resin A Having a Hyperbranched Structure> After adding acetone to 1.94 g of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane in a reaction vessel and dissolving it, 0.922 g of cyanuric chloride, 0.946 g of both-terminal amine-modified silicone oil ("KF-8010" manufactured by Shin-Etsu Chemical Co., Ltd.), and 3-aminopropyltriethoxysilane ( "KBE-903" manufactured by Shin-Etsu Chemical Co., Ltd.) 0.553 g were added and reacted at 50°C overnight. Then, ethyl acetate was added for extraction, and insoluble matters were removed by filtration. Next, the filtrate was washed with water and then dehydrated with anhydrous magnesium sulfate, and the solvent was concentrated and distilled off. The residue was crystallized from methanol to obtain a thermoplastic resin A having a hyperbranched structure of the following structure (R represents a methylene group or a phenylene group). The measured weight average molecular weight of the thermoplastic resin A was 21,600. Also, the measured glass transition temperature of the thermoplastic resin A was 80°C.

Chemical formula

[0171] <Synthesis Example 2: Synthesis of Thermoplastic Resin B Having a Hyperbranched Structure> In Synthesis Example 1, 1.94 g of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane was changed to 2.37 g of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. Except for the above matters, in the same manner as in Synthesis Example 1, a thermoplastic resin B having a hyperbranched structure shown below was obtained. The measured weight average molecular weight of the thermoplastic resin B was 10,200. Also, the measured glass transition temperature of the thermoplastic resin B was 86°C.

[0172] <Synthesis Example 3: Synthesis of Thermoplastic Resin C Having a Hyperbranched Structure> In Synthesis Example 2, the amount of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene was changed from 2.37 g to 2.65 g, and the amount of the both-end amine-modified silicone oil ("KF-8010" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 0.946 g to 0.301 g. Except for the above matters, in the same manner as in Synthesis Example 2, a thermoplastic resin C having a hyperbranched structure was obtained. The measured weight average molecular weight of the thermoplastic resin C was 8,800. Also, the measured glass transition temperature of the thermoplastic resin C was 92°C.

[0173] <Synthesis Example 4: Synthesis of Thermoplastic Resin D Having a Hyperbranched Structure> 1.24 g of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and 3.83 g of bisphenol having a phenylene ether structure ("SA90" manufactured by SABIC Innovative Plastics) were added to a reaction vessel, dissolved by adding tetrahydrofuran, and then 0.922 g of cyanuric chloride, 0.946 g of the both-end amine-modified silicone oil ("KF-8010" manufactured by Shin-Etsu Chemical Co., Ltd.), and 3-aminopropyltriethoxysilane0.553 g of “KBE-903” (manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the reaction was carried out at 50 °C overnight. Thereafter, ethyl acetate was added for extraction, and insoluble matters were removed by filtration. Next, the filtrate was washed with water and then dehydrated with anhydrous magnesium sulfate, and the solvent was concentrated and distilled off. The residue was crystallized from methanol to obtain a thermoplastic resin D having a hyperbranched structure. The weight-average molecular weight of the thermoplastic resin D was measured to be 14,200. Also, the glass transition temperature of the thermoplastic resin D was measured to be 76 °C.

[0174] <Synthesis Example 5: Synthesis of Thermoplastic Resin E Having Hyperbranched Structure> In Synthesis Example 1, the amount of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane was changed from 1.94 g to 1.24 g, and the amount of the amine-terminated silicone oil at both ends (“KF-8010” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 0.946 g to 2.88 g. Except for the above matters, a thermoplastic resin E having a hyperbranched structure was obtained in the same manner as in Synthesis Example 1. The weight-average molecular weight of the thermoplastic resin E was measured to be 20,200. Also, the glass transition temperature of the thermoplastic resin E was measured to be 78 °C.

[0175] <Synthesis Example 6: Synthesis of Thermoplastic Resin F Having Hyperbranched Structure> In Synthesis Example 1, 3-aminopropyltriethoxysilane 0.553 g of “KBE-903” (manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to 0.638 g of N-phenyl-3-aminopropyltrimethoxysilane (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.). Except for the above matters, a thermoplastic resin F having a hyperbranched structure was obtained in the same manner as in Synthesis Example 1. The weight-average molecular weight of the thermoplastic resin F was measured to be 24,500. Also, the glass transition temperature of the thermoplastic resin F was measured to be 76 °C.

[0176] <Synthesis Example 7: Synthesis of Thermoplastic Resin G Having Hyperbranched Structure> In Synthesis Example 1, 3-aminopropyltriethoxysilane 0.553 g of “KBE-903” (manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to 0.451 g of 3-mercaptopropylmethyldimethoxysilane (“KBM-802” manufactured by Shin-Etsu Chemical Co., Ltd.). Except for the above matters, a thermoplastic resin G having a hyperbranched structure was obtained in the same manner as in Synthesis Example 1. When the weight average molecular weight of the thermoplastic resin G was measured, it was 18,900. Also, when the glass transition temperature of the thermoplastic resin G was measured, it was 76°C.

[0177] <Synthesis Example 8: Synthesis of Thermoplastic Resin H Having a Hyperbranched Structure> 1.94 g of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and 0.36 g of 1-naphthol were added to tetrahydrofuran in a reaction vessel and dissolved. Then, 0.922 g of cyanuric chloride and 0.946 g of an amine-terminated silicone oil (“KF-8010” manufactured by Shin-Etsu Chemical Co., Ltd.) were added and reacted at 50°C overnight. Thereafter, ethyl acetate was added for extraction, and insoluble matters were removed by filtration. Next, the filtrate was washed with water and then dehydrated with anhydrous magnesium sulfate, and the solvent was concentrated and distilled off. The residue was crystallized from methanol to obtain a thermoplastic resin H having a hyperbranched structure. When the weight average molecular weight of the thermoplastic resin H was measured, it was 14,500. Also, when the glass transition temperature of the thermoplastic resin H was measured, it was 94°C.

[0178] <Synthesis Example 9: Synthesis of Thermoplastic Resin I Having a Hyperbranched Structure> In Synthesis Example 1, 0.946 g of an amine-terminated silicone oil (“KF-8010” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to 1.47 g of an amine-terminated silicone oil (“X-22-9409” manufactured by Shin-Etsu Chemical Co., Ltd.). Except for the above matters, a thermoplastic resin I having a hyperbranched structure was obtained in the same manner as in Synthesis Example 1. When the weight average molecular weight of the thermoplastic resin I was measured, it was 19,200. Also, when the glass transition temperature of the thermoplastic resin I was measured, it was 78°C.

[0179] <Synthesis Example 10: Synthesis of Thermoplastic Resin J with Hyperbranched Structure> In Synthesis Example 8, 0.946 g of amine-terminated silicone oil (“KF-8010” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to 3.24 g of phenol-terminated silicone oil (“KF-2201” manufactured by Shin-Etsu Chemical Co., Ltd.). Except for the above matters, in the same manner as in Synthesis Example 8, thermoplastic resin J having a hyperbranched structure was obtained. When the weight average molecular weight of thermoplastic resin J was measured, it was 28,400. Also, when the glass transition temperature of thermoplastic resin J was measured, it was 95°C.

[0180] <Synthesis Example 11: Synthesis of Thermoplastic Resin K with Hyperbranched Structure> In Synthesis Example 6, 0.946 g of amine-terminated silicone oil (“KF-8010” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to 1.03 g of carbinol-terminated silicone oil (“KF-6000” manufactured by Shin-Etsu Chemical Co., Ltd.). Except for the above matters, in the same manner as in Synthesis Example 6, thermoplastic resin K having a hyperbranched structure was obtained. When the weight average molecular weight of thermoplastic resin K was measured, it was 9,800. Also, when the glass transition temperature of thermoplastic resin K was measured, it was 81°C.

[0181] [Example 1. Preparation of Resin Composition 1] 5 parts of liquid epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., "ZX1059", a 1:1 mixture (by mass) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq), 15 parts of biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., "NC3000H", epoxy equivalent about 290), and 2 parts of thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 were dissolved by heating with stirring in 20 parts of toluene and 20 parts of MEK. After cooling the obtained solution to room temperature, 42 parts of an active ester-based curing agent (manufactured by DIC Corporation, "HP-B-8151-62T", active group equivalent 238, toluene solution with a solid content of 62%), 4 parts of a phenolic curing agent containing a triazine skeleton (manufactured by DIC Corporation, "LA-3018-50P", hydroxyl group equivalent about 151 g / eq, 2-methoxypropanol solution with a solid content of 50%), 10 parts of a phenoxy resin (manufactured by Mitsubishi Chemical Corporation, "YX7553BH30", 1:1 solution of MEK and cyclohexanone with a non-volatile content of 30% by mass), 3 parts of a curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., "1B2PZ", MEK solution with a solid content of 10% by mass), and 150 parts of an inorganic filler (spherical silica (manufactured by Admatechs Co., Ltd., "SO-C2", average particle size 0.5 μm) surface-treated with an amine-based silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573")) were mixed and uniformly dispersed with a high-speed rotary mixer to obtain Resin Composition 1.

[0182] [Example 2. Preparation of Resin Composition 2] In Example 1, 6 parts of a carbodiimide-based curing agent (manufactured by Nisshinbo Chemical Inc., "V-03", active group equivalent about 216 g / eq, toluene solution with a solid content of 50%) was used. Resin Composition 2 was obtained in the same manner as in Example 1 except for the above matters.

[0183] [Example 3. Preparation of Resin Composition 3] In Example 1, 6 parts of a thermosetting resin having a phenylene ether structure (manufactured by SABIC Innovative Plastics, "SA-9000", toluene solution with a solid content of 50%) was used. Resin Composition 3 was obtained in the same manner as in Example 1 except for the above matters.

[0184] [Example 4. Preparation of Resin Composition 4] In Example 1, 3 parts of a maleimide compound ("BMI689" manufactured by Designer Molecules, maleimide group equivalent 345) were used. Except for the above matters, Resin Composition 4 was obtained in the same manner as in Example 1.

[0185] [Example 5. Preparation of Resin Composition 5] In Example 2, 42 parts of an active ester-based curing agent ("HP-B-8151-62T" manufactured by DIC, active group equivalent 238, toluene solution with a solid content of 62%) were changed to 40 parts of an active ester-based curing agent ("PC1300-02-65MA" manufactured by Air Water, active group equivalent 199 g / eq, methyl amyl ketone solution with a solid content of 65 mass%). Except for the above matters, Resin Composition 5 was obtained in the same manner as in Example 2.

[0186] [Example 6. Preparation of Resin Composition 6] In Example 1, the amount of the thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 was changed from 2 parts to 12 parts. Except for the above matters, Resin Composition 6 was obtained in the same manner as in Example 1.

[0187] [Example 7. Preparation of Resin Composition 7] In Example 2, 2 parts of the thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 were changed to 2 parts of the thermoplastic resin B having a hyperbranched structure synthesized in Synthesis Example 2. Except for the above matters, Resin Composition 7 was obtained in the same manner as in Example 2.

[0188] [Example 8. Preparation of Resin Composition 8] In Example 2, 2 parts of the thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 were changed to 2 parts of the thermoplastic resin C having a hyperbranched structure synthesized in Synthesis Example 3. Except for the above matters, Resin Composition 8 was obtained in the same manner as in Example 2.

[0189] [Example 9. Preparation of Resin Composition 9] In Example 2, 2 parts of the thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 were changed to 2 parts of the thermoplastic resin D having a hyperbranched structure synthesized in Synthesis Example 4. A resin composition 9 was obtained in the same manner as in Example 2, except for the above matters.

[0190] [Example 10. Preparation of Resin Composition 10] In Example 2, 2 parts of the thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 were changed to 2 parts of the thermoplastic resin E having a hyperbranched structure synthesized in Synthesis Example 5. A resin composition 10 was obtained in the same manner as in Example 2, except for the above matters.

[0191] [Example 11. Preparation of Resin Composition 11] In Example 2, 2 parts of the thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 were changed to 2 parts of the thermoplastic resin F having a hyperbranched structure synthesized in Synthesis Example 6. A resin composition 11 was obtained in the same manner as in Example 2, except for the above matters.

[0192] [Example 12. Preparation of Resin Composition 12] In Example 2, 2 parts of the thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 were changed to 2 parts of the thermoplastic resin G having a hyperbranched structure synthesized in Synthesis Example 7. A resin composition 12 was obtained in the same manner as in Example 2, except for the above matters.

[0193] [Example 13. Preparation of Resin Composition 13] In Example 2, 2 parts of the thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 were changed to 2 parts of the thermoplastic resin H having a hyperbranched structure synthesized in Synthesis Example 8. A resin composition 13 was obtained in the same manner as in Example 2, except for the above matters.

[0194] [Example 14. Preparation of Resin Composition 14] In Example 2, 2 parts of the thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 were changed to 2 parts of the thermoplastic resin I having a hyperbranched structure synthesized in Synthesis Example 9. Except for the above matters, the resin composition 14 was obtained in the same manner as in Example 2.

[0195] [Example 15. Preparation of Resin Composition 15] In Example 2, 2 parts of the thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 were changed to 2 parts of the thermoplastic resin J having a hyperbranched structure synthesized in Synthesis Example 10. Except for the above matters, the resin composition 15 was obtained in the same manner as in Example 2.

[0196] [Example 16. Preparation of Resin Composition 16] In Example 2, 2 parts of the thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 were changed to 2 parts of the thermoplastic resin K having a hyperbranched structure synthesized in Synthesis Example 11. Except for the above matters, the resin composition 16 was obtained in the same manner as in Example 2.

[0197] [Comparative Example 1. Preparation of Resin Composition 17] In Example 1, 2 parts of the thermoplastic resin A having a hyperbranched structure synthesized in Synthesis Example 1 were not used. Except for the above matters, the resin composition 17 was obtained in the same manner as in Example 1.

[0198] [Production of Resin Sheet] As a support, a polyethylene terephthalate film (Toray Industries, Inc.'s "Lumirror R80", thickness 38 μm, softening point 130°C) subjected to a release treatment with an alkyd resin-based release agent ("AL-5" manufactured by Lintec Corporation) was prepared.

[0199] Resin compositions 1 to 17 were each uniformly applied onto a support using a die coater such that the thickness of the resin composition layer after drying was 30 μm, and dried at 70°C to 95°C for 3 minutes to form a resin composition layer on the support. Subsequently, the rough surface of a polypropylene film (Alphan MA-411, thickness 15 μm, manufactured by Oji Fibrex Corporation) was laminated as a protective film onto the surface of the resin composition layer that was not bonded to the support. Thereby, a resin sheet A having a support, a resin composition layer, and a protective film in this order was obtained.

[0200] [Measurement of adhesion (peel strength) with the plating conductor layer] (1) Preparation of inner layer substrate Both surfaces of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, R1515A manufactured by Panasonic Corporation) on which an inner layer circuit was formed were etched with a micro-etching agent (CZ8101 manufactured by Meck) by 1 μm to perform roughening treatment of the copper surface.

[0201] (2) Lamination of resin sheet The protective film was peeled off from resin sheet A to expose the resin composition layer. Using a batch-type vacuum pressure laminator (CVP700, a two-stage build-up laminator manufactured by Nippon Materials Co., Ltd.), it was laminated onto both surfaces of the inner layer substrate such that the resin composition layer was in contact with the inner layer substrate. Lamination was carried out by reducing the pressure for 30 seconds to adjust the atmospheric pressure to 13 hPa or less, and then pressure-bonding at 120°C and a pressure of 0.74 MPa for 30 seconds. Subsequently, a hot press was performed at 100°C and a pressure of 0.5 MPa for 60 seconds.

[0202] (3) Thermal curing of resin composition layer Thereafter, the inner layer substrate laminated with the resin sheet was placed in an oven at 130°C and heated for 30 minutes, and then transferred to an oven at 180°C and heated for 30 minutes to thermally cure the resin composition layer and form an insulating layer. Thereafter, the support was peeled off to obtain a cured substrate B having an insulating layer, an inner layer substrate, and an insulating layer in this order.

[0203] (4) Roughening treatment A desmear treatment as a roughening treatment was performed on the cured substrate B. As the desmear treatment, the following wet desmear treatment was carried out.

[0204] (Wet desmear treatment) The cured substrate B was immersed in a swelling solution (an aqueous solution of "Swelling Dip Securigant P" manufactured by Atotech Japan Co., Ltd., diethylene glycol monobutyl ether, and sodium hydroxide) at 60 °C for 5 minutes, and then immersed in an oxidizing agent solution (an aqueous solution of "Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd., with a potassium permanganate concentration of approximately 6% and a sodium hydroxide concentration of approximately 4%) at 80 °C for 20 minutes. Then, after immersion in a neutralizing solution (an aqueous solution of "Reduction Solution Securigant P" manufactured by Atotech Japan Co., Ltd., sulfuric acid) at 40 °C for 5 minutes, it was dried at 80 °C for 15 minutes.

[0205] (5) Formation of the conductor layer According to the semi-additive method, a conductor layer was formed on the roughened surface of the insulating layer. That is, the cured substrate B after the roughening treatment was immersed in an electroless plating solution containing PdCl2 at 40 °C for 5 minutes, and then immersed in an electroless copper plating solution at 25 °C for 20 minutes. Then, after annealing treatment by heating at 150 °C for 30 minutes, an etching resist was formed, and patterning was performed by etching. Thereafter, copper sulfate electrolytic plating was carried out to form a conductor layer with a thickness of 30 μm, and annealing treatment was performed at 200 °C for 60 minutes. The obtained substrate is referred to as "evaluation substrate C".

[0206] (6) Measurement of peel strength The measurement of the peel strength between the insulating layer and the plated conductor layer was carried out in accordance with Japanese Industrial Standard (JIS C6481). Specifically, a cut was made in a 10 mm wide and 100 mm long portion of the conductor layer of the evaluation substrate C, one end of this was peeled off and grasped with a gripping tool, and the load (kgf / cm) when peeling 35 mm vertically at a speed of 50 mm / min at room temperature was measured to obtain the peel strength. A tensile testing machine ("AC-50C-SL" manufactured by TSE) was used for the measurement.

[0207] [Measurement of dielectric loss tangent] The protective film was peeled off from the resin sheet A and heated at 200 °C for 90 minutes to thermoset the resin composition layer, and then the support was peeled off. The obtained cured product was designated as "Cured Product D for Evaluation". The Cured Product D for Evaluation was cut into test pieces with a width of 2 mm and a length of 80 mm. For the test pieces, the dielectric tangent was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 °C by the cavity resonance perturbation method using "HP8362B" manufactured by Agilent Technologies. Measurements were performed on three test pieces, and the average value was calculated.

[0208] [Measurement and Evaluation of Crack Resistance] (1) Lamination of Resin Sheet A A resin sheet A with the protective film peeled off so that the resin composition layer was in contact with the inner layer substrate was laminated on both sides of an inner layer substrate (Hitachi Chemical Co., Ltd.'s "MCL-E700G", conductor layer thickness 35 μm, total thickness 0.4 mm, residual copper ratio 40%) having circuit conductors (copper) formed with a wiring pattern of L / S = 8 μm / 8 μm on both sides. Such lamination was carried out using a vacuum pressure laminator (Meiki Seisakusho Co., Ltd.'s "MVLP-500"). After vacuum suction at 120 °C for 30 seconds, it was laminated by pressing for 30 seconds from above the support through a heat-resistant rubber under the conditions of a temperature of 120 °C and a pressure of 0.7 MPa. Next, under atmospheric pressure, pressing was performed for 60 seconds using a SUS mirror plate under the conditions of a temperature of 120 °C and a pressure of 0.55 MPa.

[0209] (2) Thermosetting of Resin Composition Layer Thereafter, the inner layer substrate laminated with the resin sheet was put into an oven at 130 °C and heated for 30 minutes, and then transferred to an oven at 180 °C and heated for 30 minutes to thermoset the resin composition layer and form an insulating layer. Thereafter, the support was peeled off to obtain a cured substrate E having an insulating layer, an inner layer substrate, and an insulating layer in this order.

[0210] (3) Roughening Treatment The cured substrate E was subjected to a desmear treatment as a roughening treatment. The desmear treatment was carried out in the same manner as the (wet desmear treatment) described in the above [Adhesion to Plated Conductor Layer] section to obtain a sample.

[0211] (4) Evaluation of crack resistance Among the surfaces of the insulating layers after desmear treatment of the samples, the surface of the insulating layer directly above the wiring pattern (L / S = 8 μm / 8 μm) of the inner layer substrate was observed. For 100 samples, it was confirmed whether cracks occurred on the surface of the insulating layer along the pattern shape of the inner layer substrate, and the ratio of the samples without cracks was determined. This ratio was calculated as the "yield" and evaluated according to the following criteria. 〇: Yield is 50% or more ×: Yield is less than 50%

[0212]

Table 1

[0213] In Examples 1 to 16, even when the components (D) to (G) are not contained, although there are differences to some extent, it has been confirmed that the results are the same as those of the above examples.

Claims

1. (A) an epoxy resin, (B) a curing agent, and (C) a thermoplastic resin having a hyperbranched structure, and includes (C) component has a multi-branched structure in which a structure derived from a trifunctional or higher-functional compound and a structure derived from a bifunctional compound are bonded, and the terminal has a structure derived from a monofunctional compound, (C) the trifunctional or higher-functional compound is a compound selected from the group consisting of cyanuric chloride, 2,4,6-trichloropyrimidine, and 2,4,6-trichloropyridine (C) the bifunctional compound includes a compound containing a siloxane structure and a compound not containing a siloxane structure, (C) the bifunctional compound containing a siloxane structure is a polysiloxane compound having two hydroxyl groups or -RNH2 groups in the molecule (R is a methylene group or a phenylene group), (C) the bifunctional compound not containing a siloxane structure is a compound containing a structure selected from a phenylene skeleton and a phenylene ether skeleton (C) the monofunctional compound is a resin composition which does not have an ethylenically unsaturated bond at the molecular terminal and has an alkoxysilyl group or an aryloxy group.

2. The resin composition according to claim 1, wherein the weight average molecular weight of component (C) is 1000 or more and 40000 or less.

3. The resin composition according to claim 1, wherein component (C) is a resin having a glass transition temperature of 50°C or more and 150°C or less.

4. The resin composition according to claim 1, further comprising (D) an inorganic filler.

5. The resin composition according to claim 4, wherein the content of component (D) is 50% by mass or more when the resin component in the resin composition is 100% by mass.

6. The resin composition according to claim 1, wherein component (B) includes an active ester-based curing agent.

7. A resin sheet including a support and a resin composition layer provided on the support and containing the resin composition according to any one of claims 1 to 6.

8. A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 6.

9. A semiconductor device including the printed wiring board according to claim 8.

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