TWI781918B - Resin composition, prepreg, metal foil-clad laminate, resin sheet, printed wiring board, and semiconductor device - Google Patents

Abstract

The present invention provides a resin composition having excellent permittivity, dielectric loss tangent, fine wiring embeddability, heat resistance and developability, and also having physical properties suitable for use as a protective film or interlayer insulating layer in a printed wiring board. The present invention also provides a prepreg, metal foil-clad laminate, resin sheet, printed wiring board and semiconductor device that use this resin composition. The resin composition of the present invention contains fluororesin particles (A) with silica particles adhered to the particle surfaces, and a resin component (B).

Description

Resin composition, prepreg, metal foil-clad laminate, resin sheet, printed circuit board, and semiconductor device

The present invention relates to a resin composition, a prepreg using the composition, a metal foil-clad laminate, a resin sheet, a printed circuit board, and a semiconductor device.

In recent years, the high integration and miniaturization of semiconductors widely used in electronic equipment, communication equipment, personal computers, etc. have been accelerated, and the high-speed and large-capacity data communications used in information communications have also progressed. For printed circuit boards, low dielectric constant (low Dk) and low dielectric tangent (low Df) are required in order to shorten signal transmission delay and reduce transmission loss. In order to meet these demands, the use of resin compositions having excellent electrical characteristics (low dielectric constant and low dielectric tangent) has been studied.

In addition, due to miniaturization and high density of printed circuit boards, build-up layers used in multilayer printed circuit boards are multi-layered, and miniaturization and high density of wiring are required. Therefore, the resin composition used in the build-up layer is required to have high fluidity during molding in order to embed fine wiring, and to have high heat resistance after embedding fine wiring. In such a resin composition, the use of a fluororesin filler has been studied in order to improve electrical characteristics. For example, Patent Document 1 discloses that a resin composition having excellent electrical characteristics is achieved by using a fluororesin filler and a polyphenylene ether resin together. In addition, Patent Document 2 discloses that by using a fluororesin filler and a norbornene-based resin together, a cured product has excellent electrical characteristics and adhesiveness, and a resin composition having excellent wiring embedding properties can be obtained.

[Prior Art Documents] [Patent Documents] [Patent Document 1] JP-A-2006-516297 [Patent Document 2] JP-A-2007-177073

[Problems to be Solved by the Invention] However, the inventors of the present invention have found that cured products using conventional fluororesin fillers have various problems. For example, the heat resistance of the cured product obtained in Patent Document 1 is insufficient. In addition, in Patent Document 2, the moisture absorption heat resistance after wiring embedding is insufficient.

The present invention is made in view of the above problems, and provides a resin composition excellent in dielectric constant, dielectric tangent, micro-wiring embedding property, heat resistance, and developability when used in a multilayer printed circuit board, and a pre-processed product using the composition. Immersion bodies, metal foil-clad laminates, resin sheets, printed circuit boards, and semiconductor devices. [How to solve the problem]

The present inventors found that the above-mentioned problems can be solved by using a resin composition containing silica-coated fluororesin particles (A) and a resin component (B), and completed the present invention.

That is, the present invention includes the following. [1] A resin composition comprising silica-coated fluororesin particles (A) and a resin component (B). [2] The resin composition according to [1], wherein the volume average particle diameter of the primary particles of the silica-coated fluororesin particles (A) is 5 μm or less. [3] The resin composition according to [1] or [2], wherein the content of the silica-coated fluororesin particles (A) in the resin composition is relative to the resin solid content in the resin composition 100 parts by mass is 3 to 400 parts by mass. [4] The resin composition according to any one of [1] to [3], wherein the resin component (B) contains a compound selected from maleimide compounds, cyanate compounds, epoxy resins, phenol Any one or more of the group consisting of resins, oxetane resins, benzodiazepine compounds, and compounds with ethylenically unsaturated groups.

[5] The resin composition according to any one of [1] to [4], further comprising a filler (C) other than the silica-coated fluororesin particles (A). [6] The resin composition according to any one of [1] to [5], which further contains a flame retardant (D). [7] The resin composition according to any one of [1] to [6], further comprising a photocuring initiator (E). [8] The resin composition according to [4], wherein the compound having an ethylenically unsaturated group includes an oligomer selected from bifunctional phenylene ether oligomers having vinyl groups and α-methylstyrene At least one of the group consisting of polymers. [9] The resin composition as in [4], wherein the compound having an ethylenically unsaturated group is selected from acid-modified bisphenol F-type epoxy (meth)acrylate, the following general formula (1) At least one of the group consisting of the indicated compound and diperythritol hexa(meth)acrylate;

【Chemical 1】

In the formula (1), a plurality of R _1s independently represent a hydrogen atom or a methyl group, and a plurality of R ₂ independently represent a hydrogen atom or a methyl group, and a plurality of R ₃ independently represent a hydrogen atom or a methyl group represented by the following formula (2) A substituent, a substituent represented by the following formula (3) or a hydroxyl group;

【Chemical 2】

【Chemical 3】

In formula (3), R ₄ represents a hydrogen atom or a methyl group.

[10] The resin composition according to [9], wherein the compound having an ethylenically unsaturated group includes at least a compound represented by the general formula (1). [11] A prepreg comprising: a substrate, and the resin composition according to any one of [1] to [10] impregnated or coated on the substrate. [12] A metal foil-clad laminate comprising: at least one laminated prepreg according to [11], and metal foils arranged on one or both sides of the prepreg.

[13] A resin sheet comprising: a support, and the resin composition according to any one of [1] to [10] arranged on the surface of the support. [14] A printed circuit board having the resin composition according to any one of [1] to [10]. [15] A semiconductor device comprising the resin composition according to any one of [1] to [10]. [Effect of Invention]

According to the present invention, it is possible to provide a resin composition which is excellent in dielectric constant, dielectric tangent, fine wiring embedding property, heat resistance, and developability, and has physical properties suitable for a protective film of a printed circuit board and an interlayer insulating layer. Using this composition Prepregs, metal foil-clad laminates, resin sheets, printed circuit boards, and semiconductor devices.

Hereinafter, this embodiment (hereinafter referred to as "the present embodiment") will be described in detail. The present embodiment below is an example for explaining the present invention, and does not mean that the present invention is limited to the following content. The present invention can be appropriately modified and implemented within the scope of the gist.

Also, in this specification, "(meth)acryl" means both "acryl" and its corresponding "methacryl", "(meth)acrylate" means "acrylate " and its corresponding "methacrylate", "(meth)acrylic acid" refers to both "acrylic acid" and its corresponding "methacrylic acid". Also, in this embodiment, "resin solid content" or "resin solid content in the resin composition" refers to components other than the solvent and filler in the resin composition unless otherwise specified, and "resin solid content 100 "Parts by mass" refers to 100 parts by mass of the total of components other than the solvent and the filler in the resin composition.

The resin composition of this embodiment is characterized by containing silica-coated fluororesin particles (A) and a resin component (B). Each component is explained below.

<Silica-coated fluororesin particles (A)> The silica-coated fluororesin particles (A) used in this embodiment are fluororesin particles with silica attached to the surface, and have fluororesin particles and Silicon dioxide particles attached to the surface of the fluororesin. The method of attaching the silica particles to the surface of the fluororesin particles is not particularly limited, and it can be carried out by simply mixing or applying vibration after mixing. Attaching silica particles to the surface of fluororesin particles can be carried out in a dry state. The mixing ratio of fluororesin particles and silica particles is not particularly limited. It is considered that as long as the silica particles are present on the surface of the fluororesin particles even in a small amount, the effect of improving the fluidity of the silica particles can be exhibited, and the wiring embedding performance of the resin composition of this embodiment can be improved. And the moisture absorption and heat resistance after the wiring is buried is good.

The fluororesin particles used in the silica-coated fluororesin particles (A) in this embodiment are not particularly limited, and examples thereof include polytetrafluoroethylene (PTFE), tetrafluoroethylene/perfluoroalkoxyethylene copolymer (PF A), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-chlorotrifluoroethylene copolymer (PCTFE), ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF )Wait. Among them, PTFE is preferable from the viewpoint of excellent electrical characteristics. These can be used individually by 1 type or in mixture of 2 or more types suitably.

The fluororesin particles are considered to have a good embedding property of fine wiring, and the volume average particle diameter of the primary particles is preferably 5 μm or less, more preferably 4 μm or less, and more preferably 3 μm or less. Also, from the viewpoint of good electrical characteristics, the volume average particle diameter of the primary particles is preferably 0.005 μm or more, more preferably 0.01 μm or more, and more preferably 0.02 μm or more. In addition, in this specification, "volume average particle diameter" means the arithmetic mean diameter of the particle diameter distribution based on volume. The volume average particle diameter can be measured by, for example, a wet laser diffraction/scattering method.

The content of the silica particles in the silica-coated fluororesin particles (A) is not particularly limited, but it is preferably at least 0.001% by mass relative to the mass of the fluororesin particles, preferably 0.005% by mass, in view of improving fluidity. % or more is more preferable, and more preferably 0.01% by mass or more. Also, from the viewpoint of expressing the electrical characteristics of the fluororesin particles, it is preferably at most 10% by mass, more preferably at most 5% by mass, and more preferably at most 2% by mass.

The silica particles are not particularly limited as long as the volume average particle diameter of the primary particles is smaller than the volume average particle diameter of the aforementioned fluororesin particles. Among them, from the viewpoint of expressing the electrical characteristics of the fluororesin, the volume average particle diameter of the primary particles is preferably 200 nm or less, more preferably 100 nm or less, more preferably 70 nm or less, and more preferably 50 nm or less. Also, from the viewpoint of improving fluidity, the volume average particle diameter of the primary particles is preferably 0.3 nm or more, more preferably 0.5 nm or more, and more preferably 1 nm or more.

Silica-coated fluororesin particles (A), in view of improving the embedding performance of fine wiring, the volume average particle diameter of the primary particles is preferably 5 μm or less, more preferably 4 μm or less, and more preferably 3 μm or less. Below 2 μm, it is more ideal in consideration of the embedding performance of fine wiring, better dielectric constant and dielectric tangent. Also, from the viewpoint of making the electrical characteristics good, the volume average particle diameter of the primary particles is preferably 0.005 μm or more, more preferably 0.01 μm or more, and more preferably 0.02 μm or more.

Such silica-coated fluororesin particles can also be commercially available, for example, 0.5 μm PTFE-YA (trade name), PTFE-YA4 (3.0 μm, trade name) (manufactured by Admatechs Co., Ltd.).

The content of the silicon dioxide-coated fluororesin particles (A) in the resin composition of this embodiment is not particularly limited, but considering the viewpoint of making the electrical properties of the resin composition good, the content of the resin solid content in the resin composition is 100%. Parts by mass are preferably 3 parts by mass or more, more preferably 5 parts by mass or more, more preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and more preferably 30 parts by mass or more. Also, in consideration of making the heat resistance good, it is preferably 400 parts by mass or less, more preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and 100 parts by mass relative to 100 parts by mass of resin solid content in the resin composition. Less than one serving is more ideal.

<Resin component (B)> The resin component (B) used in this embodiment can be used according to the resin composition in addition to the electrical characteristics obtained by using the fluororesin particles (A) coated with silica. Various types are used for properties such as flame retardancy, heat resistance, and thermal expansion characteristics of hardened hardened products required in the field. For example, when adhesion is required, epoxy resins are used; when heat resistance is required, maleimide compounds, cyanate compounds, and benzodiazepine compounds are used; when thermosetting or photocuring properties are required, examples are As compounds having ethylenically unsaturated groups, phenol resins, oxetane resins, and the like can also be used.

Moreover, these can be used 1 type or in mixture of 2 or more types suitably. The details of these resin components (B) are described below.

<Maleimide compound> The maleimide compound is not particularly limited as long as it has one or more maleimide groups in the molecule. Its specific examples, for example: N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidephenyl)methane, 2,2-bis{4-( 4-maleimidephenoxy)-phenyl}propane, 4,4-diphenylmethanebismaleimide, bis(3,5-dimethyl-4-maleimidebenzene base) methane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, bis(3,5-diethyl-4-maleimidephenyl)methane, Phenylmethane maleimide, o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, o-phenylene biscitraconyl Imine, m-Phenylbiscitraconimide, p-Phenylbiscitraconimide, 2,2-bis(4-(4-maleimidephenoxy)-phenyl)propane , 3,3-Dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide , 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4-diphenylether bismaleimide, 4,4-diphenyldiphenyl bismaleimide Laimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, 4,4-diphenyl Methanebiscitraconimide, 2,2-bis[4-(4-citraconimidephenoxy)phenyl]propane, bis(3,5-dimethyl-4-citraconimide Phenyl)methane, bis(3-ethyl-5-methyl-4-citraconimidephenyl)methane, bis(3,5-diethyl-4-citraconimidephenyl)methane , polyphenylmethane maleimide, novolak type maleimide compound, biphenyl aralkyl type maleimide compound, maleimide compound represented by the following formula (4), the following formula The maleimide compound represented by (5), and the prepolymer of the maleimide compound, or the prepolymer of the maleimide compound and the amine compound, etc.

【Chemical 4】

In formula (4), a plurality of R ₅ each independently represent a hydrogen atom or a methyl group. n ₁ represents an integer of 1 or more, preferably an integer representing 1-10, more preferably an integer representing 1-5.

【Chemical 5】

In formula (5), a plurality of R ₆ each independently represent a hydrogen atom or a methyl group. n ₂ represents an integer of 1 or more, preferably an integer representing 1-5. These maleimide compounds can be used individually by 1 type or in mixture of 2 or more types suitably. Among them, in consideration of excellent heat resistance, the maleimide compound represented by the aforementioned formula (4) and the compound represented by the aforementioned formula (5) are more preferable, and the maleimide compound represented by the aforementioned formula (4) is more preferable. . The maleimide compound represented by said formula (4) can use a commercial item, for example: BMI-2300 (made by Daiwa Kasei Kogyo Co., Ltd.). The maleimide compound represented by said formula (5) can also use a commercial item, for example: MIR-3000 (manufactured by Nippon Kayaku Co., Ltd.).

In the resin composition of this embodiment, the content of the maleimide compound is not particularly limited, and is preferably 0.01 to 50 parts by mass, more preferably 0.02 parts by mass, relative to 100 parts by mass of the resin solid content in the resin composition. Parts to 45 parts by mass, more preferably 0.03 parts to 20 parts by mass, more preferably 0.1 parts to 10 parts by mass, and more preferably 1 part to 7 parts by mass. When the content of the maleimide compound is within the above range, the heat resistance of the cured product tends to be further improved.

<Cyanate Compound> The cyanate compound is not particularly limited as long as it is a resin having an aromatic moiety substituted with at least one cyanooxy group (cyanate group) in the molecule.

For example, those represented by general formula (6).

【Chemical 6】

Here, in the formula, Ar ₁ represents a benzene ring, a naphthalene ring, or two benzene rings bonded by a single bond. When there are a plurality of them, they may be the same as or different from each other. Ra each independently represents a hydrogen atom, an alkyl group with 1 to 6 carbons, an aryl group with 6 to 12 carbons, an alkoxy group with 1 to 4 carbons, an alkyl group with 1 to 6 carbons, and an alkyl group with 6 to 12 carbons The base obtained by bonding the aryl group. The aromatic ring in Ra may also have substituents, and the substituents in Ar ₁ and Ra can choose any position. p represents the number of cyanooxy groups bonded to Ar ₁ , each independently being an integer of 1 to 3. q represents the number of Ra bonded to Ar ₁ , and when Ar ₁ is a benzene ring, it is 4-p, when it is a naphthalene ring, it is 6-p, and when Ar 1 is two benzene rings bonded by a single bond, it is 8-p. t represents the average repetition number, which is an integer from 0 to 50, and the cyanate compound can also be a mixture of compounds with different t series. When there are multiple Xs, they are each independently a single bond, a divalent organic group with 1 to 50 carbons (hydrogen atoms can also be replaced by heteroatoms), a divalent organic group with 1 to 10 nitrogens (such as -NRN-( Here R stands for organic group)), carbonyl (-CO-), carboxyl (-C(=O)O-), carbon dioxide carbonyl (-OC(=O)O-), sulfonyl (-SO ₂ - ), divalent sulfur atom or divalent oxygen atom.

The alkyl group of Ra in the general formula (6) may have any of a linear or branched chain structure and a cyclic structure (for example, cycloalkyl group, etc.). Also, the hydrogen atom in the alkyl group in the general formula (6) and the aryl group in Ra can also be replaced by a halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, or a cyano group, etc. . Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2,2-dimethyl propyl, cyclopentyl, hexyl, cyclohexyl, and trifluoromethyl, etc. Specific examples of aryl groups include phenyl, tolyl, mesityl, naphthyl, phenoxyphenyl, ethylphenyl, o-, m-, or p-fluorophenyl, dichlorophenyl, dicyanobenzene Base, trifluorophenyl, methoxyphenyl, and o, m or p-tolyl, etc. Alkoxy, for example: methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy, etc.

Specific examples of divalent organic groups having 1 to 50 carbon atoms in X of the general formula (6) include alkylene groups such as methylene, ethylene, trimethylene, and propylene, cyclopentylene, and cyclopentylene. Hexylene, trimethylcyclohexylene and other cycloalkylenes, biphenylmethylene, dimethylmethylene-phenylene-dimethylmethylene, fenneldiyl, and phthalidediyl (phth alidediyl) and other divalent organic groups with aromatic rings. The hydrogen atom in the divalent organic group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, a cyano group, or the like.

Examples of divalent organic groups with 1 to 10 nitrogens in X in the general formula (6) include groups represented by -N-R-N- (R is an organic group), imine groups, polyimide groups, and the like.

In addition, examples of the organic group of X in the general formula (6) include structures represented by the following general formula (7) or the following general formula (8).

【Chemical 7】

Here, in the formula, Ar ₂ represents a benzene tetrayl group, a naphthalene tetrayl group or a biphenyltetrayl group, and when u is 2 or more, they may be the same or different from each other. Rb, Rc, Rf, and Rg each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbons, an aryl group having 6 to 12 carbons, a trifluoromethyl group, or an aryl group having at least one phenolic hydroxyl group. Rd and Re are each independently selected from any one of a hydrogen atom, an alkyl group having 1 to 6 carbons, an aryl group having 6 to 12 carbons, an alkoxy group having 1 to 4 carbons, or a hydroxyl group. u represents an integer from 0 to 5.

【chemical 8】

Here, in the formula, Ar ₃ represents a benzene tetrayl group, a naphthalene tetrayl group or a biphenyl tetrayl group, and when v is 2 or more, they may be the same as or different from each other. Ri and Rj each independently represent a hydrogen atom, an alkyl group with 1 to 6 carbons, an aryl group with 6 to 12 carbons, benzyl, an alkoxy group with 1 to 4 carbons, a hydroxyl group, a trifluoromethyl group, or An aryl group substituted with at least one cyanooxy group. v represents an integer of 0 to 5, but may also be a mixture of compounds in which v is different.

In addition, X in General formula (6) can mention the divalent group represented by the following formula.

【Chemical 9】

Here, in the formula, z represents an integer of 4-7. Rk each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbons.

Specific examples of Ar ₂ in the general formula (7) and Ar ₃ in the general formula (8) can include two carbon atoms shown in the general formula (7), or two oxygen atoms shown in the general formula (8). The benzene tetrayl group at the 1,4 or 1,3 positions, the above 2 carbon atoms or 2 oxygen atoms are bonded to the 4,4', 2,4', 2,2', 2,3' 2, 6, 1, 5, 1, 6, 1 ,8-, 1,3-, 1,4-, or 2,7-position naphthalene tetrayl.

Rb, Rc, Rd, Re, Rf and Rg in general formula (7), and the alkyl and aryl groups in Ri and Rj in general formula (8) have the same meanings as those in general formula (6).

Specific examples of the cyanoxy-substituted aromatic compound represented by the above-mentioned general formula (6) may include cyanoxybenzene, 1-cyanoxy-2-, 1-cyanoxy-3-, or 1-cyanoxy- 4-Methylbenzene, 1-cyanooxy-2-, 1-cyanooxy-3-, or 1-cyanooxy-4-methoxybenzene, 1-cyanooxy-2,3-, 1 -cyanooxy-2,4-, 1-cyanooxy-2,5-, 1-cyanooxy-2,6-, 1-cyanooxy-3,4- or 1-cyanooxy-3 ,5-Dimethylbenzene, cyanoxyethylbenzene, cyanoxybutylbenzene, cyanoxyoctylbenzene, cyanoxynonylbenzene, 2-(4-cyanoxyphenyl)-2- Phenylpropane (cyanate ester of 4-α-cumylphenol), 1-cyanooxy-4-cyclohexylbenzene, 1-cyanooxy-4-vinylbenzene, 1-cyanooxy-2 - or 1-cyanooxy-3-chlorobenzene, 1-cyanooxy-2,6-dichlorobenzene, 1-cyanooxy-2-methyl-3-chlorobenzene, cyanooxynitrobenzene, 1-cyanooxy-4-nitro-2-ethylbenzene, 1-cyanooxy-2-methoxy-4-allylbenzene (cyanate of eugenol), methyl (4-cyano oxyphenyl) sulfide, 1-cyanooxy-3-trifluoromethylbenzene, 4-cyanooxybiphenyl, 1-cyanooxy-2- or 1-cyanooxy-4-acetyl Benzene, 4-Cyanooxybenzaldehyde, Methyl 4-Cyanooxybenzoate, Phenyl 4-Cyanooxybenzoate, 1-Cyanooxy-4-acetylaminobenzene, 4-Cyanooxy Benzophenone, 1-cyanooxy-2,6-di-tert-butylbenzene, 1,2-dicyanooxybenzene, 1,3-dicyanooxybenzene, 1,4-dicyanooxybenzene Benzene, 1,4-dicyanooxy-2-tert-butylbenzene, 1,4-dicyanooxy-2,4-dimethylbenzene, 1,4-dicyanooxy-2,3, 4-trimethylbenzene, 1,3-dicyanooxy-2,4,6-trimethylbenzene, 1,3-dicyanooxy-5-methylbenzene, 1-cyanooxy or 2- Cyanoxynaphthalene, 1-cyanoxynaphthalene, 4-methoxynaphthalene, 2-cyanoxy-6-methylnaphthalene, 2-cyanoxy-7-methoxynaphthalene, 2,2'-dicyanoxynaphthalene -1,1'-binaphthyl, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,6- or 2,7-two Cyanooxynaphthalene, 2,2'- or 4,4'-dicyanooxybiphenyl, 4,4'-dicyanooxyoctafluorobiphenyl, 2,4'- or 4,4'-dicyano Oxydiphenylmethane, bis(4-cyanooxy-3,5-dimethylphenyl)methane, 1,1-bis(4-cyanooxyphenyl)ethane, 1,1-bis( 4-cyanooxyphenyl) propane, 2,2-bis(4-cyanooxyphenyl)propane, 2,2-bis(4-cyanooxy-3-methylphenyl)propane, 2,2 -Bis(2-cyanooxy-5-biphenyl)propane, 2,2-bis(4-cyanooxyphenyl)hexafluoropropane, 2,2-bis(4-cyanooxy-3,5 -Dimethylphenyl) propane, 1,1-bis(4-cyanooxyphenyl)butane, 1,1-bis(4-cyanooxyphenyl)isobutane, 1,1-bis( 4-cyanooxyphenyl)pentane, 1,1-bis(4-cyanooxyphenyl) -3-Methylbutane, 1,1-bis(4-cyanooxyphenyl)-2-methylbutane, 1,1-bis(4-cyanooxyphenyl)-2,2-bis Methyl propane, 2,2-bis(4-cyanooxyphenyl)butane, 2,2-bis(4-cyanooxyphenyl)pentane, 2,2-bis(4-cyanooxyphenyl) base) hexane, 2,2-bis(4-cyanooxyphenyl)-3-methylbutane, 2,2-bis(4-cyanooxyphenyl)-4-methylpentane, 2 ,2-bis(4-cyanooxyphenyl)-3,3-dimethylbutane, 3,3-bis(4-cyanooxyphenyl)hexane, 3,3-bis(4-cyano oxyphenyl)heptane, 3,3-bis(4-cyanooxyphenyl)octane, 3,3-bis(4-cyanooxyphenyl)-2-methylpentane, 3,3 -bis(4-cyanooxyphenyl)-2-methylhexane, 3,3-bis(4-cyanooxyphenyl)-2,2-dimethylpentane, 4,4-bis( 4-cyanooxyphenyl)-3-methylheptane, 3,3-bis(4-cyanooxyphenyl)-2-methylheptane, 3,3-bis(4-cyanooxybenzene base)-2,2-dimethylhexane, 3,3-bis(4-cyanooxyphenyl)-2,4-dimethylhexane, 3,3-bis(4-cyanooxyphenyl) base)-2,2,4-trimethylpentane, 2,2-bis(4-cyanooxyphenyl)-1,1,1,3,3,3-hexafluoropropane, bis(4- Cyanooxyphenyl) phenyl methane, 1,1-bis(4-cyanooxyphenyl)-1-phenylethane, bis(4-cyanooxyphenyl)biphenylmethane, 1,1- Bis(4-cyanooxyphenyl)cyclopentane, 1,1-bis(4-cyanooxyphenyl)cyclohexane, 2,2-bis(4-cyanooxy-3-isopropylbenzene base) propane, 1,1-bis(3-cyclohexyl-4-cyanooxyphenyl)cyclohexane, bis(4-cyanooxyphenyl)diphenylmethane, bis(4-cyanooxyphenyl) base)-2,2-dichloroethylene, 1,3-bis[2-(4-cyanooxyphenyl)-2-propyl]benzene, 1,4-bis[2-(4-cyanooxy phenyl)-2-propyl]benzene, 1,1-bis(4-cyanooxyphenyl)-3,3,5-trimethylcyclohexane, 4-[bis(4-cyanooxyphenyl) base) methyl] biphenyl, 4,4-dicyanooxybenzophenone, 1,3-bis(4-cyanooxyphenyl)-2-propen-1-one, bis(4-cyanooxy Phenyl) ether, bis(4-cyanoxyphenyl) sulfide, bis(4-cyanoxyphenyl) sulfide, 4-cyanoxybenzoic acid-4-cyanoxyphenyl ester (4-cyanoxyphenyl) phenyl-4-cyanooxybenzoate), bis-(4-cyanophenyl)carbonate, 1,3-bis(4-cyanophenyl)adamantane, 1,3- Bis(4-cyanooxyphenyl)-5,7-dimethyladamantane, 1,3-bis(3-methyl-4-cyanooxyphenyl)-5,7-dimethyladamantane , 3,3-bis(4-cyanooxyphenyl)isobenzofuran-1(3H)-one (cyanate ester of phenolphthalein), 3,3-bis(4-cyanooxy-3-methyl phenyl) isobenzofuran-1(3H)-one (cyanate of o-cresol phenolphthalein), 9,9'-bis(4-cyanooxyphenyl) fluorene, 9,9-bis(4-cyanooxy-3-methylphenyl) fluorine, 9,9-bis(2-cyanooxy- 5-biphenyl) fennel, ginseng (4-cyanooxyphenyl) methane, 1,1,1-ginseng (4-cyanooxyphenyl) ethane, 1,1,3-ginseng (4-cyano oxyphenyl)propane, α,α,α'-para(4-cyanooxyphenyl)-1-ethyl-4-isopropylbenzene, 1,1,2,2-tetra(4-cyano Oxyphenyl) ethane, tetrakis (4-cyanooxyphenyl) methane, 2,4,6-para(N-methyl-4-cyanooxyanilino)-1,3,5-tri-methanone , 2,4-bis(N-methyl-4-cyanooxyanilino)-6-(N-methylanilino)-1,3,5-three -2-methylphenyl)-4,4'-oxydiphthalimide, bis(N-3-cyanooxy-4-methylphenyl)-4,4'-oxydiphthalamide Phthalimide, bis(N-4-cyanooxyphenyl)-4,4'-oxydiphthalimide, bis(N-4-cyanooxy-2-methylbenzene base)-4,4'-(hexafluoroisopropylidene)diphthalimide, ginseng(3,5-dimethyl-4-cyanoxybenzyl)isocyanurate, 2 -Phenyl-3,3-bis(4-cyanooxyphenyl)benzyl carboxamide, 2-(4-methylphenyl)-3,3-bis(4-cyanooxyphenyl)benzyl carboxamide, 2-phenyl-3,3-bis(4-cyanooxy-3-methylphenyl)benzylcarboxamide, 1-methyl-3,3-bis(4-cyanooxy phenyl)indolin-2-one, and 2-phenyl-3,3-bis(4-cyanooxyphenyl)indolin-2-one, and their prepolymers.

Among them, the prepolymer of 2,2-bis(4-cyanooxyphenyl)propane is preferable from the viewpoint of excellent heat resistance, dielectric constant, and dielectric tangent.

These cyanate compounds can be used individually by 1 type or in mixture of 2 or more types.

Also, as other specific examples of the compound represented by the above-mentioned general formula (6), for example, phenol novolac resin and cresol novolac resin (according to known methods, phenol, alkyl-substituted phenol or halogen-substituted phenol, and formalin, paraformaldehyde and other formaldehyde compounds reacted in an acidic solution), phenol novolac resin (reacted by the reaction of hydroxybenzaldehyde and phenol in the presence of an acidic ketone compound and 9,9-bis(hydroxyaryl) fennel in the presence of an acidic catalyst), phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin and biphenyl aromatic Alkyl resin (According to the known method, Ar ₂ -(CH ₂ Y) ₂ (Ar ₂ represents a phenyl group, Y represents a halogen atom. Hereinafter, this item is the same.) Dihalomethane compound and phenol compound Those obtained by reacting with an acidic catalyst or without a catalyst, those obtained by reacting a bis(alkoxymethyl) compound represented by Ar ₂ -(CH ₂ OR) ₂ and a phenol compound in the presence of an acidic catalyst, or It is obtained by reacting a bis(hydroxymethyl) compound represented by Ar ₂ -(CH ₂ OH) ₂ with a phenol compound in the presence of an acidic catalyst, or by polycondensing an aromatic aldehyde compound, an aralkyl compound, and a phenol compound obtained), phenol-modified xylene formaldehyde resin (obtained by reacting xylene formaldehyde resin and phenol compound in the presence of an acidic catalyst according to a known method), modified naphthalene formaldehyde resin (according to a known method, making naphthalene formaldehyde resin and hydroxy-substituted aromatic compound reacted in the presence of an acidic catalyst), phenol-modified dicyclopentadiene resin, phenol resin with polynaphthyl ether structure (according to known methods, make A polyvalent hydroxynaphthalene compound having two or more phenolic hydroxyl groups obtained by dehydration condensation in the presence of an alkaline catalyst), such as a phenol resin obtained by cyanate esterification in the same manner as above, and prepolymerization thereof things etc. They are not particularly limited. These cyanate compounds can be used individually by 1 type or in mixture of 2 or more types. Furthermore, it is preferable to use these cyanate compounds together with the cyanate compound represented by the above general formula (6) from the viewpoint of excellent heat resistance, dielectric constant and dielectric tangent.

Among them, phenol novolak type cyanate compounds, naphthol aralkyl type cyanate compounds, biphenyl aralkyl type cyanate compounds, naphthyl ether type cyanate compounds, xylene resin type cyanate compounds 1. The adamantane skeleton type cyanate compound is preferable, and the naphthol aralkyl type cyanate compound is particularly preferable from the viewpoint of heat resistance.

The manufacturing method of these cyanate ester compounds is not specifically limited, A well-known method can be used. The production method is, for example, a method of obtaining or synthesizing a hydroxyl-containing compound with a desired skeleton, modifying the hydroxyl group according to a known method, and cyanating the compound. The method of cyanate-esterifying a hydroxyl group includes, for example, the method described in Ian Hamerton, "Chemistry and Technology of Cyanate Ester Resins," Blackie Academic & Professional.

Cured resins using these cyanate compounds have excellent properties such as glass transition temperature, low thermal expansion, and plating adhesion. In the resin composition of the present embodiment, the content of the cyanate ester compound is not particularly limited. Considering the excellent heat resistance, dielectric constant, and dielectric tangent, it is preferably 0.1 parts by mass to 50 parts by mass, more preferably 0.2 parts by mass to 40 parts by mass, more preferably 0.3 parts by mass to 20 parts by mass, more preferably 0.5 parts by mass to 10 parts by mass, more preferably 1 part by mass to 5 parts by mass.

<Epoxy Resin> As long as the epoxy resin is a compound having two or more epoxy groups in one molecule, known products can be used appropriately, and the type is not particularly limited. Its specific example, for example: bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolak type epoxy resin, biphenyl Type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, xylenol novolak type epoxy resin, multifunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthalene skeleton modified phenolic Varnish-type epoxy resins, pernaphthyl ether-type epoxy resins, phenol aralkyl-type epoxy resins, anthracene-type epoxy resins, trifunctional phenol-type epoxy resins, tetrafunctional phenol-type epoxy resins, tricyclic isocyanurates Oxypropyl ester, glycidyl ester type epoxy resin, cycloaliphatic epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolak type epoxy resin, phenol aralkyl novolak type epoxy resin Resin, naphthol aralkyl novolak type epoxy resin, aralkyl novolak type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type Epoxy resins, polyol-type epoxy resins, phosphorus-containing epoxy resins, epoxypropylamine, compounds obtained by epoxidizing the double bonds of butadiene, polysiloxane resins containing hydroxyl groups, and epichlorohydrin Compounds obtained by the reaction, and their halides. Among them, biphenyl aralkyl type epoxy resin, pernaphthyl ether type epoxy resin, multifunctional phenol type epoxy resin, naphthalene type epoxy resin, and brominated bisphenol A type epoxy resin are excellent in flame retardancy and heat resistance. Sexually better. These epoxy resins can be used individually by 1 type or in mixture of 2 or more types suitably.

The content of the epoxy resin is not particularly limited, preferably 0.1 to 50 parts by mass, more preferably 0.2 to 45 parts by mass, more preferably 5 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition ~40 parts by mass, more preferably 10 parts by mass to 25 parts by mass, more preferably 15 parts by mass to 25 parts by mass, most preferably 12 parts by mass to 20 parts by mass. When the content of the epoxy resin is within the above range, the flame retardancy and heat resistance tend to be further improved.

<Phenol resin> The phenol resin should just be a phenol resin which has 2 or more hydroxyl groups in 1 molecule, and what is generally known can be used. For example: bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolak resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol Resin, aralkyl novolak type phenol resin, biphenyl aralkyl type phenol resin, cresol novolak type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolak resin, polyfunctional naphthol resin, anthracene Type phenol resin, naphthalene skeleton modified novolac type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol Resins, polyol-type phenol resins, phosphorus-containing phenol resins, polymerizable unsaturated hydrocarbon-containing phenol resins, hydroxyl-containing polysiloxane resins, etc., but not particularly limited. Among these phenol resins, biphenyl aralkyl type phenol resins, naphthol aralkyl type phenol resins, phosphorus-containing phenol resins, and hydroxyl-containing polysiloxane resins are preferable from the viewpoint of flame retardancy. These phenolic resins can be used individually by 1 type or in mixture of 2 or more types suitably.

The content of the phenol resin is not particularly limited, but it is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 45 parts by mass, and more preferably 0.3 parts by mass relative to 100 parts by mass of resin solids in the resin composition. ~40 parts by mass. When content of a phenol resin exists in the said range, heat resistance tends to improve more.

<Oxetane resin> As the oxetane resin, generally known ones can be used. For example: oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane Alkyl oxetane such as cyclobutane, 3-methyl-3-methoxymethyl oxetane, 3,3-bis(trifluoromethyl)perfluorooxetane, 2 -Chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl-type oxetane, OXT-101 (manufactured by Toagosei, trade name), OXT-121 (Toa Synthetic, trade name), etc., are not particularly limited. These can be used individually by 1 type or in mixture of 2 or more types suitably.

The content of the oxetane resin is not particularly limited, preferably 0.1 to 50 parts by mass, more preferably 0.2 to 45 parts by mass, and more preferably It is 0.3 mass part - 40 mass parts. When content of an oxetane resin exists in the said range, heat resistance tends to improve more.

<Benza 㗁 𠯤 compound> As the benzo 㗁 𠯤 compound, any compound having two or more dihydro benzo 2 or more rings in one molecule can be used, and generally known ones can be used. For example: bisphenol A type benzo㗁𠯤BA-BXZ (manufactured by Konishi Chemical, trade name), bisphenol F type benzo㗁𠯤BF-BXZ (manufactured by Konishi Chemical, trade name), bisphenol S type benzo㗁𠯤BS - BXZ (manufactured by Konishi Chemical Co., Ltd., trade name), phenol phenolphthalein type benzo㗁𠯤, etc., without special restrictions. These can be used individually by 1 type or in mixture of 2 or more types suitably.

There is no particular limitation on the content of the benzo 㗁𠯤 compound, preferably 0.1 to 50 parts by mass, more preferably 0.2 to 45 parts by mass, and more preferably 0.3 parts by mass to 40 parts by mass. The heat resistance tends to be further improved when the content of the benzoglyceride compound is within the above-mentioned range.

<Compounds having an ethylenically unsaturated group> In the resin composition of this embodiment, in order to improve thermosetting properties and curability by active energy rays (for example, photocurability by ultraviolet rays, etc.), an ethylenic compound may be used in combination. Saturated compounds. The compound having an ethylenically unsaturated group used in this embodiment is not particularly limited as long as it is a compound having one or more ethylenically unsaturated groups in one molecule. For example, it has a (meth)acryl group, Compounds such as vinyl. These can be used 1 type or in mixture of 2 or more types suitably.

Examples of compounds having a (meth)acryl group include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, polyethylene glycol (Meth)acrylate, polyethylene glycol (meth)acrylate monomethyl ether, phenylethyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, ( Benzyl Meth)acrylate, Tetrahydrofuryl Methyl (Meth)acrylate, Butylene Glycol Di(meth)acrylate, Hexylene Glycol Di(meth)acrylate, Neopentyl Glycol Di(meth)acrylate, Nonanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, divinyl di(meth)acrylate, polyethylene glycol di(meth)acrylate, ginseng(meth)propylene Acyloxyethyl isocyanurate, polypropylene glycol di(meth)acrylate, adipate epoxy di(meth)acrylate, bisphenoloxyethylene di(meth)acrylate, hydrogenated bisphenoloxy Ethylene (meth)acrylate, bisphenol di(meth)acrylate, ε-caprolactone modified hydroxytrimethyl acetate neopentyl glycol di(meth)acrylate, ε-caprolactone modified di Neopentylthritol hexa(meth)acrylate, ε-caprolactone modified diperythritol poly(meth)acrylate, diperythritol poly(meth)acrylate, trimethylolpropane Tri(meth)acrylate, trihydroxyethylpropane tri(meth)acrylate, and its ethylene oxide adduct, neopentylthritol tri(meth)acrylate, and its ethylene oxide Alkane adducts, neopentylthritol tetra(meth)acrylate, diperythritol hexa(meth)acrylate, and their ethylene oxide adducts, etc.

In addition, urethane (meth)acrylates that have both (meth)acryl and urethane bonds in the same molecule, and urethane (meth)acrylates that also have (meth)acryl in the same molecule Polyester (meth)acrylates with ester bonds, epoxy (meth)acrylates derived from epoxy resins and having (meth)acryl groups, and the reactivity of these bonds oligomers, etc.

The above-mentioned urethane (meth)acrylates are reactants of hydroxyl group-containing (meth)acrylates, polyisocyanates, and other alcohols as needed. For example: hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate and other hydroxyalkyl (meth)acrylates, glycerin mono(meth)acrylate, glycerol diacrylate Glycerin (meth)acrylates such as (meth)acrylates, neopentylthritol di(meth)acrylate, neopentylthritol tri(meth)acrylate, dipentyl tetrapentyl penta(meth)acrylate Sugar alcohol (meth)acrylates such as alcohol esters, and toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norcamphene diisocyanate, xylene Diisocyanate, hydrogenated xylene diisocyanate, dicyclohexyl methylene diisocyanate, and their isocyanurates, biuret reactants and other polyisocyanates react to form urethane (meth)acrylate kind.

The aforementioned epoxy (meth)acrylates are compounds having epoxy groups and carboxylate compounds of (meth)acrylic acid. For example: phenol novolak type epoxy (meth)acrylate, cresol novolak type epoxy (meth)acrylate, parahydroxyphenylmethane type epoxy (meth)acrylate, dicyclopentadiene phenol Type epoxy (meth)acrylate, bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, biphenol type epoxy (meth)acrylate, bisphenol A Novolac type epoxy (meth)acrylate, naphthalene skeleton containing epoxy (meth)acrylate, glyoxal type epoxy (meth)acrylate, heterocyclic epoxy (meth)acrylate, And these anhydride-modified epoxy (meth)acrylates, the compound represented by the said general formula (1), etc.

In the aforementioned general formula (1), a plurality of R ₁ each independently represent a hydrogen atom or a methyl group. Among them, from the viewpoint of improving the reactivity of the photohardening reaction, it is preferable to contain a hydrogen atom, and it is more preferable that all of R ₁ are hydrogen atoms.

Multiple R ₂ each independently represent a hydrogen atom or a methyl group. Among them, from the viewpoint of improving the heat resistance of the cured product, it is preferable to contain a methyl group, and it is more preferable that all R ₂ are methyl groups.

A plurality of R ₃ each independently represent a substituent represented by the aforementioned formula (2), a substituent represented by the aforementioned formula (3), or a hydroxyl group. Among them, from the viewpoint of improving heat resistance, it is preferable to contain a hydroxyl group. Also, in this embodiment, it is preferable to use a compound including a substituent represented by the above-mentioned formula (2) among a plurality of R ₃ from the viewpoint of improving developability. In this embodiment, it is preferable to use a compound including a substituent represented by the aforementioned formula (3) among a plurality of R ₃ from the viewpoint of improving heat resistance. In the aforementioned formula (3), R ₄ represents a hydrogen atom or a methyl group. Among them, a hydrogen atom is preferable from the viewpoint of improving the reactivity of the photohardening reaction.

Considering the viewpoint of improving developability, among the substituents _of all the R3s _of multiple R3s, the ratio of the substituents represented by the aforementioned formula (2) is 20% to 85%, and the ratio of the substituents represented by the aforementioned formula (3) is The ratio is preferably not less than 5% and not more than 70%, and the ratio of hydroxyl groups is preferably not less than 10% and not more than 75%. If the compound represented by the aforementioned general formula (1) contains any one or more of the following compounds (A1) to (A5), the reactivity of the photohardening reaction, the heat resistance and the developability of the cured product can be improved, and it is more desirable to contain at least Compound (A1) is more preferably, more preferably contains any two or more of (A1)~(A5), and even more preferably contains any one or more of compound (A1) and compounds (A2)~(A5). It is also desirable to contain at least compounds (A2) and (A3) as compound (A).

【chemical 10】

【chemical 11】

【chemical 12】

【chemical 13】

【Chemical 14】

In consideration of improving the developability, the acid value of the compound represented by the aforementioned general formula (1) is 30 mgKOH/g or more, and in consideration of improving the developability, the acid value is preferably 50 mgKOH/g or more. Also, in consideration of preventing dissolution by the developer after hardening with active energy rays, the acid value of the compound represented by the aforementioned general formula (1) is 120 mgKOH/g or less, and in consideration of further preventing dissolution, preferably 110 mgKOH/g or less . In addition, the "acid value" in this embodiment represents the value measured according to the method of JISK 0070:1992.

Examples of the acid anhydride-modified epoxy acrylate include acid-modified bisphenol F-type epoxy acrylate. They can also use commercially available products, which can include those represented by the aforementioned general formula (1), for example: manufactured by Nippon Kayaku (Stock), KAYARAD (registered trademark) ZCR-6001H, KAYARAD (registered trademark) ZCR-6002H, KAYARAD ( Registered trademark) ZCR-6006H, KAYARAD (registered trademark) ZCR-6007H, KAYAR AD (registered trademark) ZCA-601H (the above are product names), etc. Moreover, the Nippon Kayaku Co., Ltd. product KAYARAD (registered trademark) ZFR-1553H (brand name) is mentioned as an acid-modified bisphenol F type epoxy acrylate.

Examples of the compound having a vinyl group include vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, and bifunctional phenylene ether oligomers having a vinyl group. Examples of styrenes include styrene, methylstyrene, ethylstyrene, divinylbenzene, α-methylstyrene, and oligomers thereof. Examples of other vinyl compounds include triallyl isocyanurate, trimethylallyl isocyanurate, diallyl nadicimide, and the like.

Among these, it is preferable to be selected from the group consisting of 2-functional phenylene ether oligomers with vinyl groups, α-methylstyrene oligomers, acid-modified bisphenol F type epoxy (meth)acrylic acid Esters, compounds represented by the aforementioned general formula (1), neopentylthritol tetra(meth)acrylate, dipentylthritol hexa(meth)acrylate, cresol novolak type epoxy (meth)acrylate , bisphenol A-type epoxy (meth)acrylate, naphthalene skeleton-containing epoxy (meth)acrylate, and at least one of the group consisting of bisallyl nadicimide is preferred. If it is selected from 2 functional phenylene ether oligomers with vinyl groups, oligomers of α-methylstyrene, acid-modified bisphenol F-type epoxy (meth)acrylate, the aforementioned general formula One or more compounds selected from the group consisting of the compound represented by (1) and diperythritol hexa(meth)acrylate are more preferable from the viewpoint of obtaining good heat resistance, dielectric constant, and dielectric tangent.

When thermosetting properties are required, bifunctional phenylene ether oligomers with vinyl groups and/or α-methylstyrene oligomers can be thermally cured well and have good embedding properties of fine wiring, solder Excellent heat resistance, dielectric constant, and dielectric tangent, so it is ideal. When photohardening is required, if it contains acid-modified bisphenol F-type epoxy (meth)acrylate, the compound represented by the aforementioned general formula (1) and dipenteoerythritol hexa(meth)acrylate At least one or more of the group constituted has good embedding properties of fine wiring and solder heat resistance, and is also excellent in dielectric constant, dielectric tangent, and developability, so it is ideal. Using the aforementioned general formula (1 ) is preferable since it has better heat resistance. By including such a compound having an ethylenically unsaturated group, the heat resistance of the obtained cured product tends to be further improved. These ethylenically unsaturated group-containing compounds can be used alone or in combination of two or more as appropriate. In addition, these ethylenically unsaturated group-containing compounds may contain isomers such as structural isomers and stereoisomers, and two or more compounds having mutually different structures may be used in combination as appropriate.

The content of the compound having an ethylenically unsaturated group is not particularly limited, but is preferably 0.1 to 90 parts by mass, more preferably 0.2 to 85 parts by mass relative to 100 parts by mass of resin solids in the resin composition. When the compound which has an ethylenically unsaturated group exists in the said range, there exists a tendency for solder heat resistance to improve more. In particular, when thermal hardening is required, it can be thermally hardened well, and it is considered to obtain good embedding properties of fine wiring and solder heat resistance, dielectric constant, and dielectric tangent. The content of the compound with ethylenically unsaturated group relative to the resin The resin solid content in the composition is preferably 5 to 90 parts by mass, more preferably 7 to 85 parts by mass, and more preferably 10 to 83 parts by mass, per 100 parts by mass of resin solids. Also, when photocurability is required, the content of the compound having an ethylenically unsaturated group relative to The resin solid content in the resin composition is preferably 5 parts by mass to 90 parts by mass, more preferably 7 parts by mass to 85 parts by mass, more preferably 10 parts by mass to 80 parts by mass, more preferably 10 parts by mass, per 100 parts by mass of resin solids Parts ~ 73 parts by mass.

<Fillers (C) other than silica-coated fluororesin particles (A)> The resin composition of this embodiment may contain silica-coated Fillers (C) other than fluororesin particles (A) (hereinafter referred to as other fillers (C)). By using other fillers (C) in combination, desired properties such as flame retardancy, heat resistance, and thermal expansion properties of the cured product can be improved.

Other fillers (C) are not particularly limited as long as they are insulating, for example: natural silica, fused silica, synthetic silica, amorphous silica, Aerosil, hollow silica, etc. Silicon dioxide, white carbon, titanium dioxide, zinc oxide, magnesium oxide, zirconium oxide and other oxides, boron nitride, condensed boron nitride, silicon nitride, aluminum nitride, barium sulfate, aluminum hydroxide, aluminum hydroxide Heat-treated products (heat-treated aluminum hydroxide to reduce part of the crystal water), metal hydrates such as boehmite and magnesium hydroxide, molybdenum compounds such as molybdenum oxide and zinc molybdate, zinc borate, zinc stannate, oxide Aluminum, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, glass short fiber (including E glass, T glass, D glass, S glass, Q glass and other glass powders), insulating glass, spherical glass and other inorganic fillers, other than styrene type, butyric Diene type, acrylic type rubber powder, core-shell type rubber powder, silicone resin powder, silicone rubber powder, silicone composite powder and other organic fillers. Among them, one or more kinds selected from the group consisting of silica, aluminum hydroxide, boehmite, magnesium oxide, magnesium hydroxide, and barium sulfate are preferred. These can be used 1 type or in mixture of 2 or more types suitably. These other fillers (C) may also be surface-treated with silane coupling agents described later.

In particular, from the viewpoint of improving the heat resistance of the cured product, silica is preferable, and fused silica is particularly preferable. Specific examples of silicon dioxide include SFP-130MC manufactured by Denka Co., Ltd., SC2050-MB, SC2050-MNU, SC1050-MLE, YA010C-MFN, YA050C-MJA manufactured by Admatechs Co., Ltd., and the like.

The average particle size of other fillers (C) is not particularly limited, and the median diameter is preferably 15 μm or less in view of making the dispersibility of other fillers (C) in the resin composition good. Also, from the viewpoint of making the dispersibility of other fillers (C) in the resin composition good, the median diameter is preferably 0.005 μm or more.

In addition, in this specification, "median diameter" refers to a certain particle diameter as a reference, when the particle size distribution of the powder is divided into two sides, the number or mass of the particles on the side with the larger particle size and the particle size on the side with the smaller particle size The number or mass of the particle size accounts for 50% of the total powder. The median diameter can be measured by a wet laser diffraction and scattering method.

In the resin composition of the present embodiment, the content of other fillers (C) is not particularly limited, but from the viewpoint of improving the heat resistance of the cured product, it is preferably 5 parts by mass or more with respect to 100 parts by mass of the resin composition, and 10 parts by mass More preferably, more than 20 parts by mass, and more preferably more than 20 parts by mass. Also, from the viewpoint of improving the developability of the resin composition and the embedding property of fine wiring, it is preferably 400 parts by mass or less, more preferably 350 parts by mass or less, and still more preferably 300 parts by mass or less, based on 100 parts by mass of the resin composition. Good, more preferably 100 parts by mass or less.

<Silane coupling agent and wetting and dispersing agent> In the resin composition of this embodiment, you may contain a silane coupling agent and/or a wetting and dispersing agent within the range which does not impair the characteristic of this embodiment. By using a silane coupling agent and/or a wetting and dispersing agent in combination, desired properties such as the dispersibility of the filler and the adhesive strength between the resin and the filler can be improved.

The silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for surface treatment of fillers. Specific examples, such as vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ- Aminosilanes such as aminopropyltrimethoxysilane; epoxysilanes such as γ-glycidoxypropyltrimethoxysilane; acrylic silanes such as γ-acryloxypropyltrimethoxysilane ; N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, N-(vinylbenzene)-2-aminoethyl-3-amino Cationic silane series such as propyltrimethoxysilane hydrochloride; silane coupling agent of phenylsilane series, etc. These silane coupling agents can be used individually by 1 type or in appropriate combination of 2 or more types.

In the resin composition of the present embodiment, the content of the silane coupling agent is not particularly limited, but is usually 0.1 to 10 parts by mass relative to 100 parts by mass of the resin composition.

The wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used in coating applications. Specific examples include wetting and dispersing agents such as DISPERBYK (registered trademark)-110, 111, 118, 180, 161, BYK (registered trademark)-W996, W9010, W903 manufactured by BYK Chemie Japan Co., Ltd. These wetting and dispersing agents can be used individually by 1 type or in mixture of 2 or more types suitably. In the resin composition of this embodiment, the content of the wetting and dispersing agent is not particularly limited, but is usually 0.1 to 10 parts by mass relative to 100 parts by mass of the resin composition.

<Flame retardant (D)> In the resin composition of this embodiment, you may contain a flame retardant (D) within the range which does not impair the characteristic of this embodiment. By using the flame retardant (D) in combination, desired properties such as flame retardancy, heat resistance, and thermal expansion properties of the cured product can be improved.

As the flame retardant (D), generally known ones can be used as long as they have insulating properties. For example: brominated organic compounds such as brominated polycarbonate, decabromodiphenylethane, 4,4-dibromobiphenyl, ethylene bis-tetrabromophthalimide, etc. There are no special restrictions. These can be used individually by 1 type or in mixture of 2 or more types suitably. In the resin composition of this embodiment, the content of the flame retardant (D) is not particularly limited, and is usually 0.1 to 10 parts by mass relative to 100 parts by mass of the resin composition in the resin composition, preferably 1 to 10 parts by mass .

<Photocuring initiator (E)> In the resin composition of this embodiment, when using a resin component that can be photocured by ultraviolet rays or the like (maleimide compound, epoxy resin, ethylenically unsaturated group compound, phenol resin, oxetane resin, etc.) as the resin component (B), in order to improve its photocurability, a photocurable initiator (E) may also be included within the range that does not impair the characteristics of this embodiment. . The photocuring initiator (E) is not particularly limited, and those generally known in the field of use for photocurable resin compositions can be used.

For example: benzoine, benzoine methyl ether, benzoine ethyl ether, benzoine propyl ether, benzoine isobutyl ether and other benzoines, benzoyl peroxide, lauryl peroxide, acetyl peroxide , p-chlorobenzoyl peroxide, di-tert-butyl diperoxyphthalate and other organic peroxides, acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2, 2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-Hydroxycyclohexylbenzophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-𠰌olino-propan-1-one and other acetophenones, 2-ethylanthraquinone , 2-tertiary butyl anthraquinone, 2-chloroanthraquinone, 2-pentyl anthraquinone and other anthraquinones, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chloro Thioxanthone and other thioxanthones, acetophenone dimethyl ketal, benzyl dimethyl ketal and other ketals, benzophenone, 4-benzoyl-4'-methyldiphenylsulfide Ether, benzophenones such as 4,4'-bismethylaminobenzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethyl Phosphine oxides such as benzoyl)-phenylphosphine oxide, oxime esters such as 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyl oxime)] Free radical type photohardening initiators, diazonium salts of Lewis acids such as fluorophosphonic acid p-methoxyphenyl diazonium salt, hexafluorophosphonic acid N,N-diethylaminophenyl diazonium salt, Lewis acid such as diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroantimonate, etc. phosphonium salts of phosphonium salts, triphenylphosphonium hexafluoroantimonate and other Lewis acid phosphonium salts, other halides, three phosphonium-based initiators, borate-based initiators, and other photoacid generators and other cationic systems Photopolymerization initiator.

Among them, 2-benzyl-2-dimethylamino-1-(4-?olinophenyl)-butyl Radical photocuring initiators such as acetophenones (Irgacure (registered trademark) 369, manufactured by BASF Japan Co., Ltd.) and the like are preferable.

These photocuring initiators (E) may be used individually by 1 type or in mixture of 2 or more types suitably, and may use both radical type and cationic type initiators together.

In the resin composition of this embodiment, the content of the photocuring initiator (E) is not particularly limited. Considering that the resin composition is fully cured by active energy rays and the heat resistance is improved, relative to the resin in the resin composition 100 parts by mass of solid content is preferably at least 0.1 part by mass, more preferably at least 0.2 part by mass, more preferably at least 0.3 part by mass, and more preferably at least 1 part by mass. Also, considering the viewpoint of suppressing thermal hardening after photocuring and reducing heat resistance, it is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and 20 parts by mass or less relative to 100 parts by mass of resin solid content in the resin composition. More preferably, less than 10 parts by mass is more desirable.

<Thermosetting Accelerator> In the resin composition of the present embodiment, a thermosetting accelerator may be used in combination within the range not impairing the characteristics of the present embodiment. The thermal hardening accelerator is not particularly limited, for example: benzoyl peroxide, lauryl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide, di-tert-butyl dipthalate, etc. Peroxides; azo compounds such as azobisnitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylanilino Tertiary amines such as ethanol, tri-n-butylamine, pyridine, quinoline, N-methyl ? Cresol, cresol, resorcinol, catechol and other phenols; lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, tin oleate, dibutyltin malate, manganese naphthenate, Cobalt naphthenate, iron acetylacetonate and other organic metal salts; these organic metal salts are dissolved in compounds containing hydroxyl groups such as phenol and bisphenol; tin chloride, zinc chloride, aluminum chloride and other inorganic metal salts ; Dioctyl tin oxide, other organic tin compounds such as alkyl tin and alkyl tin oxide; 1,2-dimethylimidazole, 1-benzyl-2-phenylimidazole, 2,4,5-triphenyl Imidazole compounds such as imidazole, etc.

These thermosetting accelerators can be used individually by 1 type or in mixture of 2 or more types suitably. In the resin composition of the present embodiment, the content of the thermosetting accelerator is not particularly limited, and is usually 0.1 to 10 parts by mass relative to 100 parts by mass of the resin composition in the resin composition.

<Organic solvent> The resin composition of this embodiment may contain a solvent as needed. For example, if an organic solvent is used, the viscosity can be adjusted during the preparation of the resin composition. The type of solvent is not particularly limited as long as it can dissolve part or all of the resins in the resin composition. Its specific examples are not particularly limited, for example: ketones such as acetone, methyl ethyl ketone, and methyl cellulosulfone; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; propylene glycol monomethyl ether and ethyl esters. These organic solvents can be used individually by 1 type or in mixture of 2 or more types suitably.

<Other Components> In the resin composition of this embodiment, various high-grade resins such as thermosetting resins, thermoplastic resins and their oligomers, and elastomers that have not been listed so far can also be used in combination within the range that does not impair the characteristics of this embodiment. Molecular compounds; flame-retardant compounds not listed so far; additives, etc. These are not particularly limited as long as they are general users. For example, the flame retardant compounds include nitrogen-containing compounds such as melamine and benzoguanamine, compounds containing 㗁𠯤 rings, phosphate compounds of phosphorus compounds, aromatic condensed phosphates, halogen-containing condensed phosphates, and the like. Examples of additives include ultraviolet absorbers, antioxidants, fluorescent whitening agents, photosensitizers, dyes, pigments, thickeners, lubricants, defoamers, surface regulators, gloss agents, polymerization inhibitors, and the like. These components can be used individually by 1 type or in mixture of 2 or more types suitably. In the resin composition of the present embodiment, the contents of other components are not particularly limited, and are usually 0.1 to 10 parts by mass relative to 100 parts by mass of the resin composition.

The resin composition of this embodiment is prepared by appropriately mixing the silica-coated fluororesin particles (A), the resin component (B), and any other desired components described above. The resin composition of this embodiment is suitable for use as a varnish when producing a prepreg and a resin sheet of this embodiment described later. <Manufacturing method of resin composition> The method of manufacturing the resin composition of the present embodiment is not particularly limited, for example, a method of sequentially mixing the above-mentioned components in a solvent and stirring them sufficiently.

When producing the resin composition, known treatments (stirring, mixing, kneading treatment, etc.) for uniformly dissolving or dispersing each component may be performed as needed. Specifically, the dispersion of the silica-coated fluororesin particles (A) to the resin composition can be improved by performing the stirring and dispersing treatment using a stirring tank equipped with a stirrer having an appropriate stirring capacity. The above stirring, mixing and kneading treatment can use such as ultrasonic homogenizer and other stirring devices for the purpose of dispersion, three-rollers, ball mills, bead mills, sand mills and other devices for the purpose of mixing, or revolution or self-rotating mixing devices and other well-known devices are properly carried out. Moreover, when preparing the resin composition of this embodiment, an organic solvent can be used as needed. The type of the organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition, and specific examples thereof are as described above. ＜Use＞

The resin composition of this embodiment can be used in applications requiring insulating resin compositions, and is not particularly limited. It can be used in insulating resin sheets such as photosensitive films, photosensitive films with supports, prepregs, and circuit boards (laminates). laminates, multilayer printed circuit boards, etc.), solder resist, underfill materials, die bonding materials, semiconductor sealing materials, hole filling resins, parts filling resins, etc. Among them, resin compositions for insulating layers of multilayer printed circuit boards and solder resists are suitable.

<Prepreg> The prepreg of the present embodiment is obtained by impregnating or coating the resin composition of the above-mentioned present embodiment on the substrate. The method for producing the prepreg is not particularly limited as long as it is a method of producing the prepreg by combining the resin composition of the present embodiment with the base material. Specifically, after the resin composition of this embodiment is impregnated or coated on the substrate, it is semi-cured by a method of drying at 120-220°C for about 2-15 minutes to produce the prepreg of this embodiment . At this time, the adhesion amount of the resin composition to the substrate, that is, the amount of the resin composition relative to the total amount of the semi-cured prepreg (including the filler), is preferably in the range of 20 to 99% by mass.

As the base material used when manufacturing the prepreg of this embodiment, known ones used for various printed circuit board materials can be used. For example: E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass, spherical glass and other glass fibers, inorganic fibers other than glass such as quartz, polyimide, polyamide, Organic fibers such as polyester, woven fabrics such as liquid crystal polyester, but not particularly limited thereto. As the shape of the base material, woven fabrics, non-woven fabrics, rovings, cut strand mats, surface mats, etc. are known, and all of them can be used. A base material can be used individually by 1 type or in combination of 2 or more types. In addition, the thickness of the base material is not particularly limited. For laminated board applications, the range of 0.01~0.2mm is ideal, especially for woven fabrics that have been treated with ultra-fiber opening and pore blockage. The point of view of dimension stability is ideal. Furthermore, glass woven fabrics surface-treated with silane coupling agents such as epoxy silane treatment and amino silane treatment are ideal from the viewpoint of moisture absorption and heat resistance. Also, the liquid crystal polyester woven fabric is ideal in terms of electrical characteristics.

<Metal foil-clad laminate> The metal-clad laminate of this embodiment is the above-mentioned prepreg in which at least one sheet or more is laminated together, and the metal disposed on one or both sides of the prepreg. The foils are laminated and formed. Specifically, it can be produced by stacking one or more sheets of the aforementioned prepreg, arranging metal foils such as copper and aluminum on one or both sides thereof, and laminating and forming them. The metal foil used here is not particularly limited as long as it is used as a printed circuit board material, and copper foil such as rolled copper foil and electrolytic copper foil is preferable. Also, the thickness of the metal foil is not particularly limited, but is preferably 2 to 70 μm, more preferably 3 to 35 μm. Forming conditions can adopt the methods of laminated boards and multilayer boards for common printed circuit boards. For example, multi-stage presses, multi-stage vacuum presses, continuous forming machines, autoclave forming machines, etc. can be used to form laminates at a temperature of 180~350°C, a heating time of 100~300 minutes, and a surface pressure of 20~100kg/cm ² , to manufacture the metal foil-clad laminate of the present invention. In addition, the above-mentioned prepreg may be combined with a wiring board for an inner layer produced separately to form a multi-layer board. The method of manufacturing a multi-layer board, for example, arranging 35 μm copper foil on both sides of the above-mentioned prepreg, performing lamination under the above-mentioned conditions, forming an inner layer circuit, and performing blackening treatment on this circuit to form an inner layer circuit board, Afterwards, the inner layer circuit board and the above-mentioned prepreg are alternately arranged one by one, and then the copper foil is arranged on the outermost layer, and the above-mentioned conditions are preferably laminated and formed under vacuum to produce a multi-layer board.

<Resin sheet> In addition, the resin sheet of this embodiment can be obtained by apply|coating the solution which melt|dissolved the resin composition of this embodiment mentioned above in a solvent, and drying it on a support body. The support used here, for example: polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylene tetrafluoroethylene copolymer film, and coating on the surface of these films Release film obtained by adding a release agent, organic film base material such as polyimide film, conductive foil such as copper foil and aluminum foil, plate shape such as glass plate, SUS plate, FRP, etc., there are no special restrictions.

Furthermore, the resin composition layer of the resin sheet in this embodiment may be protected by a protective film. By protecting the resin composition layer side with a protective film, it is possible to prevent dirt, etc. from adhering to the surface of the resin composition layer, etc., or to prevent damage. As the protective film, a film made of the same material as the above-mentioned resin film can be used. The thickness of the protective film is not particularly limited, preferably in the range of 1 μm to 50 μm, more preferably in the range of 5 μm to 40 μm. If the thickness is less than 1 μm, the handleability of the protective film tends to decrease, and if it exceeds 50 μm, the cost performance tends to be poor. Also, the protective film is preferably one in which the adhesive force between the resin composition layer and the protective film is smaller than the adhesive force between the resin composition layer and the support.

Coating method, for example, the solution obtained by dissolving the resin composition of this embodiment in a solvent is coated on the support with a rod coater, die coater, doctor blade, Baker applicator, etc. to obtain a support and a resin sheet A method of forming a one-piece laminate. Moreover, after drying, a support body may be peeled or etched from a laminated sheet, and a resin sheet may be made into an independent single-layer sheet. Also, by supplying a solution obtained by dissolving the resin composition of the present embodiment in a solvent into a mold having a sheet-shaped cavity, drying, etc., to form a sheet, a single sheet can be obtained without using a support. layers.

Also, when the resin sheet (single-layer or laminated sheet) of this embodiment is produced, the drying conditions when removing the solvent are not particularly limited. Considering that if it is low temperature, the solvent is likely to remain in the resin composition, and if it is high temperature, the drying conditions of the resin composition will be reduced. From the point of view that hardening will proceed, it is better to carry out at a temperature of 20°C~200°C for 1~90 minutes. Also, the thickness of the resin layer of the resin sheet (single-layer or laminated sheet) of this embodiment can be adjusted by the concentration of the solution of the resin composition of this embodiment and the coating thickness, and is not particularly limited. If the thickness is increased, the solvent is likely to remain during drying, so it is preferably 0.1-500 μm.

<Printed Wiring Board> The metal foil-clad laminate and the resin sheet of this embodiment can be ideally used as a printed wiring board. The printed circuit board can be manufactured according to the usual method, and the manufacturing method is not particularly limited. An example of a method of manufacturing a printed circuit board using a metal foil-clad laminate is shown below. First, a metal foil-clad laminate such as the above-mentioned copper-clad laminate is prepared. Then, etching is performed on the surface of the metal foil-clad laminate to form an inner layer circuit to produce an inner layer substrate. For the surface of the inner layer circuit of the inner layer substrate, if necessary, perform surface treatment to improve the adhesion strength, and then overlap the required number of pieces of the above-mentioned prepreg on the surface of the inner layer circuit, and then laminate the metal for the outer layer circuit on the outside. The foil is integrally formed by heating and pressing. In this manner, a multilayer laminate was produced in which a base material and an insulating layer made of a cured product of a thermosetting resin composition were formed between metal foils for an inner layer circuit and an outer layer circuit. Next, after processing the through-holes and via holes on the multi-layer laminated board, a plated metal film is formed on the wall of the hole to conduct the inner layer circuit and the metal foil for the outer layer circuit, and then Etching is performed on the metal foil for the outer layer circuit to form the outer layer circuit and make a printed circuit board.

The printed circuit board obtained in the above production example has an insulating layer and a conductive layer formed on the surface of the insulating layer, and the insulating layer is composed of the resin composition of the above-mentioned embodiment. That is, the above-mentioned prepreg of the present embodiment (the base material and the resin composition of the present embodiment impregnated or coated on the base material), the layer of the resin composition of the metal foil-clad laminate of the above-mentioned present embodiment (The layer composed of the resin composition of the present invention) is composed of an insulating layer containing the resin composition of this embodiment.

An example of the manufacturing method of the printed circuit board using a resin sheet is shown below. The resin sheet of this embodiment is suitably used as an interlayer insulating layer of a printed circuit board, and can be obtained by laminating one or more of the above-mentioned resin sheets and curing them. Specifically, it can be manufactured according to the following method.

The resin composition layer side of the resin sheet of this embodiment is molded on one side or both sides of the circuit board. Molding conditions can adopt the usual method of laminated boards and multilayer boards for printed circuit boards, and can also be formed by vacuum lamination. Examples of circuit substrates include glass epoxy substrates, metal substrates, ceramic substrates, silicon substrates, semiconductor sealing resin substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. In addition, here, a circuit board refers to a board|substrate in which the conductor layer (circuit) processed by patterning was formed in one side or both sides of the board|substrate mentioned above. In addition, in a multilayer printed circuit board formed by alternately stacking conductive layers and insulating layers, one or both sides of the outermost layer of the multilayer printed circuit board become a substrate of a patterned conductive layer (circuit), which is also included here. Refers to the circuit substrate. In addition, the surface of the conductive layer may be subjected to roughening treatment such as blackening treatment and copper etching in advance. In the molding step, if the resin sheet has a protective film, after peeling and removing the protective film, the resin sheet and the circuit board are preheated if necessary, and the resin composition layer is pressure-bonded to the circuit board while applying pressure and heating. The resin sheet of this embodiment is preferably laminated on the circuit board under reduced pressure using a vacuum lamination method.

The conditions of the lamination step are not particularly limited, for example: the crimping temperature (lamination temperature) is preferably 50°C~140°C, the crimping pressure is preferably 1kgf/cm ² ~15kgf/cm ² , and the crimping time is preferably 5 seconds to 300 seconds, and the lamination is preferably carried out under reduced pressure with an air pressure of 20mmHg or less. In addition, the lamination step may be a batch method or a continuous method using a roll. The vacuum lamination method can be performed using a commercially available vacuum laminator. Commercially available vacuum laminator, for example: 2-stage build-up laminator manufactured by Nikko Materials Co., Ltd.

Hole processing is performed to form vias, through holes, and the like. Hole processing can be performed using any one of known methods such as NC drill, carbon dioxide gas laser, UV laser, YAG laser, and plasma, or a combination of two or more of them if necessary. When the resin sheet is a photocurable resin composition, hole processing may be performed by exposure and image development.

Before or after the hole processing, a post-baking step is performed as necessary to form an insulating layer (cured product). Examples of the post-baking step include an ultraviolet ray irradiation step using a high-pressure mercury lamp, a heating step using a clean oven, and the like. When irradiating ultraviolet rays, the irradiation dose can be adjusted as necessary, and irradiation can be performed at an irradiation dose of about 0.05 J/cm ² to 10 J/cm ² , for example. In addition, the heating conditions can be appropriately selected according to the type and content of the resin components in the resin composition, preferably in the range of 150°C~220°C for 20 minutes~180 minutes, more preferably 160°C~200°C for 30 minutes~ Choose from a range of 150 minutes.

When there is a conductor layer on the surface of the insulating layer, the outer layer circuit can be formed by forming a plated metal film on the wall surface of the hole to conduct the inner layer circuit and the metal foil for the outer layer circuit, and then etching the metal foil for the outer layer circuit. Manufacture printed circuit boards.

If there is no conductive layer on the surface of the insulating layer, then dry plating or wet plating is used to form a conductive layer on the surface of the insulating layer. For dry plating, known methods such as vapor deposition, sputtering, and ion plating can be used. In the vapor deposition method (vacuum vapor deposition method), for example, a support is placed in a vacuum container, and a metal is heated and evaporated to form a metal film on the insulating layer. The sputtering method is also, for example, placing the support in a vacuum container, introducing an inert gas such as argon, and applying a DC voltage to make the free inert gas collide with the target metal, and use the knocked-out metal to form a metal on the insulating layer. metal film.

In the case of wet plating, the surface of the insulating layer that has been formed is sequentially subjected to swelling treatment using swelling solution, roughening treatment using oxidant, and neutralization treatment using neutralizing solution, so that the surface of the insulating layer roughen. The swelling treatment by swelling liquid is carried out by immersing the insulating layer in the swelling liquid at 50° C. to 80° C. for 1 minute to 20 minutes. Examples of the swelling solution include alkali solutions, and examples of the alkali solution include sodium hydroxide solutions, potassium hydroxide solutions, and the like. Commercially available swelling liquid, for example, APPDE S (registered trademark) MDS-37 manufactured by Uemura Industrial Co., Ltd. The roughening treatment by using an oxidizing agent is performed by immersing the insulating layer in an oxidizing agent solution at 60° C. to 80° C. for 5 minutes to 30 minutes. Oxidants, such as: potassium permanganate dissolved in aqueous solution of sodium hydroxide, alkaline permanganate solution of sodium permanganate, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, etc. Also, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Commercially available oxidizing agents, for example: alkaline permanganic acid solutions such as APPDES (registered trademark) MDE-40 and APPDES (registered trademark) ELC-SH manufactured by Uemura Industrial Co., Ltd. The neutralization treatment with the neutralizing solution is carried out by immersing in the neutralizing solution for 1 minute to 10 minutes at 30°C to 50°C. The neutralizing solution should preferably be an acidic aqueous solution, and the commercially available product can include APPDES (registered trademark) MDN-62 manufactured by Uemura Industrial Co., Ltd.

Next, a conductive layer is formed by combining electroless plating and electrolytic plating. It is also possible to form a plating photoresist with a pattern opposite to that of the conductor layer, and form the conductor layer only by electroless plating. Subsequent pattern forming methods are, for example, subtractive method, semi-additive method, and the like.

<Semiconductor Device> The semiconductor device of the present embodiment includes an interlayer insulating layer including the resin composition of the present embodiment, and can be specifically manufactured by the following method. A semiconductor device can be manufactured by mounting a semiconductor chip on the conductive portion of the multilayer printed circuit board of this embodiment. Here, the conduction point is the point where the electrical signal is transmitted in the multilayer printed circuit board, which can be on the surface or buried. Also, the semiconductor wafer is not particularly limited as long as it is an electrical circuit element made of a semiconductor.

The mounting method of the semiconductor chip when manufacturing the semiconductor device of this embodiment is not particularly limited as long as it can make the semiconductor chip function. The mounting method of the build-up layer (BBUL), the mounting method of using the anisotropic conductive film (ACF), the mounting method of using the non-conductive film (NCF), etc.

Moreover, a semiconductor device can also be manufactured by laminating|stacking the resin sheet of this embodiment on a semiconductor wafer. After lamination, it can be manufactured by the same method as the aforementioned multilayer printed wiring board. [Example]

Hereinafter, the present invention will be described more specifically according to synthesis examples and examples, but the present invention is not limited to these examples.

[Synthesis Example 1] (Synthesis of Cyanate Compound) 300 g (1.28 mol in terms of OH group) and 194.6 g (1.92 mol) (1.5 mol relative to 1 mol of hydroxyl group) was dissolved in 1800 g of dichloromethane, and named solution 1.

Cyanogen chloride 125.9g (2.05mol) (1.6mol relative to hydroxyl 1mol), dichloromethane 293.8g, 36% hydrochloric acid 194.5g (1.92mol) (relative to hydroxyl 1mol is 1.5mol), water 1205.9g in Keep the liquid temperature at -2~-0.5°C under stirring, and add solution 1 for 30 minutes. After the filling of solution 1, stir at the same temperature for 30 minutes, and then add the solution obtained by dissolving 65 g (0.64 mol) of triethylamine (0.5 mol relative to 1 mol of hydroxyl) in 65 g of dichloromethane (solution 2). After solution 2 was added, it was stirred at the same temperature for 30 minutes to complete the reaction. After that, the reaction solution was left to stand, and the organic phase and the aqueous phase were separated. The obtained organic phase was washed 5 times with 1300 g of water. The electrical conductivity of the wastewater washed with water for the fifth time was 5 μS/cm, and it was confirmed that the removable ionic compounds could be sufficiently removed by washing with water. The organic phase washed with water was concentrated under reduced pressure, and finally concentrated to dryness at 90° C. for 1 hour to obtain 331 g of the target naphthol aralkyl-type cyanate compound (SNCN) (orange sticky substance). The mass average molecular weight Mw of the obtained SNCN was 600. Also, the IR spectrum of SNCN shows the absorption at 2250 cm ^-1 (cyanate group) and does not show the absorption of hydroxyl group.

[Synthesis Example 2] (Synthesis of 2-functional phenylene ether oligomers with vinyl groups) Add CuBr 23.88g (17.4mmol ), N,N'-di-tert-butylethylenediamine 0.75g (4.4mmol), n-butyldimethylamine 28.04g (277.6mmol), toluene 2600g, stirred at a reaction temperature of 40°C, and pre-dissolved in 2,2',3,3',5,5'-hexamethyl-(1,1'-biphenol)-4,4'-diol 129.3g (0.48mol) of 2300g methanol, 2,6 -Dimethylphenol 233.7g (1.92mol), 2,3,6-trimethylphenol 64.9g (0.48mol), N,N'-di-tert-butylethylenediamine 0.51g (2.9 mmol), A mixed solution of 10.90g (108.0mmol) of n-butyldimethylamine was added dropwise for 230 minutes while mixing nitrogen and air to form a mixed gas with an oxygen concentration of 8% and bubbling at a flow rate of 5.2L/min. , and stir. After the dropwise addition, 1500 g of water in which 19.89 g (52.3 mmol) of tetrasodium ethylenediaminetetraacetate was dissolved was added to stop the reaction. The aqueous layer and the organic layer were separated, and the organic layer was washed with 1N aqueous hydrochloric acid solution and then with pure water. The obtained solution was concentrated to 50 wt% by an evaporator to obtain 836.5 g of a toluene solution of a bifunctional phenylene ether oligomer. 2 The number average molecular weight of the functional phenylene ether oligomer is 986, the weight average molecular weight is 1530, and the hydroxyl equivalent is 471.

(Synthesis of Vinyl Compounds) In a reactor equipped with a stirring device, a thermometer, and a reflux tube, 836.5 g of a toluene solution of bifunctional phenylene ether oligomers, vinyl benzyl chloride (trade names CMS-P, AGC Seimichemical Co., Ltd.) 162.6 g, 1600 g of dichloromethane, 12.95 g of benzyldimethylamine, 420 g of pure water, and 178.0 g of 30.5 wt% NaOH aqueous solution were stirred at a reaction temperature of 40°C. After stirring for 24 hours, the organic layer was washed with 1N aqueous hydrochloric acid solution and then with pure water. The obtained solution was concentrated by an evaporator, and it solidified by dripping into methanol, and the solid was collected by filtration, and it vacuum-dried to obtain 503.5 g of a vinyl compound. The number average molecular weight of the vinyl compound was 1187, the weight average molecular weight was 1675, and the vinyl equivalent was 590 g/vinyl.

[Example 1] (Manufacture of resin composition and prepreg) Methyl ethyl ketone (hereinafter sometimes referred to as MEK) slurry ( 0.5 μm PTFE-YA (trade name), volume average particle size of primary particles 0.5 μm, 20% by mass of non-volatile components, 250 parts by mass (manufactured by Admatechs Co., Ltd.) (50 parts by mass in terms of non-volatile components), as cyanide 2.1 parts by mass of SNCN obtained in Synthesis Example 1 of ester compound, prepolymer of 2,2-bis(4-cyanophenyl)propane (CA210 (trade name), cyanate equivalent 139, Mitsubishi Gas Chemical (manufactured by Co., Ltd.) 6.6 parts by mass, brominated bisphenol A type epoxy resin (E153 (trade name), epoxy equivalent 400, secondary hydroxyl group content 0.3meq/g, manufactured by DIC Co., Ltd.) 10.6 parts by mass, 77.5 parts by mass of the vinyl compound (number average molecular weight: 1187, vinyl equivalent: 590 g/vinyl) obtained in Synthesis Example 2 as a compound having an ethylenically unsaturated group, α-methylstyrene oligomer (KA3085 (trade name), mass average molecular weight: 664, manufactured by Eastman Chemical Company, USA) 3.2 parts by mass, MEK slurry of vinylsilane-treated silica (SC2050MNU (trade name), medium A diameter of 0.5 μm, 70% by mass of non-volatile content, and 71.4 parts by mass (manufactured by Admatechs) (50 parts by mass in terms of non-volatile content) were mixed to obtain a varnish (resin composition solution). The varnish was diluted with methyl ethyl ketone, dip-coated on E-glass woven fabric with a thickness of 0.1mm, and heated and dried at 160°C for 5 minutes to obtain a prepreg with a resin content of 50% by mass.

(Manufacturing of inner layer circuit board) For the glass cloth base material BT resin double-sided copper clad laminate (copper foil thickness 12μm, thickness 0.2mm, Mitsubishi Gas Chemical Co., Ltd.) On both sides of CCL (registered trademark)-HL83 2NS (trade name)), the copper surface was roughened with CZ8100 (trade name) manufactured by MEC Co., Ltd. to obtain an inner layer circuit board.

(Fabrication of metal foil-clad laminate) The above-mentioned prepreg was arranged on the top and bottom of the inner layer circuit board, and electrolytic copper foil (3EC-M3-VLP (trade name), manufactured by Mitsui Kinzoku Co., Ltd.) with a thickness of 12 μm was arranged on the top and bottom. , lamination molding was carried out at a pressure of 30 kgf/cm ² and a temperature of 220°C for 120 minutes to obtain a metal foil-clad laminate in which an inner layer circuit board, a resin composition layer, and a copper foil were laminated.

(Preparation of cured product for evaluation) Four sheets of the aforementioned prepreg were stacked, and 12 μm thick electrolytic copper foil (3EC-M3-VLP (trade name), manufactured by Mitsui Kinzoku Co., Ltd.) was placed up and down, under a pressure of 30 kgf /cm ² and a temperature of 220° C. for 120 minutes to obtain a metal foil-clad laminate with an insulating layer thickness of 0.4 mm. The entire metal foil of the obtained metal foil-clad laminate was etched away to obtain a cured product for evaluation.

[Example 2] MEK slurry (PTFE-YA4 (trade name) , the volume average particle diameter of the primary particle is 3.0 μm, the non-volatile content is 40% by mass, and Admatechs (stock) system) is changed to 125 mass parts (according to the non-volatile content conversion, it is 50 mass parts). In addition, it is the same as that of Example 1 A varnish was similarly prepared to obtain a prepreg, a metal foil-clad laminate, and a cured product for evaluation.

[Example 3] MEK slurry (0.5 μm PTFE-YA (trade name), volume average particle diameter of the primary particle 0.5 μm, 20% by mass of non-volatile components, 250 parts by mass (manufactured by Admatechs Co., Ltd.) (50 parts by mass in terms of non-volatile components), 2.0 parts by mass of SCNN obtained in Synthesis Example 1 of a cyanate compound, 2, Prepolymer of 2-bis(4-cyanophenyl)propane (CA210 (trade name), cyanate equivalent 139, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 6.2 parts by mass, bisbrominated epoxy resin Synthesis example 2 of 10.0 parts by mass of phenol A-type epoxy resin (E153 (trade name), epoxy equivalent 400, secondary hydroxyl group content 0.3 meq/g, manufactured by DIC Co., Ltd.) as a compound having an ethylenically unsaturated group The obtained vinyl compound (the number average molecular weight is 1187, and the vinyl equivalent is 590 g/vinyl) 72.8 parts by mass, α-methylstyrene oligomer (KA3085 (trade name), mass average molecular weight: 664, US Eastman Chemical Company) 3.0 parts by mass, MEK slurry of vinylsilane-treated silica as another filler (C) (SC2050MNU (trade name), median diameter 0.5 μm, non-volatile content 70% by mass, Admatec hs (stock) Manufactured) 71.4 parts by mass (50 parts by mass in terms of non-volatile components), brominated polycarbonate (FG8500 (trade name), manufactured by Teijin Co., Ltd., bromine content 58% by weight) as a flame retardant (D) 6 parts by mass were mixed to obtain a varnish. Thereafter, the same procedure as in Example 1 was carried out to obtain a prepreg, a metal foil-clad laminate, and a cured product for evaluation.

[Example 4] (Manufacture of resin composition and resin sheet) MEK slurry (0.5 μm PTFE-YA (trade name) , volume average particle diameter of primary particles 0.5 μm, 20% by mass of non-volatile components, 250 parts by mass (manufactured by Admatechs Co., Ltd.) (50 parts by mass in terms of non-volatile components), obtained as Synthesis Example 1 of cyanate compound 2.1 parts by mass of SNCN, 6.6 parts by mass of prepolymer of 2,2-bis(4-cyanophenyl)propane (CA210 (trade name), cyanate equivalent 139, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10.6 parts by mass of brominated bisphenol A type epoxy resin (E153 (trade name), epoxy equivalent 400, secondary hydroxyl content 0.3 meq/g, manufactured by DIC Co., Ltd.) 77.5 parts by mass of the vinyl compound (number average molecular weight: 1187, vinyl equivalent weight: 590 g/vinyl) obtained in Synthesis Example 2 of unsaturated group compound, α-methylstyrene oligomer (KA3085 (trade name), Mass average molecular weight: 664, manufactured by Eastman Chemical Company, USA) 3.2 parts by mass, MEK slurry of vinylsilane-treated silica (SC2050MNU (trade name), median diameter 0.5 μm, non-volatile component) as other filler (C) 70% by mass, Admatec hs Co., Ltd.) 71.4 parts by mass (50 parts by mass in terms of non-volatile components) were mixed to obtain a varnish. These varnishes were coated on an electrolytic copper foil (3EC-M2S-VLP (trade name), manufactured by Mitsui Kinzoku Co., Ltd.) with a thickness of 12 μm, and heated and dried at 120° C. for 5 minutes to obtain a copper foil as a support. The thickness of the resin composition layer is a resin sheet of 40 μm.

(Preparation of metal foil-clad laminate) The resin surface of the above-mentioned resin sheet with copper foil as a support was placed on the inner layer circuit board used in Example 1, and the process was carried out at a pressure of 30kgf/cm ² and a temperature of 220°C for 120 minutes. The laminate molding of the inner layer circuit board, the resin composition layer and the copper foil are laminated to obtain a metal foil-clad laminate.

(Preparation of cured product for evaluation) All metal foils of the obtained metal foil-clad laminate were etched away to obtain a cured product for evaluation.

[Comparative Example 1] The silica-coated fluororesin particles (A) were replaced with PTFE dispersion (EXP. FD-030 (trade name), median diameter 0.5 μm, non-volatile content 40% by mass, DIC ( Co., Ltd.) 125 parts by mass (50 parts by mass in terms of non-volatile components), the same procedure as in Example 3 was carried out to prepare a varnish to obtain a prepreg, a metal foil-clad laminate, and a cured product for evaluation.

[Comparative Example 2] MEK slurry (SC2050MNU (trade name), medium 0.5 μm in diameter, 70% by mass of non-volatile content, 142.9 parts by mass (manufactured by Admatechs Co., Ltd.) (100 parts by mass in terms of non-volatile content), and the same procedure as in Example 1 was carried out to prepare a varnish and obtain a prepreg , a metal foil-clad laminate, and a hardened product for evaluation.

[Example 5] MEK slurry (0.5 μm PTFE-YA (trade name), volume average particle diameter of primary particles 0.5 μm, 20% by mass of non-volatile components, 250 parts by mass (manufactured by Admatechs Co., Ltd.) (50 parts by mass in terms of non-volatile components), a maleimide compound (BMI-2300 ( trade name), Daiwa Chemical Industry Co., Ltd.) 3.5 parts by mass, biphenyl aralkyl type epoxy resin (NC3000H (trade name), Nippon Kayaku Co., Ltd.) 19.8 parts by mass as epoxy resin, Propylene glycol monomethyl ether acetate (hereinafter sometimes referred to as PMA) solution of acid-modified bisphenol F-type epoxy acrylate compound with ethylenically unsaturated group (KAYARAD (registered trademark) ZFR-1553H (trade name) , 68% by mass of non-volatile components, acid value: 70mgKOH/g, manufactured by Nippon Kayaku Co., Ltd.) 77.6 parts by mass (52.8 parts by mass in terms of non-volatile components), diperythritol hexaacrylate (KAYARAD ( Registered trademark) DPHA (trade name), Nippon Kayaku (Co., Ltd.) 18.9 parts by mass, 2-benzyl-2-dimethylamino-1-(4-𠰌line) as photocuring initiator (E) Substituted phenyl)-butan-1-one (Irgacure (registered trademark) 369 (trade name), BASF Japan (stock)) 5 parts by mass were blended, stirred with an ultrasonic homogenizer to obtain a solution of varnish (resin composition) ). These varnishes were coated on a PET film (Unipeel (registered trademark) TR1-38, manufactured by Unitika Co., Ltd., trade name) with a thickness of 38 μm, and heated and dried at 80° C. for 7 minutes to obtain a PET film as a support. The thickness of the resin composition layer is a resin sheet of 40 μm.

(Preparation of laminated body for evaluation) The resin surface of the above-mentioned resin sheet using the PET film as a support was placed on the inner layer circuit board used in Example 1, and a vacuum laminator (manufactured by Nikko Materials Co., Ltd.) was used. After 30 seconds of vacuum suction (below 5.0 MPa), lamination molding was performed at a pressure of 10kgf/cm ² and a temperature of 70°C for 30 seconds. Lamination molding was then performed at a pressure of 10 kgf/cm ² and a temperature of 70° C. for 60 seconds to obtain a laminate in which an inner layer circuit board, a resin composition layer, and a support were laminated. The obtained laminate was subjected to an exposure step of irradiating ultraviolet rays of 200 mJ/cm ² , the support was peeled off, and developed with a 1 mass % sodium carbonate aqueous solution to prepare a laminate for evaluation.

(Preparation of cured product for evaluation) The above-mentioned resin sheet was irradiated with ultraviolet rays of 200 mJ/cm ² , heat-treated at 180° C. for 120 minutes and baked, and then the support was peeled off to obtain a cured product for evaluation.

[Example 6] MEK slurry (0.5 μm PTFE-YA (trade name), volume average particle diameter of the primary particles 0.5 μm) as the silica-coated PTFE filler as the silica-coated fluororesin particles (A) , 20% by mass of non-volatile components, 100 parts by mass of Admatechs Co., Ltd. (manufactured by Admatechs Co., Ltd.) (20 parts by mass in terms of non-volatile components), maleimide compound (BMI-2300 (trade name), manufactured by Daiwa Chemical Industry Co., Ltd.) 3.5 parts by mass, 19.8 parts by mass of biphenyl aralkyl type epoxy resin (KAYARAD (registered trademark) NC3000H (trade name), manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin, as an epoxy resin having ethylenically unsaturated groups Compound PMA solution of acid-modified bisphenol F-type epoxy acrylate compound (KAYARAD (registered trademark) ZFR-1553H (trade name), non-volatile content 68% by mass, acid value: 70 mgKOH/g, Nippon Kayaku Co., Ltd. )) 77.6 parts by mass (52.8 parts by mass in terms of non-volatile components), diperythritol hexaacrylate (KAYARAD (registered trademark) DPHA (trade name), manufactured by Nippon Kayaku Co., Ltd.) 18.9 parts by mass 42.9 parts by mass of ME K slurry of epoxysilane-treated silica as another filler (C) (SC2050MB (trade name), median diameter 0.5 μm, non-volatile content 70% by mass, manufactured by Admatechs Co., Ltd.) 30 parts by mass in terms of non-volatile components), 2-benzyl-2-dimethylamino-1-(4-?olinophenyl)-butan-1- as a photocuring initiator (E) 5 parts by mass of ketone (Irgacure (registered trademark) 369 (trade name), manufactured by BASF Japan Co., Ltd.) was blended, stirred with an ultrasonic homogenizer, and a varnish was obtained. Thereafter, it carried out similarly to Example 5, and obtained the resin sheet, the laminated body for evaluation, and the cured product for evaluation.

[Example 7] MEK slurry (PTFE-YA4 (trade name) of silica-coated PTFE filler having a volume average particle diameter of 3.0 μm as primary particles of silica-coated fluororesin particles (A) was used , the volume average particle diameter of the primary particles is 3.0 μm, the non-volatile content is 40% by mass, Admatechs Co., Ltd.) 125 parts by mass (50 parts by mass in terms of non-volatile components), and the varnish is prepared in the same manner as in Example 5 except that , to obtain a resin sheet, a laminate for evaluation, and a cured product for evaluation.

[Example 8] PMA solution (KAYARAD (registered trademark) ZFR-1553H (trade name), non-volatile component 68 wt. %, acid value: 70mgKOH/g, Nippon Kayaku Co., Ltd.) is replaced by the PMA solution (KAYARAD (registered trademark) ZCR-6007H (trade name) of TrisP-PA epoxy acrylate compound represented by formula (4) , 65% by mass of non-volatile components, acid value: 70mgKOH/g, manufactured by Nippon Kayaku Co., Ltd.) 81.2 parts by mass (52.8 parts by mass in terms of non-volatile components), except that it is carried out in the same manner as in Example 5 to prepare The varnish was used to obtain a resin sheet, a laminate for evaluation, and a cured product for evaluation. In addition, the above-mentioned KAYARAD (registered trademark) ZCR-6007H is a mixture containing the above-mentioned compound (A1) and any one or more of the above-mentioned compounds (A2) to (A5).

[Comparative Example 3] The silica-coated fluororesin particles (A) were replaced with PTFE dispersion (EXP. FD-030 (trade name), median diameter 0.5 μm, non-volatile content 40% by mass, DIC ( Co., Ltd.) 125 parts by mass (50 parts by mass in terms of non-volatile components), a varnish was prepared in the same manner as in Example 5, and a resin sheet, a laminate for evaluation, and a cured product for evaluation were obtained.

[Comparative Example 4] MEK slurry (SC2050MB (trade name), medium 0.5 μm in diameter, 70% by mass of non-volatile components, 71.4 parts by mass of Admatechs Co., Ltd. (manufactured by Admatechs Co., Ltd.) (50 parts by mass in terms of non-volatile components), except that a varnish was prepared in the same manner as in Example 5 to obtain a resin sheet and evaluation Laminates and cured products for evaluation.

[Measurement and evaluation of physical properties] The metal foil-clad laminate, the laminate for evaluation, and the cured product for evaluation were measured and evaluated according to the following methods. Their results are summarized in Tables 1-3.

<Wiring embedding property> A test piece of a 50mm×50mm metal-clad laminate with all the copper foil etched away except for one half of one side, or a test piece of a 50mm×50mm laminate for evaluation, using a pressure cooker The testing machine (manufactured by Hirayama Seisakusho, PC-3 type) was treated at 121°C and 2 atmospheres for 5 hours, then dipped in solder at 260°C for 60 seconds, and the appearance changes were visually observed and evaluated according to the following criteria. ⊚: No swelling occurred in any of the five test pieces. ◯: Protrusion occurred in 1 of 5 test pieces. ×: Swelling occurred in 2 or more of the 5 test pieces.

<Solder heat resistance> Let the test piece of the metal foil-clad laminate 50mm×50mm or the test piece of the laminate for evaluation 50mm×50mm be floated in the solder at 280°C for 30 minutes to visually observe whether there is any abnormality in the appearance, and follow the The following benchmark evaluation. ◯: No swelling occurred in any of the five test pieces. ×: One or more of the five test pieces was raised.

<Dielectric constant, dielectric tangent> The dielectric constant and dielectric tangent of 10 GHz were measured by the cavity resonator perturbation method (Agilent (registered trademark) 8722ES, manufactured by Agilent Technologies) of the test piece of the cured product for evaluation.

<Developability> After visually observing the developed surface of the laminate for evaluation, it was observed by SEM (magnification: 1000 times), and the presence or absence of residue was evaluated according to the following criteria. ○: There is no development residue in the square area of 30 mm, and the developability is excellent. ×: There are development residues in the square area of 30 mm, and the developability is poor.

<Heat Resistance (Glass Transition Temperature)> Using a DMA device (Dynamic Viscoelasticity Measuring Device DMAQ800 (trade name) manufactured by TA INSTRUMENT Co., Ltd.), the cured product for evaluation was heated up at 10°C/min, and the position of the peak of LossModulus was defined as the glass transition temperature (Tg).

【Table 1】

【Table 2】

【table 3】

As can be seen from Table 1, Table 2, and Table 3, Examples 1 to 8 are excellent in wiring embedding property and heat resistance, and have good dielectric constant and dielectric tangent. Among them, in Example 1, Example 4, and Example 5, the wiring embedding property and the dielectric constant were good. In Example 8, the heat resistance (Tg) was higher and was good. On the other hand, comparative examples 1 to 4 are not satisfactory in wiring embedding property, heat resistance and dielectric constant. Therefore, according to the present invention, a resin composition excellent in dielectric constant, dielectric tangent, fine wiring embedment property, heat resistance, and developability, a prepreg, a metal foil-clad laminate, and a resin sheet using the composition can be obtained. , printed circuit boards and semiconductor devices.

Claims (12)

A resin composition comprising silica-coated fluororesin particles (A) and a resin component (B), wherein the volume-average particle diameter of the primary particles of the silica-coated fluororesin particles (A) is 2 μm or less, The resin component (B) contains a compound having an ethylenically unsaturated group, and the compound having an ethylenically unsaturated group includes a compound selected from difunctional phenylene ether oligomers having vinyl groups, α-methylbenzene In the group consisting of oligomers of ethylene, acid-modified bisphenol F-type epoxy (meth)acrylate, compounds represented by the following general formula (1), and dineopentaerythritol hexa(meth)acrylate at least one of them;

In the formula (1), a plurality of R _1s independently represent a hydrogen atom or a methyl group, and a plurality of R ₂ independently represent a hydrogen atom or a methyl group, and a plurality of R ₃ independently represent a hydrogen atom or a methyl group represented by the following formula (2) A substituent, a substituent represented by the following formula (3) or a hydroxyl group;

In formula (3), R ₄ represents a hydrogen atom or a methyl group. Such as the resin composition of claim 1, wherein the content of the silicon dioxide-coated fluororesin particles (A) in the resin composition is relative to 100 parts by mass of the resin solid content in the resin composition. 3~400 parts by mass. Such as the resin composition of claim 1, wherein the resin component (B) further contains a compound selected from maleimide compounds, cyanate compounds, epoxy resins, phenol resins, oxetane Resin, and benzo

Any one or more of the group consisting of compounds. If the resin composition of claim 1, it further contains filler (C) other than the silicon dioxide-coated fluororesin particles (A). For example, the resin composition of item 1 of the scope of the patent application further contains a flame retardant (D). For example, the resin composition of claim 1 of the patent scope further contains a photocuring initiator (E). The resin composition of claim 1, wherein the compound having an ethylenically unsaturated group includes at least the compound represented by the general formula (1). A prepreg, comprising: a base material, and the resin composition according to any one of items 1 to 7 of the patent application scope impregnated or coated on the base material. A metal foil-clad laminate, comprising: at least one or more laminated prepregs according to claim 8, and metal foils arranged on one or both sides of the prepregs. A resin sheet, comprising: a support body, and a resin composition according to any one of items 1 to 7 of the scope of the patent application arranged on the surface of the support body. A printed circuit board with the resin composition according to any one of items 1 to 7 in the scope of the patent application. A semiconductor device having the resin composition according to any one of items 1 to 7 of the patent application scope.