JP2018030974A - Resin composition, prepreg, metal foil-clad laminate, laminate resin sheet, resin sheet, and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition excellent in copper foil peel strength, plating peel strength, flexural strength, water absorption, dielectric constant, thermal expansion coefficient, and heat weight loss, and a prepreg, a metal foil-clad laminate, a laminate resin sheet, a resin sheet, and a printed wiring board prepared with the resin composition.SOLUTION: A resin composition contains a cyanate compound (A), a maleimide compound (B), and an acrylate compound (C) having an epoxy group, a (meth) acrylate group, and a bisphenol A type skeleton.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, a prepreg, a metal foil-clad laminate, a laminated resin sheet, a resin sheet, and a printed wiring board.

  In recent years, high integration and miniaturization of semiconductors widely used in electronic devices, communication devices, personal computers and the like have been accelerated. As a result, various characteristics required for semiconductor package laminates used for printed wiring boards have become increasingly severe. The required properties include, for example, properties such as low water absorption, moisture absorption heat resistance, flame retardancy, low dielectric constant, low dielectric loss tangent, low thermal expansion coefficient, heat resistance, chemical resistance, and high plating peel strength. However, so far, these required characteristics have not always been satisfied.

  As a printed wiring board material having excellent dielectric properties, for example, a resin composition containing a bifunctional polyphenylene ether resin having a specific structure, a thermosetting resin, and a curing agent for the thermosetting resin is known. (For example, refer to Patent Document 1).

JP 2005-112981 A

  However, the technique described in Patent Document 1 has a problem that copper foil peel strength and plating peel strength are inferior.

  The present invention has been made in view of the above problems, a resin composition excellent in copper foil peel strength, plating peel strength, bending strength, water absorption, dielectric constant, thermal expansion coefficient, thermal weight reduction rate, and An object is to provide a prepreg, a metal foil-clad laminate, a laminated resin sheet, a resin sheet, and a printed wiring board using the resin composition.

  The present inventors diligently studied to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by using the specific acrylate compound (C), and the present invention has been completed.

That is, the present invention is as follows.
[1]
A cyanate ester compound (A);
A maleimide compound (B);
An acrylate compound (C) having an epoxy group, a (meth) acrylate group, and a bisphenol A-type skeleton,
Resin composition.
[2]
The acrylate compound (C) includes a compound represented by the following formula (1).
[1] The resin composition according to [1].
(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, It is a substituent selected from the group consisting of an alkoxyl group having 1 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a hydroxyl group, an amide group, and a halogen atom, and n is an integer of 1 to 20. )
[3]
Content of the said acrylate compound (C) is 0.5-30 mass parts with respect to 100 mass parts of resin solid content,
The resin composition as described in [1] or [2].
[4]
From the group consisting of a compound (H) having a polymerizable unsaturated group other than the epoxy resin (D), the phenol resin (E), the okitacene resin (F), the benzoxazine resin (G), and the acrylate compound (C). Further containing one or more selected components,
The resin composition according to any one of [1] to [3].
[5]
Further containing a filler (I),
The resin composition according to any one of [1] to [4].
[6]
Content of the said filler (I) is 50-1600 mass parts with respect to 100 mass parts of resin solid content,
[5] The resin composition according to [5].
[7]
A substrate;
The resin composition according to any one of [1] to [6], impregnated or coated on the substrate.
Prepreg.
[8]
The prepreg according to [7], wherein at least one sheet is laminated;
A metal foil disposed on one or both sides of the prepreg,
Metal foil-clad laminate.
[9]
A support;
The resin composition according to any one of [1] to [6], disposed on the surface of the support,
Laminated resin sheet.
[10]
Including the resin composition according to any one of [1] to [6],
Resin sheet.
[11]
An insulating layer;
A conductor layer formed on the surface of the insulating layer,
The insulating layer includes the resin composition according to any one of [1] to [6].
Printed wiring board.

  According to the present invention, a copper foil peel strength, plating peel strength, bending strength, water absorption rate, dielectric constant, thermal expansion coefficient, thermal weight reduction rate, and a prepreg and metal using the resin composition A foil-clad laminate, a laminated resin sheet, a resin sheet, and a printed wiring board can be provided.

  Hereinafter, the embodiment of the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to this, and various modifications are possible without departing from the scope of the present invention. It is.

(Resin composition)
The resin composition of this embodiment contains a cyanate ester compound (A), a maleimide compound (B), an acrylate compound (C) having an epoxy group, a (meth) acrylate group, and a bisphenol A skeleton. To do.

[Cyanate ester compound (A)]
The cyanate ester compound (A) used in the present embodiment is not particularly limited as long as it is a resin having in its molecule an aromatic moiety substituted with at least one cyanate group (cyanate ester group).

For example, what is represented by General formula (2) is mentioned.
Here, in the formula, Ar ₁ represents a single bond of a benzene ring, a naphthalene ring or two benzene rings. When there are a plurality, they may be the same or different. Each Ra is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 6 carbon atoms and an alkyl group having 6 to 12 carbon atoms. A group to which an aryl group is bonded is shown. The aromatic ring in Ra may have a substituent, and the substituent in Ar ₁ and Ra can be selected at any position. p is a number of cyanate groups bonded to Ar _1, is an integer of 1 to 3 independently. q indicates the number of Ra bonded to Ar _1, and 4-p when Ar ₁ is a benzene ring, 6-p when Ar ₁ is a naphthalene ring, and 8-p when two benzene rings are a single bond. . t represents an average number of repetitions and is an integer of 0 to 50, and the other cyanate ester compound may be a mixture of compounds having different t. When there are a plurality of Xs, each independently represents a single bond, a divalent organic group having 1 to 50 carbon atoms (a hydrogen atom may be substituted with a hetero atom), or a divalent group having 1 to 10 nitrogen atoms. An organic group (for example, —N—R—N— (wherein R represents an organic group)), a carbonyl group (—CO—), a carboxy group (—C (═O) O—), a carbonyl dioxide group ( —OC (═O) O—), a sulfonyl group (—SO ₂ —), a divalent sulfur atom, or a divalent oxygen atom.

  The alkyl group in Ra of the general formula (2) may have any of a linear or branched chain structure and a cyclic structure (for example, a cycloalkyl group).

  In addition, the hydrogen atom in the alkyl group in the general formula (2) and the aryl group in Ra is substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, or a cyano group. Also good.

  Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1-ethylpropyl group, 2,2-dimethylpropyl group. Group, cyclopentyl group, hexyl group, cyclohexyl group, and trifluoromethyl group.

  Specific examples of the aryl group include phenyl group, xylyl group, mesityl group, naphthyl group, phenoxyphenyl group, ethylphenyl group, o-, m- or p-fluorophenyl group, dichlorophenyl group, dicyanophenyl group, trifluorophenyl. A group, a methoxyphenyl group, and an o-, m- or p-tolyl group. Furthermore, examples of the alkoxyl group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group.

  Specific examples of the divalent organic group having 1 to 50 carbon atoms in X of the general formula (2) include a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, a trimethylcyclohexylene group, and biphenylyl. Examples include a methylene group, dimethylmethylene-phenylene-dimethylmethylene group, fluorenediyl group, and phthalidodiyl group. 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 alkoxyl group such as a methoxy group or a phenoxy group, a cyano group, or the like.

  Examples of the divalent organic group having 1 to 10 nitrogen atoms in X of the general formula (2) include an imino group and a polyimide group.

Moreover, as an organic group of X in General formula (2), what is a structure represented by the following general formula (3) or the following general formula (4) is mentioned, for example.
Here, in the formula, Ar ₂ represents a benzenetetrayl group, a naphthalenetetrayl group or a biphenyltetrayl group, and when u is 2 or more, they may be the same as or different from each other. Rb, Rc, Rf and Rg are each independently an aryl having at least one hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group, or a phenolic hydroxy group. Indicates a group. Rd and Re are each independently selected from any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, and a hydroxy group. . u represents an integer of 0 to 5.
In the formula, Ar ₃ represents a benzenetetrayl group, a naphthalenetetrayl group or a biphenyltetrayl group, and when v is 2 or more, they may be the same or different from each other. Ri and Rj are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxyl group having 1 to 4 carbon atoms, a hydroxy group, a trifluoromethyl group, Or an aryl group substituted with at least one cyanato group. v represents an integer of 0 to 5, but may be a mixture of compounds having different v.

Furthermore, as X in General formula (2), the bivalent group represented by a following formula is mentioned.
Here, in the formula, z represents an integer of 4 to 7. Rk each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Specific examples of Ar ₃ of Ar ₂ and of the general formula (3) (4), two carbon atoms shown in the general formula (3), or two oxygen atoms shown in the general formula (4) A benzenetetrayl group bonded to the 1,4-position or the 1,3-position, the two carbon atoms or the two oxygen atoms are in the 4,4′-position, 2,4′-position, 2,2′-position, 2 , 3′-position, 3,3′-position, or 3,4′-position, and the above two carbon atoms or two oxygen atoms are in the 2,6-position, 1,5-position , 1,6-position, 1,8-position, 1,3-position, 1,4-position, or 2,7-position.

  Rb, Rc, Rd, Re, Rf and Rg in the general formula (3), and the alkyl group and aryl group in Ri and Rj in the general formula (4) have the same meanings as those in the general formula (2).

Specific examples of the cyanato-substituted aromatic compound represented by the general formula (2) include cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methylbenzene, 1 -Cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methoxybenzene, 1-cyanato-2,3-, 1-cyanato-2,4-, 1-cyanato-2,5-, 1-cyanato-2,6-, 1-cyanato-3,4- or 1-cyanato-3,5-dimethylbenzene, cyanatoethylbenzene, cyanatobutylbenzene, cyanatooctylbenzene, cyanatononylbenzene, 2- (4-cyanaphenyl) -2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenze 1-cyanato-2- or 1-cyanato-3-chlorobenzene, 1-cyanato-2,6-dichlorobenzene, 1-cyanato-2-methyl-3-chlorobenzene, cyanatonitrobenzene, 1-cyanato-4-nitro 2-ethylbenzene, 1-cyanato-2-methoxy-4-allylbenzene (eugenol cyanate), methyl (4-cyanatophenyl) sulfide, 1-cyanato-3-trifluoromethylbenzene, 4-cyanatobiphenyl, 1-cyanato-2- or 1-cyanato-4-acetylbenzene, 4-cyanatobenzaldehyde, 4-cyanatobenzoic acid methyl ester, 4-cyanatobenzoic acid phenyl ester, 1-cyanato-4-acetaminobenzene, 4- Cyanatobenzophenone, 1-cyanato-2,6-di-tert -Butylbenzene, 1,2-dicyanatobenzene, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,4-dicyanato-2-tert-butylbenzene, 1,4-dicyanato-2,4 -Dimethylbenzene, 1,4-dicyanato-2,3,4-dimethylbenzene, 1,3-dicyanato-2,4,6-trimethylbenzene, 1,3-dicyanato-5-methylbenzene, 1-cyanato or 2 -Cyanatonaphthalene, 1-cyanato-4-methoxynaphthalene, 2-cyanato-6-methylnaphthalene, 2-cyanato-7-methoxynaphthalene, 2,2'-dicyanato-1,1'-binaphthyl, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,6- or 2,7-dicyanatosinaphthalene, 2,2'- or 4,4'- Dicyanato Biphenyl, 4,4′-dicyanatooctafluorobiphenyl, 2,4′- or 4,4′-dicyanatodiphenylmethane, bis (4-cyanato-3,5-dimethylphenyl) methane, 1,1-bis (4 -Cyanatophenyl) ethane, 1,1-bis (4-cyanatophenyl) propane, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis (4-cyanato-3-methylphenyl) Propane, 2,2-bis (2-cyanato-5-biphenylyl) propane, 2,2-bis (4-cyanatophenyl) hexafluoropropane, 2,2-bis (4-cyanato-3,5-dimethyl) Phenyl) propane, 1,1-bis (4-cyanatophenyl) butane, 1,1-bis (4-cyanatophenyl) isobutane, 1,1-bis (4-cyanatophenyl) pe Tan, 1,1-bis (4-cyanatophenyl) -3-methylbutane, 1,1-bis (4-cyanatophenyl) -2-methylbutane, 1,1-bis (4-cyanatophenyl) -2 , 2-dimethylpropane, 2,2-bis (4-cyanatophenyl) butane, 2,2-bis (4-cyanatophenyl) pentane, 2,2-bis (4-cyanatophenyl) hexane, 2, 2-bis (4-cyanatophenyl) -3-methylbutane, 2,2-bis (4-cyanatophenyl) -4-methylpentane, 2,2-bis (4-cyanatophenyl) -3,3- Dimethylbutane, 3,3-bis (4-cyanatophenyl) hexane, 3,3-bis (4-cyanatophenyl) heptane, 3,3-bis (4-cyanatophenyl) octane, 3,3-bis (4-cyanatopheny ) -2-methylpentane, 3,3-bis (4-cyanatophenyl) -2-methylhexane, 3,3-bis (4-cyanatophenyl) -2,2-dimethylpentane, 4,4-bis (4-Cyanatophenyl) -3-methylheptane, 3,3-bis (4-cyanatophenyl) -2-methylheptane, 3,3-bis (4-cyanatophenyl) -2,2-dimethylhexane 3,3-bis (4-cyanatophenyl) -2,4-dimethylhexane, 3,3-bis (4-cyanatophenyl) -2,2,4-trimethylpentane, 2,2-bis (4 -Cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, bis (4-cyanatophenyl) phenylmethane, 1,1-bis (4-cyanatophenyl) -1-phenylethane Bis (4-cyanato Phenyl) biphenylmethane, 1,1-bis (4-cyanatophenyl) cyclopentane, 1,1-bis (4-cyanatophenyl) cyclohexane, 2,2-bis (4-cyanato-3-isopropylphenyl) propane 1,1-bis (3-cyclohexyl-4-cyanatophenyl) cyclohexane, bis (4-cyanatophenyl) diphenylmethane, bis (4-cyanatophenyl) -2,2-dichloroethylene, 1,3-bis [ 2- (4-Cyanatophenyl) -2-propyl] benzene, 1,4-bis [2- (4-cyanatophenyl) -2-propyl] benzene, 1,1-bis (4-cyanatophenyl) -3,3,5-trimethylcyclohexane, 4- [bis (4-cyanatophenyl) methyl] biphenyl, 4,4-dicyanatobenzopheno 1,3-bis (4-cyanatophenyl) -2-propen-1-one, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) sulfide, bis (4-cyanatophenyl) Sulfone, 4-cyanatobenzoic acid-4-cyanatophenyl ester (4-cyanatophenyl-4-cyanatobenzoate), bis- (4-cyanatophenyl) carbonate, 1,3-bis (4-cyanatophenyl) Adamantane, 1,3-bis (4-cyanatophenyl) -5,7-dimethyladamantane, 3,3-bis (4-cyanatophenyl) isobenzofuran-1 (3H) -one (cyanate of phenolphthalein) ), 3,3-bis (4-cyanato-3-methylphenyl) isobenzofuran-1 (3H) -one (o-cresolphthalein Nate), 9,9'-bis (4-cyanatophenyl) fluorene, 9,9-bis (4-cyanato-3-methylphenyl) fluorene, 9,9-bis (2-cyanato-5-biphenylyl) Fluorene, tris (4-cyanatophenyl) methane, 1,1,1-tris (4-cyanatophenyl) ethane, 1,1,3-tris (4-cyanatophenyl) propane, α, α, α ′ -Tris (4-cyanatophenyl) -1-ethyl-4-isopropylbenzene, 1,1,2,2-tetrakis (4-cyanatophenyl) ethane, tetrakis (4-cyanatophenyl) methane, 2,4 , 6-Tris (N-methyl-4-cyanatoanilino) -1,3,5-triazine, 2,4-bis (N-methyl-4-cyanatoanilino) -6- (N-methylanilino) -1,3 -Triazine, bis (N-4-cyanato-2-methylphenyl) -4,4'-oxydiphthalimide, bis (N-3-cyanato-4-methylphenyl) -4,4'-oxydiphthalimide, bis (N-4-cyanatophenyl) -4,4′-oxydiphthalimide, bis (N-4-cyanato-2-methylphenyl) -4,4 ′-(hexafluoroisopropylidene) diphthalimide, tris (3 , 5-Dimethyl-4-cyanatobenzyl) isocyanurate, 2-phenyl-3,3-bis (4-cyanatophenyl) phthalimidine, 2- (4-methylphenyl) -3,3-bis (4-si Anatophenyl) phthalimidine, 2-phenyl-3,3-bis (4-cyanato-3-methylphenyl) phthalimidine, 1-methyl-3,3-bis (4-cyanato) Eniru) indolin-2-one, and 2-phenyl-3,3-bis (4-cyanatophenyl) include indolin-2-one. Other specific examples of the compound represented by the general formula (2) include phenol novolac resins and cresol novolac resins (phenol, alkyl-substituted phenol or halogen-substituted phenol, formalin, paraformaldehyde, etc. by a known method). Of formaldehyde compound in an acidic solution), trisphenol novolak resin (reacted hydroxybenzaldehyde and phenol in the presence of an acidic catalyst), fluorene novolak resin (fluorenone compound and 9,9-). bis (hydroxyaryl) fluorenes those reacted in the presence of an acid catalyst), phenol aralkyl resins, cresol aralkyl resin, a naphthol aralkyl resin and a biphenyl aralkyl resin (a known method, Ar ₄ - ( H ₂ Y) ₂ (Ar ₄ represents a phenyl group, Y. Below a halogen atom, in this paragraph as well. A bishalogenomethyl compound and a phenol compound such as represented by) an acidic catalyst or no catalyst A reaction product, a reaction product of a bis (alkoxymethyl) compound represented by Ar ₄ — (CH ₂ OR) ₂ and a phenol compound in the presence of an acidic catalyst, or Ar ₄ — (CH ₂ OH) ₂ represented by reacting a bis (hydroxymethyl) compound and a phenol compound in the presence of an acidic catalyst, or a polycondensation of an aromatic aldehyde compound, an aralkyl compound and a phenol compound) Phenol-modified xylene formaldehyde resin (existing acidic catalyst with xylene formaldehyde resin and phenol compound by a known method) Modified), modified naphthalene formaldehyde resin (reacted in the presence of an acidic catalyst with a naphthalene formaldehyde resin and a hydroxy-substituted aromatic compound by a known method), phenol-modified dicyclopentadiene resin, polynaphthylene Phenol resins such as phenol resins having an ether structure (polyhydric hydroxynaphthalene compound having two or more phenolic hydroxy groups in one molecule by dehydration condensation in the presence of a basic catalyst) , Cyanates by the same method as described above, and prepolymers thereof. These are not particularly limited. These other cyanate ester compounds can be used alone or in combination.

  Among them, phenol novolac type cyanate ester compound, naphthol aralkyl type cyanate ester compound, biphenyl aralkyl type cyanate ester compound, naphthylene ether type cyanate ester compound, xylene resin type cyanate ester compound, adamantane skeleton type cyanate ester Compounds are preferred, and naphthol aralkyl cyanate compounds are particularly preferred.

  The cured resin using these cyanate ester compounds has excellent properties such as glass transition temperature, low thermal expansion, and plating adhesion.

  It does not specifically limit as a manufacturing method of these cyanate ester compounds (A), A well-known method can be used. Examples of such production methods include a method of obtaining or synthesizing a hydroxy group-containing compound having a desired skeleton, and modifying the hydroxy group by a known method to form cyanate. Examples of the method for cyanating a hydroxy group include the method described in Ian Hamerton, “Chemistry and Technology of Cyanate Esters Resins,” “Blackie Academic & Professional”.

  The content of the cyanate ester compound (A) is preferably 1 to 90 parts by mass, more preferably 20 to 75 parts by mass, further preferably 100 parts by mass of the resin solid content in the resin composition. Is 40-60 parts by mass. When the content of the cyanate ester compound (A) is 1 part by mass or more, the coefficient of thermal expansion tends to be further reduced.

  In the present embodiment, “resin solid content” means a component in the resin composition excluding the solvent and filler (I), unless otherwise specified, and “resin solid content of 100 parts by mass”. Means that the total of the components excluding the solvent and filler (I) in the resin composition is 100 parts by mass.

[Maleimide compound (B)]
The maleimide compound (B) is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule, 4,4-diphenylmethane bismaleimide, phenylmethane maleimide, m-phenylene bismaleimide, 2, 2-bis (4- (4-maleimidophenoxy) -phenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1 , 6-Bismaleimide- (2,2,4-trimethyl) hexane, 4,4-diphenyl ether bismaleimide, 4,4-diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3 -Bis (4-maleimidophenoxy) benzene, novolac maleimide compound, Prepolymer phenyl aralkyl type maleimide and prepolymers, or a maleimide compound and an amine compound of these maleimide compounds. These maleimide compounds can be used alone or in combination.

  Among these, a novolak type maleimide compound and a biphenylaralkyl type bismaleimide are preferable. By using such a maleimide compound (B), the heat resistance tends to be further improved.

  The content of the maleimide compound (B) is preferably 1 to 90 parts by mass, more preferably 20 to 75 parts by mass, and further preferably 40 to 60 parts by mass with respect to 100 parts by mass of the resin solid content. is there. When the content of the maleimide compound (B) is 1 part by mass or more, the heat resistance tends to be further improved.

[Acrylate compound (C)]
The acrylate compound (C) is not particularly limited as long as it is a compound having an epoxy group, a (meth) acrylate group, and a bisphenol A skeleton, and examples thereof include a compound represented by the following formula (1). Thus, by using an acrylate compound (C) having both an epoxy group and a (meth) acrylate group and having a bisphenol A skeleton, copper foil peel strength, plating peel strength, and bending strength are further improved. The water absorption, dielectric constant, thermal expansion coefficient, and thermal weight reduction rate tend to be further reduced. In addition, a commercial item can also be used as an acrylate compound (C). Although it does not specifically limit as a commercial item, For example, Shin-Nakamura Chemical Co., Ltd. make, NK oligo EA-1010N etc. are mentioned.
(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, It is a substituent selected from the group consisting of an alkoxyl group having 1 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a hydroxy group, an amide group, and a halogen atom, and n is an integer of 1 to 20. )

  The hydrocarbon group having 1 to 10 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. It is done. The hydrocarbon group may be linear, branched or cyclic.

  Although it does not specifically limit as a C1-C10 alkoxyl group, For example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a heptyloxy group, a hexyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group Groups.

  The aryloxy group having 6 to 10 carbon atoms is not particularly limited, and examples thereof include a phenoxy group, a 2-methylphenoxy group, and a 4-t-butylphenoxy group.

Of the compounds represented by the formula (1), compounds in which R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ are all hydrogen atoms are preferred.

  The content of the acrylate compound (C) is preferably 0.5 to 30 parts by mass, more preferably 3 to 25 parts by mass, and further preferably 5 to 15 parts by mass with respect to 100 parts by mass of the resin solid content. Part. When the content of the acrylate compound (C) is 0.5 parts by mass or more, the copper foil peel strength, plating peel strength, and bending strength are further improved, and the water absorption rate, dielectric constant, thermal expansion coefficient, thermal weight reduction rate Tend to be lower.

[Filler (I)]
It is preferable that the resin composition of this embodiment further contains a filler (I). Although it does not specifically limit as filler (I), For example, an inorganic filler and an organic filler are mentioned. The filler (I) may be used alone or in combination of two or more.

  Examples of the inorganic filler include, but are not limited to, silicas such as natural silica, fused silica, synthetic silica, amorphous silica, aerosil, and hollow silica; silicon compounds such as white carbon; titanium white, zinc oxide, magnesium oxide, Metal oxides such as zirconium oxide; nitrides such as boron nitride, agglomerated boron nitride, silicon nitride, and aluminum nitride; metal sulfates such as barium sulfate; aluminum hydroxide, aluminum hydroxide heat-treated products (heat treatment of aluminum hydroxide) In addition, metal hydrates such as boehmite and magnesium hydroxide; molybdenum compounds such as molybdenum oxide and zinc molybdate; zinc compounds such as zinc borate and zinc stannate; alumina, Clay, kaolin, talc, calcined clay, calcined kaolin Baked talc, mica, E glass, A glass, NE glass, C glass, L glass, D glass, S glass, M glass G20, short glass fiber (E glass, T glass, D glass, S glass, Q glass Glass fine powders, etc.), hollow glass, spherical glass and the like.

  Further, the organic filler is not particularly limited, and examples thereof include rubber powder such as styrene type powder, butadiene type powder, acrylic type powder; core shell type rubber powder; silicone resin powder; silicone rubber powder; It is done.

  Of these, one or more selected from the group consisting of silica, aluminum hydroxide, boehmite, magnesium oxide and magnesium hydroxide are preferred. By using such a filler (I), the thermal expansion coefficient of the cured product of the resin composition tends to be further reduced.

  The content of the filler (I) is preferably 50 to 1600 parts by mass, more preferably 60 to 1200 parts by mass, and further preferably 70 to 1000 parts by mass with respect to 100 parts by mass of the resin solid content. Yes, particularly preferably 80 to 800 parts by mass. When the content of the filler (I) is 50 parts by mass or more, the thermal expansion coefficient tends to be further reduced.

[Silane coupling agent and wetting and dispersing agent]
The resin composition of this embodiment may further contain a silane coupling agent or a wetting and dispersing agent.

  Although it will not specifically limit if it is a silane coupling agent generally used for the surface treatment of an inorganic substance as a silane coupling agent, For example, (gamma) -aminopropyl triethoxysilane, N-beta- (aminoethyl) -gamma Aminosilane compounds such as aminopropyltrimethoxysilane; Epoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane; Acrylicsilane compounds such as γ-acryloxypropyltrimethoxysilane; N-β- (N- Cationic silane compounds such as vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride; phenylsilane compounds and the like. A silane coupling agent may be used individually by 1 type, or may use 2 or more types together.

  The wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used for paints. For example, DISPER-110, 111, 118, 180, 161, BYK-W996 manufactured by Big Chemie Japan Co., Ltd. , W9010, W903, and the like.

[Other ingredients]
The resin composition of the present embodiment may contain other components as necessary in addition to the above components. Although it does not specifically limit as another component, For example, the compound (H) which has an epoxy resin (D), a phenol resin (E), an oxetane resin (F), a benzoxazine compound (G), and a polymerizable unsaturated group 1) or more selected from the group consisting of

(Epoxy resin (D))
As the epoxy resin (D), generally known compounds can be used as long as they are compounds having two or more epoxy groups in one molecule, and the kind thereof is not particularly limited. Specific examples thereof include bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolak. Type epoxy resin, xylene novolac type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthalene skeleton modified novolak type epoxy resin, naphthylene ether type epoxy resin, phenol aralkyl type epoxy resin, anthracene type epoxy resin, trifunctional Phenol type epoxy resin, tetrafunctional phenol type epoxy resin, triglycidyl isocyanurate, glycidyl ester type epoxy resin, alicyclic epoxy Fatty, dicyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, phenol aralkyl novolak type epoxy resin, naphthol aralkyl novolak type epoxy resin, aralkyl novolak type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclo Pentadiene type epoxy resin, polyol type epoxy resin, phosphorus-containing epoxy resin, compound obtained by epoxidizing double bond such as glycidylamine, butadiene, etc., compound obtained by reaction of hydroxyl group-containing silicone resin and epichlorohydrin, or halides thereof Etc. These epoxy resins can be used alone or in combination of two or more.

Among these, the epoxy resin is preferably at least one selected from the group consisting of biphenyl aralkyl type epoxy resins, naphthylene ether type epoxy resins, polyfunctional phenol type epoxy resins, and naphthalene type epoxy resins. By including such an epoxy resin, the flame retardancy and heat resistance of the obtained cured product tend to be further improved.

(Phenolic resin (E))
As the phenol resin (E), generally known one can be used as long as it is a phenol resin having two or more hydroxy groups in one molecule, and the kind thereof is not particularly limited. Specific examples thereof include bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolac type. Phenol resin, biphenyl aralkyl type phenol resin, cresol novolac type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolac resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolak type phenol resin, phenol aralkyl type phenol resin Naphthol aralkyl type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type phenolic resin Nord resins, alicyclic phenolic resins, polyol-type phenolic resin, a phosphorus-containing phenol resin, a hydroxyl group-containing silicone resins and the like, but is not particularly limited. These phenol resins can be used individually by 1 type or in combination of 2 or more types.

(Oxetane resin (F))
Generally well-known thing can be used as oxetane resin (F), The kind is not specifically limited. Specific examples thereof include alkyl oxetanes such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3 ′. -Di (trifluoromethyl) perfluoxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl type oxetane, OXT-101 (trade name, manufactured by Toagosei), OXT-121 (produced by Toagosei) Product name). These oxetane resins can be used alone or in combination of two or more.

(Benzoxazine compound (G))
As the benzoxazine compound (G), generally known compounds can be used as long as they have two or more dihydrobenzoxazine rings in one molecule, and the kind thereof is not particularly limited. Specific examples thereof include bisphenol A-type benzoxazine BA-BXZ (trade name, manufactured by Konishi Chemical) bisphenol F-type benzoxazine BF-BXZ (trade name, manufactured by Konishi Chemical), bisphenol S-type benzoxazine BS-BXZ (product manufactured by Konishi Chemical) Name). These benzoxazine compounds can be used alone or in combination.

(Compound having a polymerizable unsaturated group (H))
As the compound (J) having a polymerizable unsaturated group other than the acrylate compound (C), generally known compounds can be used, and the kind thereof is not particularly limited. Specific examples thereof include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, divinylbiphenyl; methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polypropylene glycol di ( Mono- or polyhydric alcohol (meth) such as (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate Acrylates; Epoxy (meth) acrylates such as bisphenol A type epoxy (meth) acrylate and bisphenol F type epoxy (meth) acrylate; , Allyl ether, propylene, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl isophthalate, allyl compounds such as diallyl maleate, and a benzocyclobutene resin. These compounds having an unsaturated group can be used alone or in combination.

[Curing accelerator]
The resin composition of this embodiment may further contain a curing accelerator. Although it does not specifically limit as a hardening accelerator, For example, imidazoles, such as triphenylimidazole; benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate, etc. Organic peroxides; azo compounds such as azobisnitrile; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine , Pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, tertiary amines such as N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcin, catechol ; Organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetone; these organic metal salts are phenol, bisphenol, etc. Inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; ditinyl tin oxide, and other organic tin compounds such as alkyl tin and alkyl tin oxide. Among these, triphenylimidazole promotes the curing reaction and is particularly preferable because it tends to have excellent glass transition temperature and coefficient of thermal expansion.

〔solvent〕
The resin composition of this embodiment may further contain a solvent. By including the solvent, the viscosity at the time of preparing the resin composition is lowered, the handling property is further improved, and the impregnation property to the base material described later tends to be further improved.

  The solvent is not particularly limited as long as it can dissolve a part or all of the resin component in the resin composition. For example, ketones such as acetone, methyl ethyl ketone, and methyl cellosolve; aromatics such as toluene and xylene Group hydrocarbons; amides such as dimethylformamide; propylene glycol monomethyl ether and acetate thereof. A solvent may be used individually by 1 type, or may use 2 or more types together.

[Method for producing resin composition]
Although the manufacturing method of the resin composition of this embodiment is not specifically limited, For example, the method of mix | blending each component with a solvent one by one and fully stirring is mentioned. At this time, in order to uniformly dissolve or disperse each component, known processes such as stirring, mixing, and kneading can be performed. Specifically, the dispersibility of the filler (I) with respect to the resin composition can be improved by performing the stirring and dispersing treatment using a stirring tank provided with a stirrer having an appropriate stirring ability. The above stirring, mixing, and kneading treatment can be appropriately performed using, for example, a known device such as a ball mill or a bead mill for mixing, or a revolving or rotating mixing device.

  Moreover, when preparing the resin composition of this embodiment, an organic solvent can be used as needed. The kind of the organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition. Specific examples thereof are as described above.

[Use]
The resin composition of this embodiment can be suitably used as a prepreg, a metal foil-clad laminate, a laminated resin sheet, a resin sheet, or a printed wiring board. Hereinafter, a prepreg, a metal foil-clad laminate, a laminated resin sheet, a resin sheet, or a printed wiring board will be described.

[Prepreg]
The prepreg of this embodiment has a base material and the resin composition impregnated or coated on the base material. The manufacturing method of a prepreg can be performed according to a conventional method, and is not specifically limited. For example, after impregnating or applying the resin component in the present embodiment to the base material, by semi-curing (B stage) by heating in a dryer at 100 to 200 ° C. for 1 to 30 minutes, The prepreg of this embodiment can be produced.

  The content of the resin composition (including the filler (I)) is preferably 30 to 90% by mass, more preferably 35 to 85% by mass, and still more preferably 40% with respect to the total amount of the prepreg. -80 mass%. When the content of the resin composition is within the above range, the moldability tends to be further improved.

  It does not specifically limit as a base material, The well-known thing used for various printed wiring board materials can be selected suitably according to the intended use and performance, and can be used. Although it does not specifically limit as a specific example of the fiber which comprises a base material, For example, glass fibers, such as E glass, D glass, S glass, Q glass, spherical glass, NE glass, L glass, T glass; Quartz etc. Inorganic fibers other than glass: polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont), copolyparaphenylene 3,4'oxydiphenylene terephthalamide (Technola (registered trademark), Teijin Techno Products ( A wholly aromatic polyamide such as 2,6-hydroxynaphthoic acid / parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Kuraray Co., Ltd.), polyester such as Zexion (registered trademark, manufactured by KB Seiren); Polyparaphenylene benzoxazole (Zylon (registered trademark), manufactured by Toyobo Co., Ltd.), polyimide Which organic fibers, and the like. Among these, from the viewpoint of a low thermal expansion coefficient, at least one selected from the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth, and organic fibers is preferable. These base materials may be used individually by 1 type, or may use 2 or more types together.

Although it does not specifically limit as a shape of a base material, For example, a woven fabric, a nonwoven fabric, roving, a chopped strand mat, a surfacing mat, etc. are mentioned. The weaving method of the woven fabric is not particularly limited, and for example, plain weave, Nanako weave, twill weave and the like are known, and can be appropriately selected from these known ones depending on the intended use and performance. . In addition, a glass woven fabric whose surface is treated with a fiber-opening treatment or a silane coupling agent is preferably used. Although the thickness and mass of the substrate are not particularly limited, those having a thickness of about 0.01 to 0.3 mm are preferably used. In particular, from the viewpoint of strength and water absorption, the substrate is preferably a glass woven fabric having a thickness of 200 μm or less and a mass of 250 g / m ² or less, and a glass woven fabric made of glass fibers of E glass, S glass, and T glass. More preferred.

[Laminated resin sheet]
The laminated resin sheet of this embodiment has a support and the resin composition disposed on the support. The laminated resin sheet is used as one means for thinning, and can be produced, for example, by directly applying and drying a resin composition on a support such as a metal foil or a film.

  Although it does not specifically limit as a support body, The well-known thing used for various printed wiring board materials can be used. For example, polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, polycarbonate film, ethylene tetrafluoroethylene copolymer film, and Organic film base materials such as release films with release agents applied to the surfaces of these films, conductor foils such as aluminum foil, copper foil, and gold foil, plate-like inorganic systems such as glass plates, SUS plates, and FPR A film is mentioned. Among these, electrolytic copper foil and PET film are preferable.

  Examples of the coating method include a method in which a solution obtained by dissolving the resin composition of the present embodiment in a solvent is coated on a support with a bar coater, a die coater, a doctor blade, a baker applicator, or the like.

  The laminated resin sheet is preferably one obtained by applying the resin composition to a support and then semi-curing (B-stage). Specifically, for example, after the resin composition is applied to a support such as a copper foil, it is semi-cured by a method of heating in a dryer at 100 to 200 ° C. for 1 to 60 minutes, and a laminated resin sheet is obtained. The manufacturing method etc. are mentioned. The amount of the resin composition attached to the support is preferably in the range of 1 to 300 μm in terms of the resin thickness of the laminated resin sheet.

[Resin sheet]
The resin sheet of this embodiment contains a resin composition. The resin sheet is formed by molding a resin composition into a sheet shape. The manufacturing method of a resin sheet can be performed according to a conventional method, and is not specifically limited. For example, it can be obtained by peeling or etching the support from the laminated resin sheet. In addition, without using a sheet base material, a solution obtained by dissolving the resin composition of the present embodiment in a solvent is supplied into a mold having a sheet-like cavity and dried to be formed into a sheet shape. A resin sheet (single layer resin sheet) can also be obtained.

[Metal foil-clad laminate]
The metal foil-clad laminate of this embodiment includes at least one or more of the prepregs laminated and a metal foil disposed on one or both sides of the prepreg. That is, the metal foil-clad laminate of this embodiment is obtained by laminating and curing the prepreg and the metal foil.

  The conductor layer can be a metal foil such as copper or aluminum. Although the metal foil used here will not be specifically limited if it is used for printed wiring board material, Well-known copper foils, such as a rolled copper foil and an electrolytic copper foil, are preferable. Moreover, although the thickness of a conductor layer is not specifically limited, 1-70 micrometers is preferable, More preferably, it is 1.5-35 micrometers.

The molding method and molding conditions of the metal foil-clad laminate are not particularly limited, and general techniques and conditions of a printed wiring board laminate and a multilayer board can be applied. For example, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, etc. can be used at the time of forming a metal foil-clad laminate. In forming a metal foil-clad laminate, the temperature is generally 100 to 350 ° C., the pressure is ^{2 to} 100 kgf / cm ² , and the heating time is generally 0.05 to 5 hours. Furthermore, if necessary, post-curing can be performed at a temperature of 150 to 350 ° C. Also, a multilayer board can be formed by laminating and combining the above-described prepreg and a separately prepared wiring board for an inner layer.

[Printed wiring board]
The printed wiring board of this embodiment is a printed wiring board including an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer includes the resin composition. The metal foil-clad laminate can be suitably used as a printed wiring board by forming a predetermined wiring pattern. The above metal foil-clad laminate has a low coefficient of thermal expansion, good moldability and chemical resistance, and is particularly effectively used as a printed wiring board for semiconductor packages that require such performance. Can do.

  Specifically, the printed wiring board of this embodiment can be manufactured by the following method, for example. First, the metal foil-clad laminate (such as a copper-clad laminate) is prepared. An inner layer circuit is formed by etching the surface of the metal foil-clad laminate to produce an inner layer substrate. The inner layer circuit surface of this inner layer substrate is subjected to a surface treatment to increase the adhesive strength as necessary, then the required number of the above-mentioned prepregs are stacked on the inner layer circuit surface, and a metal foil for outer layer circuits is stacked on the outer side. Then, it is integrally molded by heating and pressing. In this way, a multilayer laminate is produced in which an insulating layer made of a cured material of the base material and the thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit. Next, after this multi-layer laminate is subjected to drilling for through holes and via holes, desmear treatment is performed to remove smears, which are resin residues derived from the resin component contained in the cured product layer. . After that, a plated metal film is formed on the wall surface of this hole to connect the inner layer circuit and the metal foil for the outer layer circuit, and the outer layer circuit is formed by etching the metal foil for the outer layer circuit to produce a printed wiring board. Is done.

  The printed wiring board obtained in the above production example has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer includes the above-described resin composition of the present embodiment. That is, the above-mentioned prepreg (the base material and the above-described resin composition attached thereto) and the metal foil-clad laminate resin composition layer (the layer composed of the above-mentioned resin composition) include the above-described resin composition. An insulating layer is formed.

  In the case where a metal foil-clad laminate is not used, a printed wiring board may be produced by forming a conductor layer serving as a circuit on the prepreg, the laminated resin sheet, or the resin composition. At this time, a method of electroless plating can be used for forming the conductor layer.

  The printed wiring board of the present embodiment is a semiconductor because the above-mentioned insulating layer has excellent characteristics such as copper foil peel strength, plating peel strength, bending strength, water absorption, dielectric constant, thermal expansion coefficient, and thermal weight reduction rate. It can be used particularly effectively as a printed wiring board for a package.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. The present invention is not limited in any way by the following examples.

[Synthesis Example 1] Synthesis of 1-naphthol aralkyl type cyanate ester resin (SNCN) In a reactor, α-naphthol aralkyl resin (SN495V, OH group equivalent: 236 g / eq., Manufactured by Nippon Steel Chemical Co., Ltd.) 300 g (OH group equivalent 1.28 mol) and triethylamine 194.6 g (1.92 mol) (1.5 mol with respect to 1 mol of hydroxy group) were dissolved in 1800 g of dichloromethane, and this was used as solution 1.

  125.9 g (2.05 mol) of cyanogen chloride (1.6 mol with respect to 1 mol of hydroxy group), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol with respect to 1 mol of hydroxy group), While maintaining 1205.9 g of water at a liquid temperature of −2 to −0.5 ° C. with stirring, Solution 1 was poured over 30 minutes. After the completion of the pouring of solution 1, after stirring at the same temperature for 30 minutes, a solution (solution 2) in which 65 g (0.64 mol) of triethylamine (0.5 mol with respect to 1 mol of hydroxy group) was dissolved in 65 g of dichloromethane was added for 10 minutes. Over time. After the end of pouring the solution 2, the reaction was completed by stirring at the same temperature for 30 minutes.

  Thereafter, the reaction solution was allowed to stand to separate an organic phase and an aqueous phase. The obtained organic phase was washed 5 times with 1300 g of water, and the electric conductivity of the waste water in the fifth washing was 5 μS / cm, and it was confirmed that the ionic compounds that could be removed were sufficiently removed by washing with water.

The organic phase after washing with water was concentrated under reduced pressure, and finally concentrated to dryness at 90 ° C. for 1 hour to obtain 331 g of the intended naphthol aralkyl-type cyanate ester compound (SNCN) (orange viscous product). The obtained SNCN had a mass average molecular weight Mw of 600. Further, the infrared absorption spectrum of SNCN showed absorption of 2250 cm ⁻¹ (cyanate ester group) and did not show absorption of hydroxy group.

Example 1
45 parts by mass of SNCN obtained by Synthesis Example 1, 45 parts by mass of a novolac-type maleimide compound (manufactured by Daiwa Kasei Kogyo Co., Ltd., BMI-2300), an acrylate compound represented by the following formula (1 ′) (Shin Nakamura Chemical Industries ( Co., Ltd., NK Oligo EA-1010N) 10 parts by mass, fused silica (SC2050MB, manufactured by Admatechs Co., Ltd.) 100 parts by mass, zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.) 0.12 parts by mass And got a varnish.

(Comparative Example 1)
Instead of the acrylate compound represented by the above formula (1 ′) (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Oligo EA-1010N), an acrylate having no epoxy group and bisphenol A type skeleton (Shin-Nakamura Chemical Co., Ltd.) ), Vanaresin GH-1203) 10 parts by mass, and the amount of zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.) was 0.08 parts by mass. A varnish was obtained.

(Comparative Example 2)
Without using an acrylate compound represented by the above formula (1 ′) (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Oligo EA-1010N), the amount of SNCN used was 50 parts by mass, and a novolac maleimide compound (Daiwa Kasei Kogyo) Example 1 except that the amount of BMI-2300 used is 50 parts by mass and the amount of zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.) is 0.1 parts by mass. A varnish was obtained by the operation.

[Method for producing copper-clad laminate]
The varnish obtained as described above was impregnated and coated on a 0.1 mm thick E glass cloth, and 150 ° C., 5 ° C. using a dryer (fireproof explosion-proof steam dryer, manufactured by Takasugi Seisakusho Co., Ltd.). Heat drying for a minute, and the prepreg of 50 mass% of resin compositions was obtained. Two or eight of these prepregs are stacked, and 12 μm thick electrolytic copper foil (3EC-M3-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd.) is placed on both sides and vacuumed at a pressure of 30 kg / cm ² and a temperature of 220 ° C. for 150 minutes. Pressing was performed to obtain a copper clad laminate having an insulating layer thickness of 0.2 mm and 0.8 mm. The following evaluation was performed using the obtained copper-clad laminate. The results are shown in Table 1.

[Copper foil peel strength]
Using the test piece (30 mm × 150 mm × thickness 0.8 mm) of a copper clad laminate having an insulating layer thickness of 0.8 mm obtained as described above, a copper clad laminate test method for printed wiring boards according to JIS C6481 The peel strength of the copper foil was measured three times in accordance with (See 5.7 Peel Strength), and the average value of the lower limit values was taken as the measured value.

  The copper foil in the surface layer of the copper clad laminate having an insulating layer thickness of 0.2 mm obtained above was removed by etching, and an electroless copper plating process (name of chemical used: MCD-PL, manufactured by Uemura Kogyo Co., Ltd.) MDP-2, MAT-SP, MAB-4-C, MEL-3-APEA ver. 2) About 0.5 μm of electroless copper plating is applied to the insulating layer and dried at 130 ° C. for 1 hour. went. Subsequently, electrolytic copper plating was performed so that the thickness of the plated copper was 20 μm, and drying was performed at 180 ° C. for 1 hour. In this way, a test piece of a printed wiring board in which a conductor layer (plated copper) having a thickness of 20 μm was formed on an insulating layer having a thickness of 0.2 mm was prepared and used for evaluation of an electroless plating peel.

[Plating peel strength]
Using the test piece obtained as described above, the plating peel strength (adhesive force) was measured three times in accordance with JIS C6481, and the average value was obtained. The test piece swollen by drying after electrolytic copper plating was evaluated using a non-swollen portion. The results are shown in Table 1.

[Bending strength]
After removing the copper foils on both sides of the copper-clad laminate with an insulating layer thickness of 0.8 mm by etching, a test piece (50 mm × 25 mm × 0.8 mm) was used in accordance with JIS C 6481, and the number of tests was 5 The bending strength was measured with, and the average of the maximum values was taken as the measured value.

[Water absorption rate]
Using a test piece of a copper clad laminate having an insulating layer thickness of 0.8 mm obtained as described above, according to JIS C 6481, using a pressure cooker tester (Hirayama Seisakusho, PC-3 type), The water absorption after treatment at 121 ° C. and 2 atm for 5 hours was measured.

[Dielectric constant (Dk)]
Using the test piece obtained by removing the copper foil of the copper-clad laminate with an insulating layer thickness of 0.8 mm obtained as described above by etching, using the cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies), The measurement of the dielectric constant of 2 GHz was performed 3 times, and the average value was obtained.

[Coefficient of thermal expansion]
Using a test piece obtained by removing the copper foil of the copper clad laminate having an insulating layer thickness of 0.8 mm obtained by etching as described above, a thermomechanical analyzer (TA instrument) according to JlSC 6481 The temperature was increased from 40 ° C. to 340 ° C. at 10 ° C. per minute by the TMA method (Thermo-mechanical analysis), and the linear thermal expansion coefficient (ppm / ° C.) from 60 ° C. to 120 ° C. was measured.

[Thermal weight reduction rate]
After removing the copper foil of the copper-clad laminate having an insulating layer thickness of 0.8 mm obtained by etching as described above, the differential thermothermal gravimetric simultaneous measurement apparatus TG / DTA6200 (S) is compliant with JIS K7120-1987. -450 ° C. and 500 ° C. when heated at a start temperature of 30 ° C. and a temperature increase rate of 10 ° C./min under a nitrogen flow with a test piece of 3 mm × 3 mm × 0.8 mm, manufactured by I / I Nanotechnology Co., Ltd. The thermal weight loss rate (thermal decomposition amount (%)) at the time when the temperature reached ° C. was measured based on the following formula.
Weight reduction rate (%) = (I−J) / I × 100
I represents the weight at the starting temperature, and J represents the weight at 450 ° C. or 500 ° C.

  The resin composition of the present invention has industrial applicability as a material for prepreg, metal foil-clad laminate, laminated resin sheet, resin sheet, printed wiring board, and the like.

Claims (11)

A cyanate ester compound (A);
A maleimide compound (B);
An acrylate compound (C) having an epoxy group, a (meth) acrylate group, and a bisphenol A-type skeleton,
Resin composition. The acrylate compound (C) includes a compound represented by the following formula (1).
The resin composition according to claim 1.
(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, It is a substituent selected from the group consisting of an alkoxyl group having 1 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a hydroxyl group, an amide group, and a halogen atom, and n is an integer of 1 to 20. ) Content of the said acrylate compound (C) is 0.5-30 mass parts with respect to 100 mass parts of resin solid content,
The resin composition according to claim 1 or 2. From the group consisting of a compound (H) having a polymerizable unsaturated group other than the epoxy resin (D), the phenol resin (E), the okitacene resin (F), the benzoxazine resin (G), and the acrylate compound (C). Further containing one or more selected components,
The resin composition as described in any one of Claims 1-3. Further containing a filler (I),
The resin composition as described in any one of Claims 1-4. Content of the said filler (I) is 50-1600 mass parts with respect to 100 mass parts of resin solid content,
The resin composition according to claim 5. A substrate;
The resin composition according to any one of claims 1 to 6, which is impregnated or applied to the substrate.
Prepreg. The prepreg according to claim 7, wherein at least one sheet is laminated,
A metal foil disposed on one or both sides of the prepreg,
Metal foil-clad laminate. A support;
The resin composition according to any one of claims 1 to 6, which is disposed on a surface of the support.
Laminated resin sheet. Including the resin composition according to any one of claims 1 to 6,
Resin sheet. An insulating layer;
A conductor layer formed on the surface of the insulating layer,
The insulating layer contains the resin composition according to any one of claims 1 to 6,
Printed wiring board.