JP2018123196A - Resin composition, prepreg, metal foil-clad laminate, resin sheet, and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition that excels particularly in copper foil peel strength and glass transition temperature (Tg) among the properties required for a laminate for printed wiring boards, and provide a prepreg, a metal foil-clad laminate, a resin sheet, and a printed wiring board using the resin composition.SOLUTION: A resin composition contains a maleimide compound represented by the formula (1) (A) and a cyanate compound (B).SELECTED DRAWING: None

Description

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

  In recent years, higher 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, low water absorption, moisture absorption heat resistance, flame resistance, low dielectric constant, low dielectric loss tangent, low coefficient of thermal expansion, heat resistance, chemical resistance, high copper foil peel strength, high plating peel strength, high Properties such as glass transition temperature (high Tg) can be mentioned. 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 it is inferior in copper foil peel strength and glass transition temperature (Tg).

  The present invention has been made in view of the above problems, and among various properties required for a laminate for printed wiring boards, in particular, a resin composition excellent in copper foil peel strength and glass transition temperature (Tg), and An object is to provide a prepreg, a metal foil-clad laminate, a resin sheet, and a printed wiring board using the resin composition.

  As a result of intensive studies to solve the above-described problems, the present inventors have been able to increase the copper foil peel strength and the glass transition temperature (Tg) particularly in a laminated board for printed wiring boards by using a specific maleimide compound. The present inventors have found that this can be done and have completed the present invention.

That is, the present invention is as follows.
[1]
A maleimide compound (A) represented by the following formula (1);
A cyanate ester compound (B);
Containing a resin composition.

[2]
The content of the maleimide compound (A) in the resin composition is 1 to 90 parts by mass with respect to 100 parts by mass of the resin solid content.
[1] The resin composition according to [1].

[3]
The cyanate ester compound (B) includes a naphthol aralkyl type cyanate ester compound,
The resin composition as described in [1] or [2].

[4]
Further containing a filler (C),
The resin composition according to any one of [1] to [3].

[5]
Further containing at least one member selected from the group selected from maleimide compounds other than the maleimide compound (A), epoxy resins, phenol resins, oxetane resins, benzoxazine compounds, and compounds having a polymerizable unsaturated group To
The resin composition according to any one of [1] to [4].

[6]
Content in the resin composition of the said filler (C) is 50-1600 mass parts with respect to 100 mass parts of resin solid content,
The resin composition as described in [4] or [5].

[7]
A substrate;
The resin composition according to any one of [1] to [6], impregnated or coated on the substrate;
Prepreg with

[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;
A metal foil-clad laminate.

[9]
The resin sheet containing the resin composition as described in any one of [1]-[6].

[10]
An insulating layer;
A conductor layer formed on the surface of the insulating layer;
Have
The insulating layer includes the resin composition according to any one of [1] to [6].
Printed wiring board.

  According to the present invention, among various properties required for a laminate for a printed wiring board, in particular, a resin composition excellent in copper foil peel strength and glass transition temperature (Tg), and a prepreg and metal using the resin composition A foil-clad laminate, a resin sheet, and a printed wiring board can be provided.

  Hereinafter, embodiments of the present invention (hereinafter referred to as “present embodiments”) will be described in detail. However, the present invention is not limited thereto, and various modifications can be made without departing from the scope of the present invention. is there. In the present embodiment, “resin solid content” means a component in the resin composition excluding the solvent and filler (C) unless otherwise specified, and “resin solid content 100 parts by mass”. Means that the total of the components excluding the solvent and filler (C) in the resin composition is 100 parts by mass.

(Resin composition)
The resin composition of this embodiment contains a maleimide compound (A) and a cyanate ester compound (B).

[Maleimide compound (A)]
The maleimide compound (A) used in this embodiment is a bismaleimide of 1,3-bis (aminomethyl) cyclohexane represented by the following formula (1).

  This maleimide compound (A) can be synthesized, for example, by the method described in JP-A-9-249645. Specifically, the maleimide compound (A) can be produced by reacting 1,3-bis (aminomethyl) cyclohexane and maleic anhydride.

  In this reaction, generally, maleic anhydride is used in an amount twice as much as 1,3-bis (aminomethyl) cyclohexane, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, or aprotic such as dimethylformamide and dimethylacetamide are used. A first stage reaction performed at a reaction temperature of about 0 to 15 ° C. using a polar solvent as a reaction solvent is first performed to obtain a predetermined bis-maleamic acid as an intermediate.

  In the second stage reaction, generally, the formed bis-maleamic acid is not particularly separated, and a basic catalyst such as triethylamine is added to the reaction mixture at about 0.01 to 0.1 with respect to the bis-maleamic acid. Further, a dehydrating agent such as acetic anhydride is added at a molar ratio of about 1 to 3 with respect to the bis-maleamic acid, and the reaction is performed at a reaction temperature of about 15 to 50 ° C. for about 1 to 3 hours. The maleimide compound (A) represented by the above formula (1) as a cyclization reaction product is obtained.

  Content of a maleimide compound (A) is not specifically limited, Preferably it is 1-90 mass parts with respect to 100 mass parts of resin solid content, More preferably, it is 30-70 mass parts, More preferably, it is 40. It is -60 mass parts, Especially preferably, it is 45-55 mass parts. When the content of the maleimide compound (A) is within the above range, the copper foil peel strength of the resulting cured product is improved, and the glass is used even though the maleimide compound (A) has a fatty chain in the molecular skeleton. The transition temperature (Tg) tends to improve.

[Cyanate ester compound (B)]
The cyanate ester compound (B) 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).

  As an example of such a cyanate ester compound (B), one represented by the following formula (2) can be mentioned.

Here, in the formula (2), Ar ₁ represents a single bond of a benzene ring, a naphthalene ring or two benzene rings, and when there are a plurality of them, 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 6 to 12 carbon atoms. Represents a group bonded to the aryl group. The aromatic ring in Ra may have a substituent, and the substituent in Ar ₁ and Ra can be selected at any position. p indicates the number of cyanate groups bonded to Ar _1, is an integer of 1 to 3 independently. q represents 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 single-bonded. is there. t represents an average number of repetitions and is in the range of 0 to 50. The cyanate ester compound (B) 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 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 Formula (2) and the aryl group in Ra 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, or a cyano group. 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 in the formula (2) include a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, a trimethylcyclohexylene group, and a biphenylylmethylene group. Group, dimethylmethylene-phenylene-dimethylmethylene group, fluorenediyl group, phthalidodiyl group and the like. 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 formula (2) include an imino group and a polyimide group.

  Moreover, as an organic group of X in Formula (2), what is a structure represented by following formula (3) or following formula (4) is mentioned, for example.

Here, in Formula (3), 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 each independently have 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. An aryl group is shown. 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. The u represents an integer of 0 to 5.

Here, in the formula (4), 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. 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, Alternatively, it represents an aryl group substituted with at least one cyanato group. v represents an integer of 0 to 5, but v may be a mixture of different compounds.

  Furthermore, as X in 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.

Equation (3) Specific examples of Ar ₃ of Ar ₂ and (4) of the formula (3) two two oxygen atoms shown in the carbon atom or the formula (4) shown in the 1,4-position Alternatively, a benzenetetrayl group bonded to the 1,3-position, the above two carbon atoms or two oxygen atoms are in the 4,4′-position, 2,4′-position, 2,2′-position, 2,3′-position, The biphenyltetrayl group bonded to the 3,3′-position or the 3,4′-position and the two carbon atoms or the 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, naphthalenetetrayl group.

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

  Specific examples of the cyanato-substituted aromatic compound represented by the above 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-cyanphenyl) -2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenzene, -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-cyanato Benzophenone, 1-cyanato-2,6-di-tert-butyl Tylbenzene, 1,2-dicyanatobenzene, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,4-dicyanato-2-tert-butylbenzene, 1,4-dicyanato-2,4-dimethyl Benzene, 1,4-dicyanato-2,3,4-dimethylbenzene, 1,3-dicyanato-2,4,6-trimethylbenzene, 1,3-dicyanato-5-methylbenzene, 1-cyanato or 2-si Anatonaphthalene, 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'-dicyanana 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-cyanatopheny) ) Pentane, 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-Cyanatov Enyl) -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-dimethyl Hexane, 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-phenyl Ethane, bis (4-si Natophenyl) 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-dicyanatobenzo Enone, 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-cyanato) Phenyl) adamantane, 1,3-bis (4-cyanatophenyl) -5,7-dimethyladamantane, 3,3-bis (4-cyanatophenyl) isobenzofuran-1 (3H) -one (for phenolphthalein) Cyanate), 3,3-bis (4-cyanato-3-methylphenyl) isobenzofuran-1 (3H) -one (o-cresolphthalein) Cyanate), 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)- , 3,5-triazine, bis (N-4-cyanato-2-methylphenyl) -4,4′-oxydiphthalimide, bis (N-3-cyanato-4-methylphenyl) -4,4′-oxy Diphthalimide, 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-Cyanatophenyl) phthalimidine, 2-phenyl-3,3-bis (4-cyanato-3-methylphenyl) phthalimidine, 1-methyl-3,3-bis 4-cyanatophenyl) indolin-2-one, and 2-phenyl-3,3-bis (4-cyanatophenyl) include indolin-2-one.

Further, other specific examples of the compound represented by the above formula (2) include phenol novolak resins and cresol novolak resins (such as phenol, alkyl-substituted phenol or halogen-substituted phenol, formalin, paraformaldehyde and the like by a known method). Formaldehyde compound reacted 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 - (CH ₂ ) ₂ (Ar ₄ represents a phenyl group, Y represents a halogen atom. Hereinafter, the same.) A bishalogenomethyl compound and a phenol compound such as represented by is reacted with an acid catalyst or no catalyst in this paragraph A compound obtained by reacting a bis (alkoxymethyl) compound and a phenol compound represented by Ar ₄ — (CH ₂ OR) ₂ in the presence of an acidic catalyst, or Ar ₄ — (CH ₂ OH) ₂ A bis (hydroxymethyl) compound and a phenol compound represented by the above formula in the presence of an acidic catalyst, or a polycondensation of an aromatic aldehyde compound, an aralkyl compound and a phenol compound), phenol modification Xylene formaldehyde resin (reacts xylene formaldehyde resin and phenolic compound in the presence of an acidic catalyst by a known method. Modified naphthalene formaldehyde resin (reacted naphthalene formaldehyde resin and hydroxy-substituted aromatic compound in the presence of an acidic catalyst by a known method), phenol-modified dicyclopentadiene resin, polynaphthylene ether structure A phenol resin such as a phenol resin (a polyhydric hydroxy naphthalene compound having two or more phenolic hydroxy groups in one molecule by dehydration condensation in the presence of a basic catalyst), Examples thereof include those cyanated by the same method, and prepolymers thereof, and these are not particularly limited. These cyanate ester compounds (B) can be used alone or in combination of two or more.

  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 (B) has excellent properties such as glass transition temperature (Tg) and plating adhesion.

  A method for producing these cyanate ester compounds (B) is not particularly limited, and a 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 (B) is preferably 1 to 90 parts by mass, more preferably 30 to 70 parts by mass, and still more preferably 45 to 55 parts by mass with respect to 100 parts by mass of the resin solid content. Part. When the content of the cyanate ester compound (B) is within the above range, the heat resistance and chemical resistance of the obtained cured product tend to be further improved.

  The ratio (β / α) of the number (β) of cyanate groups (cyanate groups) of the cyanate ester compound (B) to the number (α) of maleimide groups of the maleimide compound (A) is preferably 0. It is 30 or more, More preferably, it is 0.30-2.0, More preferably, it is 0.40-1.1. When this ratio (β / α) is within the above range, the glass transition temperature (Tg) of the obtained cured product tends to be further improved.

[Filler (C)]
It is preferable that the resin composition of this embodiment further contains a filler (C). It does not specifically limit as a filler (C), For example, an inorganic filler and an organic filler are mentioned. A filler (C) can be used individually by 1 type or in combination of 2 or more types.

  The inorganic filler is not particularly limited, and examples thereof include 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, aggregated boron nitride, silicon nitride and aluminum nitride; metal sulfates such as barium sulfate; aluminum hydroxide and 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, calcined talc, ma F, E glass, A glass, NE glass, C glass, L glass, D glass, S glass, M glass G20, short glass fibers (glass fine powder such as E glass, T glass, D glass, S glass, Q glass, etc. Etc.), hollow glass, spherical glass and the like.

  The organic filler is not particularly limited, and examples thereof include rubber powders such as styrene type powder, butadiene type powder, and 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 (C), the thermal expansion coefficient of the obtained cured product tends to be further reduced.

  The content of the filler (C) is preferably 50 to 1600 parts by mass, more preferably 60 to 1200 parts by mass, and still more 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 (C) is within the above range, the thermal expansion coefficient of the obtained cured product tends to further decrease.

[Other ingredients]
The resin composition of the present embodiment may contain other components as necessary in addition to the above components. Other components are not particularly limited, and are selected from, for example, maleimide compounds other than maleimide compound (A), epoxy resins, phenol resins, oxetane resins, benzoxazine compounds, and compounds having a polymerizable unsaturated group. Any 1 or more types are mentioned among groups.

(Maleimide compounds other than maleimide compound (A))
The maleimide compound other than the maleimide compound (A) is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule (excluding the maleimide compound (A)), and 4,4-diphenylmethane Bismaleimide, phenylmethanemaleimide, m-phenylenebismaleimide, 2,2-bis (4- (4-maleimidophenoxy) -phenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebis Maleimide, 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- Ray bromide aminophenoxy) benzene, novolak maleimide compound, prepolymer, and the like of the prepolymer, or a maleimide compound and an amine compound of the biphenyl aralkyl type maleimides and their maleimide compound. Maleimide compounds other than these maleimide compounds (A) can be used singly or in combination of two or more.

  Among these, a novolak type maleimide compound and a biphenylaralkyl type bismaleimide are preferable. By using such a maleimide compound, the heat resistance of the obtained cured product tends to be further improved.

  The content of the maleimide compound other than the maleimide compound (A) is preferably 1 to 90 parts by mass, more preferably 20 to 75 parts by mass, and still more preferably 40 to 100 parts by mass with respect to 100 parts by mass of the resin solid content. 60 parts by mass. When the content of the maleimide compound other than the maleimide compound (A) is within the above range, the heat resistance of the obtained cured product tends to be further improved.

(Epoxy resin)
The epoxy resin is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule, and generally known ones can be used. 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.

  The content of the epoxy resin is preferably 1 to 90 parts by mass, more preferably 10 to 80 parts by mass, and still more preferably 20 to 60 parts by mass with respect to 100 parts by mass of the resin solid content. When content of an epoxy resin (B) exists in the said range, it exists in the tendency for the softness | flexibility of a hardened | cured material obtained, copper foil peel strength, and chemical resistance to improve more.

(Phenolic resin)
As the phenol resin, generally known resins can be used as long as they are phenol resins 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)
As the oxetane resin, generally known oxetane resins can be used, and the kind thereof is not particularly 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 singly or in combination of two or more.

(Benzoxazine compound)
As the benzoxazine compound, 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 of two or more.

(Compound having a polymerizable unsaturated group)
As the compound having a polymerizable unsaturated group, 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 a polymerizable unsaturated group can be used singly or in combination of two or more.

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

  The silane coupling agent is not particularly limited as long as it is a silane coupling agent that is generally used for inorganic surface treatment. For example, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ. Aminosilane compounds such as aminopropyltrimethoxysilane; Epoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane; Acrylic silane compounds such as γ-acryloxypropyltrimethoxysilane; N-β- (N- Cationic silane compounds such as vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride; phenylsilane compounds and the like. These silane coupling agents can be used alone or in combination of two or more.

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

[Curing accelerator]
The resin composition of this embodiment may further contain a curing accelerator. The curing accelerator is not particularly limited. 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, N, N-dimethylpyridine, N, N-dimethylaminopyridine , Tertiary amines such as 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine; phenol , Xylenol, cle Phenols such as sol, resorcin, and catechol; organometallic salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, and iron acetylacetone; Those obtained by dissolving these organic metal salts in hydroxyl-containing compounds such as phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; organic tin such as dioctyl tin oxide, other alkyl tins, and alkyl tin oxides Compounds and the like. Among these, triphenylimidazole promotes the curing reaction and is particularly preferable because it tends to have excellent glass transition temperature (Tg) 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; aroma such as toluene and xylene Group hydrocarbons; amides such as dimethylformamide; propylene glycol monomethyl ether and its acetate. These solvents can be used alone or in combination of two or more.

[Method for producing resin composition]
The manufacturing method of the resin composition of this embodiment is not specifically limited, For example, the method of mix | blending each component mentioned above in a solvent sequentially 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 (C) 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 resin sheet, or a printed wiring board. Hereinafter, these 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 is not specifically limited, It can carry out according to a conventional method. 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 (C)) 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. Specific examples of the fibers constituting the substrate are not particularly limited. For example, glass fibers such as E glass, D glass, S glass, Q glass, spherical glass, NE glass, L glass, and T glass; 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 Selen); Organic fibers such as polyparaphenylene benzoxazole (Zylon (registered trademark), manufactured by Toyobo Co., Ltd.), polyimide, etc. 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 can be used individually by 1 type or in combination of 2 or more types.

The shape of the substrate is not particularly limited, and examples thereof include woven fabric, nonwoven fabric, roving, chopped strand mat, and surfacing mat. 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. . Moreover, the thing which spread-processed these, and the glass woven fabric surface-treated with the silane coupling agent etc. are used suitably. The thickness and mass of the substrate are not particularly limited, and 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.

(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 metal foil.

  The conductor layer can be a metal foil such as copper or aluminum. The metal foil used here is not particularly limited as long as it is used for a printed wiring board material, and a known copper foil such as a rolled copper foil or an electrolytic copper foil is preferable. Moreover, the thickness of a conductor layer is not specifically limited, Preferably it is 1-70 micrometers, 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.

(Resin sheet)
The resin sheet of this embodiment contains a resin composition. The resin sheet is used as one means for thinning, and includes, for example, a resin composition formed into a sheet shape. As the resin sheet, a resin sheet (laminated resin sheet) having a support and the resin composition disposed on the support was molded into a sheet without using the support or the like. And resin sheet (single-layer resin sheet). The manufacturing method of a resin sheet is not specifically limited, It can carry out according to a conventional method. For example, the laminated resin sheet can be obtained by directly applying and drying the resin composition on a support such as a metal foil or a film. The single-layer resin sheet can be obtained by forming a solution obtained by dissolving the resin composition of the present embodiment in a solvent into a sheet having a sheet-like cavity and drying the sheet, thereby forming the sheet. it can. Moreover, a single layer resin sheet can also be obtained by peeling or etching a support body from the said laminated resin sheet.

  The support is not particularly limited, and known materials 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 a release agent applied to the surface 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 for 1 to 60 minutes in a dryer at 100 to 200 ° C. 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.

(Printed wiring board)
The printed wiring board of the present 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 surface of the inner layer circuit of the inner layer substrate is subjected to a surface treatment to increase the adhesive strength as necessary, and then the required number of the above-mentioned prepregs are stacked on the inner layer circuit surface. Are laminated and heated and pressed to form a single piece. 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. . Thereafter, a plated metal film is formed on the wall surface of the hole to connect the inner layer circuit and the metal foil for the outer layer circuit, and further, the outer layer circuit is formed by etching the metal foil for the outer layer circuit. Is manufactured.

  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.

  When a metal foil-clad laminate is not used, a printed wiring board may be produced by forming a conductor layer to be a circuit on the prepreg, the 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 this embodiment can be used particularly effectively as a printed wiring board for semiconductor packages because the above-described insulating layer is excellent in copper foil peel strength and glass transition temperature (Tg).

  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.

(Synthesis Example 2) Synthesis of bismaleimide of 1,3-bis (aminomethyl) cyclohexane Maleic anhydride (8.26 g) and dimethylformamide (30 g) were charged into a 100 ml three-necked flask, and then in an ice bath. After cooling, a solution of 1,3-bis (aminomethyl) cyclohexane (5.67 g) and dimethylformamide (30 g) was added dropwise. After completion of the dropwise addition, the solution obtained by dropping the stirred solution at 80 ° C./3 hr into a solution (1 L) of water / methanol = 1/1 is recovered, and recrystallized with methanol to obtain the following formula. A bismaleimide of 1,3-bis (aminomethyl) cyclohexane represented by (1) was obtained.

Example 1
As a maleimide compound (A), 50 parts by mass of bismaleimide (maleimide equivalent: 151 g / eq.) Of 1,3-bis (aminomethyl) cyclohexane obtained in Synthesis Example 2, and as a cyanate ester compound (B), a synthesis example 1 SNCN (cyanate equivalent: 256 g / eq.) 50 parts by mass, filler (C) as fused silica (manufactured by Admatechs Co., Ltd., SC2050MB), curing accelerator as triphenylimidazole Varnish was obtained by mixing 0.5 parts by mass (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.2 parts by mass of zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.) as a curing accelerator. The ratio (β / α) of the number (β) of the cyanate group (cyanate group) of the cyanate ester compound (B) to the number (α) of the maleimide group of the maleimide compound (A) is 0.59. is there.

(Comparative Example 1)
In place of the bismaleimide of 1,3-bis (aminomethyl) cyclohexane obtained in Synthesis Example 2, a maleimide compound represented by the following formula (5) (BMI-70, manufactured by Daiwa Kasei Kogyo Co., Ltd., maleimide equivalent: 221 g / eq.) A varnish was obtained in the same manner as in Example 1 except that 50 parts by mass were blended. The ratio (β / α) of the number (β) of the cyanate group (cyanate group) of the cyanate ester compound (B) to the number (α) of the maleimide group of the maleimide compound (A) is 0.86. is there.

[Method for producing copper-clad laminate]
The varnishes of Example 1 and Comparative Example 1 obtained as described above were impregnated and applied to an E glass cloth having a thickness of 0.1 mm, and a dryer (explosion-proof steam dryer, manufactured by Takasugi Seisakusho Co., Ltd.). ) At 165 ° C. for 5 minutes to obtain a prepreg having a resin composition of 50% by mass. 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. Using the obtained copper-clad laminate, the following characteristics were evaluated. The results are summarized in Table 1.

(Characteristic evaluation)
(Copper foil peel strength)
Using the test piece (30 mm × 150 mm × thickness 0.8 mm) of the copper clad laminate having an insulating layer thickness of 0.8 mm obtained above, the copper clad laminate test method for printed wiring boards according to JIS C6481 (5. 7) Refer to the peel strength.) The copper foil peel strength (copper foil peel strength) was measured three times to obtain an average value.

(Glass transition temperature (Tg))
The copper foil-clad laminate with an insulating layer thickness of 0.8 mm obtained above was cut into a size of 12.7 mm × 30 mm with a dicing saw, and then the copper foil on the surface was removed by etching to obtain a measurement sample. Using this measurement sample, the glass transition temperature (Tg) was measured three times by the DMA method with a dynamic viscoelasticity analyzer (manufactured by TA Instruments) in accordance with JIS C6481, and the average value was obtained.

  The resin composition of the present invention has industrial applicability as a material for prepregs, metal foil-clad laminates, resin sheets, printed wiring boards and the like.

Claims (10)

A maleimide compound (A) represented by the following formula (1);
A cyanate ester compound (B);
Containing a resin composition.
The content of the maleimide compound (A) in the resin composition is 1 to 90 parts by mass with respect to 100 parts by mass of the resin solid content.
The resin composition according to claim 1. The cyanate ester compound (B) includes a naphthol aralkyl type cyanate ester compound,
The resin composition according to claim 1 or 2. Further containing a filler (C),
The resin composition as described in any one of Claims 1-3. Further containing at least one member selected from the group selected from maleimide compounds other than the maleimide compound (A), epoxy resins, phenol resins, oxetane resins, benzoxazine compounds, and compounds having a polymerizable unsaturated group To
The resin composition as described in any one of Claims 1-4. Content in the resin composition of the said filler (C) is 50-1600 mass parts with respect to 100 mass parts of resin solid content,
The resin composition according to claim 4 or 5. A substrate;
The resin composition according to any one of claims 1 to 6, impregnated or coated on the substrate;
Prepreg with 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;
A metal foil-clad laminate.   The resin sheet containing the resin composition as described in any one of Claims 1-6. An insulating layer;
A conductor layer formed on the surface of the insulating layer;
Have
The insulating layer includes the resin composition according to any one of claims 1 to 6,
Printed wiring board.