JPWO2019044977A1 - Resin composition, prepreg, metal foil-clad laminate, resin sheet and printed wiring board - Google Patents

Abstract

A resin composition comprising an epoxy resin (A) having a repeating unit represented by the following formula (1) and having a Z average molecular weight of 1400 to 3000 and a cyanate ester compound (B) . (In formula (1), X1 represents an alkylene group having 1 to 3 carbon atoms or an alkenylene group, and each R1 independently represents a hydrogen atom or an alkyl group or alkenyl group having 1 to 3 carbon atoms.)

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, 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.

Conventionally, cyanate ester compounds have been known as printed wiring board materials having excellent heat resistance and electrical characteristics. Recently, resin compositions in which an epoxy resin, a bismaleimide compound, and the like are used in combination with a cyanate ester compound are used as semiconductors. Widely used for high-performance printed wiring board materials such as plastic packages.
For example, Patent Documents 1 and 2 propose a resin composition comprising a cyanate ester compound and an epoxy resin, which is excellent in properties such as adhesion, low water absorption, moisture absorption heat resistance, and insulation reliability.
Patent Document 3 proposes a thermosetting resin composition including a cyanate ester compound and an epoxy resin, which is excellent in heat resistance and flame retardancy.

International Publication No. 2013/065694 International Publication No. 2014/203866 International Publication No. 2015/064064

  Although it can be said that the resin compositions described in Patent Documents 1 and 2 have good physical properties with respect to adhesion, low water absorption, moisture absorption heat resistance, and insulation reliability, from the viewpoint of heat resistance, they are still improved. There is room. Furthermore, there is still room for improvement in the resin composition described in Patent Document 3, which is said to be excellent in heat resistance.

  The present invention has been made in view of the above problems, and an object thereof is to provide a resin composition, a prepreg, a metal foil-clad laminate, a resin sheet, and a printed wiring board that exhibit excellent heat resistance. To do.

  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 a cyanate ester compound together with an epoxy resin having a specific structure and a specific molecular weight, and the present invention has been completed.

That is, the present invention includes the following aspects.
[1]
An epoxy resin (A) having a repeating unit represented by the following formula (1) and having a Z average molecular weight of 1400 or more and 3000 or less;
A cyanate ester compound (B);
Containing a resin composition.
(In formula (1), X ₁ represents an alkylene group having 1 to 3 carbon atoms or an alkenylene group, and each R ₁ independently represents a hydrogen atom or an alkyl group or alkenyl group having 1 to 3 carbon atoms.)
[2]
Resin composition as described in [1] whose content of the said epoxy resin (A) is 1-90 mass parts with respect to 100 mass parts of resin solid content.
[3]
A kind selected from the group consisting of an epoxy resin other than the epoxy resin (A) represented by the formula (1), a maleimide compound, a phenol resin, an oxetane resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group. The resin composition according to [1] or [2], further containing the above.
[4]
The resin composition according to any one of [1] to [3], further containing a filler (C).
[5]
Resin composition as described in [4] whose content of the said filler (C) is 50-1600 mass parts with respect to 100 mass parts of resin solid content.
[6]
A substrate;
The resin composition according to any one of [1] to [5], impregnated or coated on the substrate;
Having a prepreg.
[7]
The prepreg according to [6], wherein at least one sheet is laminated;
A metal foil disposed on one or both sides of the prepreg;
A metal foil-clad laminate.
[8]
The resin sheet which has the resin composition in any one of [1]-[5].
[9]
An insulating layer;
A conductor layer formed on the surface of the insulating layer;
Have
The printed wiring board in which the said insulating layer contains the resin composition in any one of [1]-[5].

  According to the present invention, it is possible to provide a resin composition, a prepreg, a metal foil-clad laminate, a resin sheet, and a printed wiring board that exhibit excellent heat resistance.

  DESCRIPTION OF EMBODIMENTS Hereinafter, a mode for carrying out 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 can be made without departing from the gist thereof. Is possible.

  The resin composition of this embodiment includes an epoxy resin (A) having a repeating unit represented by the following formula (1) and having a Z average molecular weight of 1400 or more and 3000 or less, and a cyanate ester compound (B). Containing. Since it is comprised in this way, the resin composition of this embodiment can express the outstanding heat resistance.

(In formula (1), X ₁ represents an alkylene group having 1 to 3 carbon atoms or an alkenylene group, and each R ₁ independently represents a hydrogen atom or an alkyl group or alkenyl group having 1 to 3 carbon atoms.)

  Hereinafter, each component which comprises the resin composition of this embodiment is demonstrated.

[Epoxy resin (A)]
The epoxy resin (A) in this embodiment has a repeating unit represented by the above formula (1).
X ₁ in formula (1) represents an alkylene group having 1 to 3 carbon atoms or an alkenylene group, and preferably a methylene group.
R ₁ in formula (1) each independently represents a hydrogen atom or an alkyl group or alkenyl group having 1 to 3 carbon atoms, preferably a hydrogen atom.
The number of repeating units represented by the formula (1) is an integer of 1 or more, and preferably 1 or more and 5 or less, more preferably 2 or more and 4 or less, from the viewpoint of heat resistance and moldability. In addition, as long as it has the predetermined repeating unit in this embodiment and has a predetermined Z average molecular weight, the epoxy resin (A) may be only one kind of epoxy resin having one repeating unit number. And the mixture of 2 or more types of epoxy resins from which the number of repeating units differs may be sufficient. When the epoxy resin (A) is a mixture of two or more types of epoxy resins having different numbers of repeating units, it may contain an epoxy resin having a number of repeating units of 1, but the number of repeating units is 2 or more. When the epoxy resin to be included is included, the Z average molecular weight of the epoxy resin (A) is 1400 or more and 3000 or less.

In this embodiment, from the viewpoint of heat resistance, the repeating unit represented by the above formula (1) is preferably a repeating unit represented by the following formula (1-1).

In the present embodiment, from the viewpoint of heat resistance, one end of the repeating structure represented by the above formula (1) is a hydrogen atom and the other is a group represented by the following formula (1-2). It is preferable that
(In formula (1-2), each R ₁ independently represents a hydrogen atom or an alkyl or alkenyl group having 1 to 3 carbon atoms.)

Although the epoxy resin (A) in this embodiment is not limited to the following, For example, the epoxy resin represented by following formula (1-3) can be included, More specifically, for example, following formula (1) -4) can be included.
(In formula (1-3), X ₁ represents an alkylene group having 1 to 3 carbon atoms or an alkenylene group, R ₁ each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkenyl group; Is one of which is a hydrogen atom and the other is a group represented by the above formula (1-2).)

  The Z average molecular weight of the epoxy resin (A) in the present embodiment is 1400 or more and 3000 or less, preferably 1500 or more and 2500 or less, more preferably 1600 or more and 2000 or less, from the viewpoint of heat resistance and moldability.

  The content of the epoxy resin (A) in the present embodiment can be appropriately set according to the desired properties, and is not particularly limited, but from the viewpoint of improving the heat resistance, the resin solid content is 100 parts by mass. 1 to 90 parts by mass, more preferably 30 to 70 parts by mass, and still more preferably 40 to 60 parts by mass.

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

  It does not specifically limit as a manufacturing method of the epoxy resin (A) in this embodiment, A well-known method can be used. The epoxy resin (A) can also be obtained as a commercial product, and examples thereof include, but are not limited to, “EPICLON EXA-4710H-70M” manufactured by DIC Corporation.

[Cyanate ester compound (B)]
The cyanate ester compound (B) is not particularly limited as long as it is a compound having in its molecule an aromatic moiety substituted with at least one cyanate group (cyanate ester group). The resin composition using the cyanate ester compound (B) has excellent properties such as glass transition temperature, low thermal expansion, plating adhesion, and the like when cured.

  Examples of the cyanate ester compound (B) include, but are not limited to, those represented by the following formula (2).

In the above formula (2), 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 represents the number of Ra bonded to Ar _1, and is 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 above 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, but are not limited to, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1-ethylpropyl group, Examples include 2,2-dimethylpropyl group, cyclopentyl group, hexyl group, cyclohexyl group, and trifluoromethyl group.
Specific examples of the aryl group include, but are not limited to, phenyl group, xylyl group, mesityl group, naphthyl group, phenoxyphenyl group, ethylphenyl group, o-, m- or p-fluorophenyl group, dichlorophenyl group, dicyano. Examples thereof include a phenyl group, a trifluorophenyl group, a methoxyphenyl group, and an o-, m- or p-tolyl group.
Examples of the alkoxyl group include, but are not limited to, 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 formula (2) are not limited to the following, but include a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, and trimethyl. Examples include a cyclohexylene group, a biphenylylmethylene group, a dimethylmethylene-phenylene-dimethylmethylene group, a fluorenediyl group, and a 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 formula (2) include, but are not limited to, an imino group and a polyimide group.

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

(In the above 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 or different from each other. Rb, Rc , Rf, and Rg each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group, or an aryl group having at least one phenolic hydroxy 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 (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 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 a cyanato group. (Indicates at least one substituted aryl group. V represents an integer of 0 to 5, but the cyanate ester compound may be a mixture of compounds having different v.)

  Furthermore, as X in Formula (2), the bivalent group represented by a following formula is mentioned.

(In the above formula, z represents an integer of 4 to 7. Each Rk independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

Specific examples of Ar ₃ in the formula (3) Ar ₂ and (4) of the two carbon atoms shown in formula (3), or two oxygen atoms shown in formula (4), 1,4 Benzenetetrayl group bonded to position or 1,3 position, the above two carbon atoms or two oxygen atoms are 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 2, 6-position, 1, 5-position, 1, 6 Naphthalenetetrayl group bonded to the 1-position, 1,8-position, 1,3-position, 1,4-position, or 2,7-position.
Rb, Rc, Rd, Re, Rf and Rg in formula (3), and the alkyl group and aryl group in Ri and Rj in formula (4) have the same meaning as the alkyl group and aryl group in Ra in formula (2). It is.

  Specific examples of the cyanato-substituted aromatic compound represented by the above formula (2) are not limited to the following, but 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, cyanato Nonylbenzene, 2- (4-cyanphenyl) -2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato 4-vinylbenzene, 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-acetamino Benzene, 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'- Is 4,4′-dicyanatobiphenyl, 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-dimethylphenyl) propane, 1,1-bis (4-cyanatophenyl) butane, 1,1-bis (4-cyanatophenyl) isobutane, 1,1-bi (4-cyanatophenyl) 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-si Anatophenyl) hexane, 2,2-bis (4-cyanatophenyl) -3-methylbutane, 2,2-bis (4-cyanatophenyl) -4-methylpentane, 2,2-bis (4-cyanato) Phenyl) -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-cyanatophenyl) -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-si Anatophenyl) -1-pheni Ethane, bis (4-cyanatophenyl) 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-dicyanatobenzophenone, 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 ( 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- ( -Methylanilino) -1,3,5-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 ′-(hexafluoro Isopropylidene) 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 3,3-bis (4-cyanatophenyl) indolin-2-one, and 2-phenyl-3,3-bis (4-cyanatophenyl) include indolin-2-one.

Moreover, as another specific example of the compound represented by the above formula (2), although not limited to the following, a phenol novolak resin and a cresol novolak resin (by a known method, phenol, alkyl-substituted phenol or halogen-substituted phenol, Formaldehyde and paraformaldehyde and other formaldehyde compounds reacted in an acidic solution), trisphenol novolac resin (hydroxybenzaldehyde and phenol reacted in the presence of an acidic catalyst), fluorene novolak resin (fluorenone compound) And 9,9-bis (hydroxyaryl) fluorenes in the presence of an acidic catalyst), phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins and biphenyl aralkyl resins (known methods) _{More, Ar 4 - (CH 2 Y} ) 2 (. Ar 4 represents a phenyl group, Y represents a halogen atom and the same in this paragraph.) And bishalogenomethyl compounds represented by the phenol compound obtained by reacting an acidic catalyst or no catalyst, Ar 4 _- (CH 2 _oR) expressed by such bis ₂ (alkoxymethyl) that a compound with a phenol compound is reacted in the presence of an acidic catalyst, or, A reaction product of a bis (hydroxymethyl) compound represented by Ar ₄ — (CH ₂ OH) ₂ and a phenol compound in the presence of an acidic catalyst, or an aromatic aldehyde compound, an aralkyl compound and a phenol compound. Polycondensed), phenol-modified xylene formaldehyde resin (by known methods, xylene formaldehyde resin and Enol compound reacted in the presence of acidic catalyst), modified naphthalene formaldehyde resin (reacted naphthalene formaldehyde resin and hydroxy-substituted aromatic compound in the presence of acidic catalyst by a known method), phenol modified Dicyclopentadiene resin, phenol resin having a polynaphthylene ether structure (by a known method, a polyhydric hydroxynaphthalene compound having two or more phenolic hydroxy groups in one molecule is subjected to dehydration condensation in the presence of a basic catalyst. And the like, and those prepolymers thereof.

  The above-mentioned cyanate ester compound (B) can be used individually by 1 type or in mixture of 2 or more types.

  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.

  Specific examples of the naphthol aralkyl cyanate include naphthol aralkyl cyanate represented by the formula (5). By using such a naphthol aralkyl type cyanate ester, a cured product having a lower thermal expansion coefficient tends to be obtained.

(In formula (5), each R ⁶ independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferable. In the formula, n ₂ represents an integer of 1 or more. Upper limit of n ₂ The value is usually 10 and preferably 6)

  The content of the cyanate ester compound (B) can be appropriately set according to the desired characteristics, and is not particularly limited. However, from the viewpoint of obtaining a cured product having a lower thermal expansion coefficient, the content of the resin solid content is 100 parts by mass. On the other hand, 1-90 mass parts is preferable, More preferably, it is 30-70 mass parts, More preferably, it is 40-60 mass parts.

[Filler (C)]
The resin composition of the present embodiment preferably further contains a filler (C) from the viewpoints of thermal expansion characteristics, dimensional stability, flame retardancy, thermal conductivity, dielectric characteristics, and the like. As a filler (C), a well-known thing can be used suitably, The kind is not specifically limited. In particular, a filler generally used in laminated plate applications can be suitably used as the filler (C). Specific examples of the filler (C) include natural silica, fused silica, synthetic silica, amorphous silica, aerosil, hollow silica and other silicas, white carbon, titanium white, zinc oxide, magnesium oxide, zirconium oxide and other oxides. , Boron nitride, Aggregated boron nitride, Silicon nitride, Aluminum nitride, Barium sulfate, Aluminum hydroxide, Aluminum hydroxide heat-treated product (Aluminum hydroxide is heat-treated and part of crystal water is reduced), boehmite, water Metal hydrates such as magnesium oxide, molybdenum compounds such as molybdenum oxide and zinc molybdate, zinc borate, zinc stannate, alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass , A-glass, NE-glass, C-glass, L-glass, D-gas S, S-glass, M-glass G20, short glass fibers (including fine glass powders such as E glass, T glass, D glass, S glass, and Q glass), hollow glass, spherical glass, and other inorganic fillers In addition to the material, rubber powders such as styrene type, butadiene type, and acrylic type, core shell type rubber powder, and organic fillers such as silicone resin powder, silicone rubber powder, and silicone composite powder can be used. These fillers can be used alone or in combination of two or more.
Among these, one or more selected from the group consisting of silica, aluminum hydroxide, boehmite, magnesium oxide, and magnesium hydroxide is preferable. By using these fillers, characteristics such as thermal expansion characteristics, dimensional stability, and flame retardancy of the resin composition tend to be further improved.

  The content of the filler (C) in the resin composition of the present embodiment can be appropriately set according to desired characteristics, and is not particularly limited, but from the viewpoint of moldability of the resin composition, the resin solid content is When it is 100 mass parts, it is preferable to set it as 50-1600 mass parts, More preferably, it is 50-750 mass parts, More preferably, it is 50-300 mass parts, Most preferably, it is 50-200 mass parts. .

  Here, when the filler (C) is contained in the resin composition, it is preferable to use a silane coupling agent or a wetting and dispersing agent in combination. As a silane coupling agent, what is generally used for the surface treatment of an inorganic substance can be used suitably, and the kind is not specifically limited. Specific examples of the silane coupling agent include, but are not limited to, aminosilanes such as γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, and γ-glycid. Epoxysilanes such as xylpropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinylsilanes such as γ-methacryloxypropyltrimethoxysilane, vinyl-tri (β-methoxyethoxy) silane, N Examples include cationic silanes such as -β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride and phenylsilanes. A silane coupling agent can be used individually by 1 type or in combination of 2 or more types. Moreover, as a wet dispersing agent, what is generally used for coating materials can be used suitably, The kind is not specifically limited. As the wetting and dispersing agent, a copolymer-based wetting and dispersing agent is preferably used, and may be a commercially available product. Specific examples of commercially available products include, but are not limited to, Disperbyk-110, 111, 161, 180, BYK-W996, BYK-W9010, BYK-W903, BYK-W940 and the like manufactured by Big Chemie Japan Co., Ltd. It is done. Wet dispersants can be used alone or in combination of two or more.

[Other ingredients]
Furthermore, in the resin composition of the present embodiment, an epoxy resin other than the epoxy resin (A) represented by the above formula (1) (hereinafter referred to as “other epoxy resin”) as long as the desired characteristics are not impaired. And a maleimide compound, a phenol resin, an oxetane resin, a benzoxazine compound, a compound having a polymerizable unsaturated group, and the like. By using these in combination, desired properties such as flame retardancy and low dielectric property of a cured product obtained by curing the resin composition tend to be improved.

(Other epoxy resins)
The other epoxy resin is not represented by the formula (1), and any known epoxy resin can be used as long as it has two or more epoxy groups in one molecule. Is not particularly limited. Specifically, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, bisphenol A novolac type epoxy resin, glycidyl ester type epoxy resin, aralkyl novolak Type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, cresol novolac type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthalene skeleton modified novolak type epoxy resin, phenol aralkyl Type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, alicyclic ester Carboxy resin, a polyol type epoxy resins, phosphorus-containing epoxy resin, glycidyl amine, glycidyl ester, compounds of the double bonds epoxidized in butadiene, such as a compound obtained by reaction of a hydroxyl-group-containing silicon resin with epichlorohydrin. Among these epoxy resins, biphenyl aralkyl type epoxy resins, naphthylene ether type epoxy resins, polyfunctional phenol type epoxy resins, and naphthalene type epoxy resins are preferable in terms of flame retardancy and heat resistance. These epoxy resins can be used alone or in combination of two or more.

(Maleimide compound)
As the maleimide compound, generally known compounds can be used as long as they have one or more maleimide groups in one molecule. For example, 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-phenylene bismaleimide, 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, polyphenylmethane maleimide, novolac maleimide, biphenylaralkyl maleimide, and these maleimide compounds Prepolymer Or although prepolymer of the maleimide compound and amine compound, but is not particularly limited. These maleimide compounds can be used alone or in combination. Of these, novolac maleimide compounds and biphenylaralkyl maleimide compounds are particularly preferred.

(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. 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. Among these phenol resins, biphenyl aralkyl type phenol resins, naphthol aralkyl type phenol resins, phosphorus-containing phenol resins, and hydroxyl group-containing silicone resins are preferable in terms of flame retardancy. 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. For example, oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, alkyloxetane such as 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3-di (trifluoro) Methyl) perfluoxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl type oxetane, OXT-101 (trade name, manufactured by Toagosei Co., Ltd.), OXT-121 (trade name, manufactured by Toagosei Co., Ltd.) Although it is mentioned, it is not particularly limited. These oxetane resins can be used alone or in combination.

(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. For example, 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 (trade name, manufactured by Konishi Chemical), P -D type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), Fa type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) and the like can be mentioned, but are not particularly limited. These benzoxazine compounds can be used alone or in combination.

(Compound having a polymerizable unsaturated group)
As the compound having a polymerizable unsaturated group, generally known compounds can be used. For example, vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, divinylbiphenyl, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polypropylene glycol di (meth) acrylate, Mono- or polyhydric alcohol (meth) acrylates such as trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol And epoxy (meth) acrylates such as A-type epoxy (meth) acrylate and bisphenol F-type epoxy (meth) acrylate, and benzocyclobutene resin. But it is not particularly limited. These compounds having an unsaturated group can be used alone or in combination. The “(meth) acrylate” is a concept including acrylate and methacrylate corresponding to the acrylate.

(Curing accelerator)
Moreover, the resin composition of this embodiment may contain the hardening accelerator for adjusting a hardening rate suitably as needed. As this hardening accelerator, what is generally used as hardening accelerators, such as a cyanate ester compound and an epoxy resin, can be used suitably, The kind is not specifically limited. Specific examples of the curing accelerator include zinc octylate, zinc naphthenate, cobalt naphthenate, copper naphthenate, iron acetylacetone, nickel octylate, manganese octylate, etc., phenol, xylenol, cresol, resorcin, catechol Phenol compounds such as octylphenol and nonylphenol, alcohols such as 1-butanol and 2-ethylhexanol, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, Imidazoles such as 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and Derivatives of imidazoles such as carboxylic acids or anhydrides thereof, dicyandiamide, benzyldimethylamine, amines such as 4-methyl-N, N-dimethylbenzylamine, phosphine compounds, phosphine oxide compounds, Phosphorium salt compounds, phosphorus compounds such as diphosphine compounds, epoxy-imidazole adduct compounds, benzoyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl Examples thereof include peroxides such as peroxycarbonate and azo compounds such as azobisisobutyronitrile. A hardening accelerator can be used individually by 1 type or in combination of 2 or more types.
The usage-amount of a hardening accelerator can be suitably adjusted in consideration of the hardening degree of resin, the viscosity of a resin composition, etc., and is not specifically limited. 0.005-10 mass parts may be sufficient as the usage-amount of a hardening accelerator with respect to 100 mass parts of resin solid content in a resin composition.

(Other additives)
Furthermore, the resin composition of the present embodiment includes various thermosetting resins such as other thermosetting resins, thermoplastic resins and oligomers thereof, elastomers and the like within a range in which desired characteristics are not impaired. In addition, various additives can be used in combination. These are not particularly limited as long as they are generally used. Specific examples of the flame retardant compound include, but are not limited to, bromine compounds such as 4,4′-dibromobiphenyl, phosphoric acid esters, melamine phosphate, phosphorus-containing epoxy resins, nitrogen compounds such as melamine and benzoguanamine, and oxazine Examples thereof include a ring-containing compound and a silicone compound. Examples of various additives include, but are not limited to, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, and flow modifiers. , Lubricants, antifoaming agents, dispersants, leveling agents, brighteners, polymerization inhibitors and the like. These may be used alone or in combination of two or more as desired.

(Organic solvent)
In addition, the resin composition of this embodiment can contain an organic solvent as needed. In this case, the resin composition of the present embodiment can be used as an aspect (solution or varnish) in which at least a part, preferably all, of the various resin components described above are dissolved or compatible with an organic solvent. Any known organic solvent can be used as long as it dissolves or is compatible with at least a part, preferably all of the above-mentioned various resin components, and the kind thereof is not particularly limited. . Specific examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, cellosolv solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, and isoamyl acetate. And ester solvents such as methyl methoxypropionate and methyl hydroxyisobutyrate, polar solvents such as amides such as dimethylacetamide and dimethylformamide, and nonpolar solvents such as aromatic hydrocarbons such as toluene and xylene. These can be used alone or in combination of two or more.

  The resin composition of the present embodiment can be prepared according to a conventional method, and the epoxy resin (A) represented by the formula (1), the cyanate ester compound (B), and other optional components described above are uniformly added. If it is a method by which the resin composition to contain is obtained, the preparation method will not be specifically limited. For example, the epoxy resin (A) represented by the formula (1) and the cyanate ester compound (B) are blended sequentially in a solvent, and the resin composition of this embodiment can be easily prepared by sufficiently stirring. it can.

  In preparing the resin composition, a known process (such as stirring, mixing, kneading process) for uniformly dissolving or dispersing each component can be performed. For example, when uniformly dispersing the filler (C), the dispersibility with respect to the resin composition is enhanced 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 / spinning mixing device.

Although the resin composition of this embodiment is not limited to the following, For example, it can be used as a constituent material of a prepreg, a metal foil tension laminated board, a printed wiring board, a resin sheet, and a semiconductor package. For example, a prepreg can be obtained by impregnating or applying a solution obtained by dissolving the resin composition of the present embodiment in a solvent to a base material and drying.
Also, a peelable plastic film is used as a substrate, and a solution obtained by dissolving the resin composition of the present embodiment in a solvent is applied to the plastic film and dried to obtain a build-up film or a dry film solder resist. be able to. Here, the solvent can be dried by drying at a temperature of 20 ° C. to 150 ° C. for 1 to 90 minutes.
Moreover, the resin composition of this embodiment can also be used in the uncured state which dried the solvent, and can also be used in the semi-cured (B-stage) state as needed.

  Hereinafter, the prepreg of this embodiment will be described in detail. The prepreg of this embodiment has a base material and the resin composition impregnated or coated on the base material. The manufacturing method of the prepreg of this embodiment will not be specifically limited if it is a method of manufacturing a prepreg combining the resin composition of this embodiment, and a base material. Specifically, after impregnating or applying the resin composition of the present embodiment to a substrate, it is semi-cured by a method of drying for about 2 to 15 minutes in a dryer at 120 to 220 ° C. The prepreg of the embodiment can be manufactured. At this time, the amount of the resin composition attached to the substrate, that is, the content of the resin composition (including the filler (C)) with respect to the total amount of the prepreg after semi-curing is in the range of 20 to 99% by mass. Is preferred.

  As a base material used when manufacturing the prepreg of this embodiment, the well-known thing used for various printed wiring board materials may be used. Examples of such a substrate include glass fibers such as E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass, and spherical glass, and inorganic fibers other than glass such as quartz, Examples thereof include organic fibers such as polyimide, polyamide, and polyester, and woven fabrics such as liquid crystal polyester, but are not particularly limited thereto. As the shape of the substrate, woven fabric, non-woven fabric, roving, chopped strand mat, surfacing mat, and the like are known, and any of these may be used. A base material can be used individually by 1 type or in combination of 2 or more types as appropriate. Among the woven fabrics, a woven fabric that has been subjected to ultra-opening treatment or plugging treatment is particularly preferable from the viewpoint of dimensional stability. Furthermore, a glass woven fabric surface-treated with a silane coupling agent such as an epoxy silane treatment or an amino silane treatment is preferable from the viewpoint of moisture absorption heat resistance. A liquid crystal polyester woven fabric is preferable from the viewpoint of electrical characteristics. Furthermore, the thickness of the substrate is not particularly limited, but is preferably in the range of 0.01 to 0.2 mm for use in a laminated board.

The metal foil-clad laminate of the present embodiment has at least one or more of the above-described prepregs laminated and a metal foil disposed on one or both sides of the prepreg. Specifically, it is produced by laminating and forming a metal foil such as copper or aluminum on one side or both sides of one prepreg or a plurality of prepregs stacked. be able to. Although the metal foil used here will not be specifically limited if it is used for printed wiring board material, Copper foil, such as a rolled copper foil and an electrolytic copper foil, is preferable. Moreover, although the thickness of metal foil is not specifically limited, It is preferable in it being 2-70 micrometers, and it is more preferable in it being 3-35 micrometers. As a molding condition, a technique used when producing a normal laminated board for a printed wiring board and a multilayer board can be employed. For example, using a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, or an autoclave molding machine, lamination molding is performed under conditions of a temperature of 180 to 350 ° C., a heating time of 100 to 300 minutes, and a surface pressure of 20 to 100 kg / cm ^2. As a result, the metal foil-clad laminate of this embodiment can be manufactured. Moreover, a multilayer board can also be produced by laminating and molding the above prepreg and a separately produced wiring board for the inner layer. As a method for producing a multilayer board, for example, a 35 μm copper foil is disposed on both surfaces of one prepreg described above, laminated under the above conditions, an inner layer circuit is formed, and blackening treatment is performed on this circuit. To form an inner layer circuit board. Further, this inner layer circuit board and the above prepreg are alternately disposed one by one, and a copper foil is further disposed on the outermost layer, and lamination molding is performed under the above conditions, preferably under vacuum. In this way, a multilayer board can be produced.

  The metal foil-clad laminate of this embodiment can be suitably used as a printed wiring board by further forming a pattern. The printed wiring board can be manufactured according to a conventional method, and the manufacturing method is not particularly limited. Hereinafter, an example of the manufacturing method of a printed wiring board is shown. First, the metal foil-clad laminate described above is prepared. Next, an inner layer substrate is manufactured by performing an etching process on the surface of the metal foil-clad laminate to form an inner layer circuit. The inner layer circuit surface of the inner layer substrate is subjected to a surface treatment for increasing the adhesive strength as necessary, and then the required number of the prepregs described above are stacked on the inner layer circuit surface. Further, a metal foil for an outer layer circuit is laminated on the outside, and is integrally formed 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 drilling a through hole or a via hole in the multilayer laminate, a plated metal film is formed on the wall surface of the hole to electrically connect the inner layer circuit and the outer layer metal foil. Furthermore, the printed circuit board is manufactured by performing an etching process on the metal foil for the outer layer circuit to form the outer layer circuit.

  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 prepreg of the present embodiment described above (the base material and the resin composition of the present embodiment impregnated or applied thereto), the layer of the resin composition of the metal foil-clad laminate of the present embodiment described above (the present embodiment). The layer made of the resin composition) is composed of an insulating layer containing the resin composition of the present embodiment.

The resin sheet of this embodiment refers not only to a resin sheet (laminated sheet) including a support and a layer of the resin composition disposed on the surface of the support, but also removes the support from the laminated sheet. Only the resin composition layer (single-layer sheet) corresponds to the resin sheet of this embodiment. That is, the resin sheet of this embodiment has the resin composition of this embodiment.
The laminated sheet can be obtained by applying a solution obtained by dissolving the resin composition in a solvent to a support and drying it. Although it does not specifically limit as a support body used here, For example, the mold release agent was apply | coated to the surface of a polyethylene film, a polypropylene film, a polycarbonate film, a polyethylene terephthalate film, an ethylene tetrafluoroethylene copolymer film, and these films. Examples thereof include organic film base materials such as release films and polyimide films, conductive foils such as copper foil and aluminum foil, and plate-like inorganic films such as glass plates, SUS plates, and FRP. As a coating method, for example, a solution in which the above resin composition is dissolved in a solvent is coated on the support with a bar coater, a die coater, a doctor blade, a baker applicator, etc. Is a method of producing a laminated sheet in which are integrated. Moreover, a single layer sheet | seat can also be obtained by peeling or etching a support body from the resin sheet obtained by drying after application | coating. In addition, the solution obtained by dissolving or dissolving the resin composition of the present embodiment in a solvent is supplied into a mold having a sheet-like cavity and dried to form a sheet, thereby supporting the support. A single layer sheet can also be obtained without using.

  In addition, in preparation of the resin sheet or single layer sheet of this embodiment, the drying conditions at the time of removing a solvent are not specifically limited, However, It is preferable to make it dry for 1 to 90 minutes at the temperature of 20 to 200 degreeC. When the temperature is 20 ° C. or higher, the solvent can be prevented from remaining in the resin composition, and when the temperature is 200 ° C. or lower, the progress of curing of the resin composition can be suppressed. Moreover, the thickness of the resin layer in the resin sheet or single layer sheet of this embodiment can be adjusted with the density | concentration and application | coating thickness of the resin composition of this embodiment, and is not specifically limited. However, the thickness is preferably 0.1 to 500 μm. When the thickness of the resin layer is 500 μm or less, the solvent is less likely to remain during drying.

  Hereinafter, the present embodiment will be described more specifically using examples and comparative examples. This embodiment is not limited at all by the following examples.

(Synthesis Example 1) Synthesis of cyanate ester compound 1-naphthol aralkyl resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) 300 g (OH group conversion 1.28 mol) and triethylamine 194.6 g (1.92 mol) (based on 1 mol of hydroxy group) 1.5 mol) was dissolved in 1800 g of dichloromethane.
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) ), 1205.9 g of water was poured over 30 minutes while stirring at a liquid temperature of −2 to −0.5 ° C. 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 organic phase obtained was washed 5 times with 1300 g of water. Since the electric conductivity of the waste water in the fifth washing with water was 5 μS / cm, it was confirmed that the ionic compound could be 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 desired naphthol aralkyl-type cyanate ester compound (SNCN) (orange viscous product). The obtained SNCN had a mass average molecular weight Mw of 600. Further, the IR spectrum of SNCN showed an absorption of 2250 cm ⁻¹ (cyanate ester group) and no absorption of a hydroxy group.

Example 1
50 parts by mass of SNCN obtained in Synthesis Example 1, 50 parts by mass of an epoxy resin (“EPICLON EXA-4710H-70M” manufactured by DIC Corporation) having a repeating unit represented by the following formula (1-1), fused silica A varnish was obtained by mixing 100 parts by mass (SC2050MB, manufactured by Admatex Co., Ltd.) and 0.05 parts by mass of zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.). This varnish was diluted with methyl ethyl ketone, impregnated and coated on a 0.1 mm thick E glass woven fabric, and dried by heating at 165 ° C. for 5 minutes to obtain a prepreg having a resin content of 50 mass%. In addition, EPICLON EXA-4710H-70M was previously subjected to molecular weight measurement described later, and its Z-average molecular weight was specified as 1810.

8 and 4 sheets of the obtained prepregs were stacked, and 12 μm thick electrolytic copper foil (3EC-M3-VLP, manufactured by Mitsui Kinzoku Co., Ltd.) was placed up and down at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. Lamination molding was performed for 120 minutes to obtain metal foil-clad laminates with insulating layer thicknesses of 0.8 mm and 0.4 mm. Using the obtained metal foil-clad laminate, a solder float test and a glass transition temperature measurement were performed as described below. The results are shown in Table 1.

(Comparative Example 1)
In Example 1, instead of using 50 parts by mass of the epoxy resin represented by the formula (1), a biphenylaralkyl type epoxy resin represented by the following formula (6) (NC-3000-FH, Nippon Kayaku Co., Ltd.) Product) A prepreg having a resin content of 50% by mass was obtained in the same manner as in Example 1 except that 50 parts by mass was used and zinc octylate was changed to 0.11 part by mass. Further, metal foil-clad laminates having a thickness of 0.8 mm and 0.4 mm were obtained in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained metal foil-clad laminate.

(In formula (6), n represents an integer of 0 to 15)

(Comparative Example 2)
In Example 1, instead of using 50 parts by mass of the epoxy resin represented by the formula (1), a naphthalene type epoxy resin represented by the following formula (7) (“EPICLON HP-4710” manufactured by DIC Corporation) A prepreg having a resin content of 50% by mass was obtained in the same manner as in Example 1 except that 50 parts by mass was used and that the zinc octylate was changed to 0.10 parts by mass. In addition, EPICLON HP-4710 was previously subjected to molecular weight measurement described later, and its Z-average molecular weight was specified as 1330. Further, metal foil-clad laminates having a thickness of 0.8 mm and 0.4 mm were obtained in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained metal foil-clad laminate.

[Measurement method and evaluation method]
(1) Molecular weight measurement About 10 mg of epoxy resin was dissolved in 5 mL of tetrahydrofuran and filtered through a 0.45 μm filter. The solution was subjected to gel permeation chromatography (GPC) under the following conditions to determine the molecular weight distribution. It was measured. The molecular weight at each elution position of the GPC curve obtained via the molecular weight calibration curve was set to Mi, the number of molecules was set to Ni, and the Z average molecular weight Mz was calculated by the following equation.
Mz = Σ (Ni · Mi ³ ) / Σ (Ni · Mi ² )
(conditions)
Detector: Differential refractive index detector (RI-504, Showa Denko)
Column: TSKgel SuperHZ4000, SuperHZ2500, SuperHZ1000 (1 each, length 15 cm x inner diameter 6.0 mm) manufactured by Tosoh Corporation
Solvent: Tetrahydrofuran Flow rate: 0.45 mL / min
Column temperature: 40 ° C
Standard sample: Monodispersed polystyrene manufactured by Tosoh Corporation Data processing: GPC data processing system manufactured by TRC

(2) Solder float test Prepare three samples of metal foil-clad laminate 50mm x 50mm with 0.4mm insulation layer thickness, and float on 300 ° C solder for 30 minutes, abnormal appearance (delamination occurs) The presence or absence of was confirmed by visual judgment. Based on the number of samples in which an abnormality was observed, the evaluation was performed according to the following criteria.
○: 0 pieces △: 1-2 pieces ×: 3 pieces

(3) Glass transition temperature (Tg)
The obtained copper foil-clad laminate with an insulating layer thickness of 0.8 mm was cut into a size of 12.7 mm × 30 mm with a dicing saw, and then the surface copper foil was removed by etching to obtain a measurement sample. Using this measurement sample, the storage elastic modulus E ′ and loss elastic modulus E ″ were measured by the DMA method with a dynamic viscoelasticity analyzer (TA Instruments) in accordance with JIS C6481, and E ″ And the peak value of tan δ (= E ″ / E ′) was evaluated as Tg, and the heat resistance was evaluated.

  This application consists of a Japanese patent application filed with the Japan Patent Office on August 31, 2017 (Japanese Patent Application No. 2017-167497) and a Japanese patent application filed with the Japan Patent Office on November 1, 2017 (Japanese Patent Application No. 2017-2111967), the contents of which are incorporated herein by reference.

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

Claims (9)

An epoxy resin (A) having a repeating unit represented by the following formula (1) and having a Z average molecular weight of 1400 or more and 3000 or less;
A cyanate ester compound (B);
Containing a resin composition.
(In formula (1), X ₁ represents an alkylene group having 1 to 3 carbon atoms or an alkenylene group, and each R ₁ independently represents a hydrogen atom or an alkyl group or alkenyl group having 1 to 3 carbon atoms.)   The resin composition of Claim 1 whose content of the said epoxy resin (A) is 1-90 mass parts with respect to 100 mass parts of resin solid content.   A kind selected from the group consisting of an epoxy resin other than the epoxy resin (A) represented by the formula (1), a maleimide compound, a phenol resin, an oxetane resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group. The resin composition according to claim 1 or 2, further comprising the above.   The resin composition according to any one of claims 1 to 3, further comprising a filler (C).   The resin composition according to claim 4, wherein the content of the filler (C) is 50 to 1600 parts by mass with respect to 100 parts by mass of the resin solid content. A substrate;
The resin composition according to any one of claims 1 to 5, impregnated or coated on the base material,
Having a prepreg. The prepreg according to claim 6, 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 which has the resin composition as described in any one of Claims 1-5. An insulating layer;
A conductor layer formed on the surface of the insulating layer;
Have
The printed wiring board in which the said insulating layer contains the resin composition as described in any one of Claims 1-5.