JP2018080264A - 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 excellent particularly in plating peel strength, low water absorption and a low dielectric loss tangent among various properties required for a laminate for a printed wiring board; and a prepreg, a metal foil-clad laminate, a resin sheet and a printed wiring board that employ the resin composition.SOLUTION: The resin composition contains an active ester resin (A) represented by the general formula (1) in the figure, and an epoxy resin (B). (In the general formula (1), X each independently represent a hydrogen atom, a benzoyl naphthyl group, or Z; Y is represented by the specified general formula (2); Z are each independently selected from a hydrogen atom and groups represented by the specified general formulas (3) and (4); and n and k are each independently an integer from 1 to 10.)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 printed wiring board laminates are becoming increasingly severe. The required properties include, for example, properties such as low water absorption, moisture absorption heat resistance, flame retardancy, low dielectric constant, low dielectric loss tangent, low thermal expansion coefficient, heat resistance, chemical resistance, and high plating peel strength. However, so far, these required characteristics have not always been satisfied.

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

JP 2005-112981 A

  However, the technique described in Patent Document 1 has a problem that it is inferior in plating peel strength, low water absorption, and low dielectric loss tangent.

  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 plating peel strength, low water absorption, and low dielectric loss tangent, and An object of the present invention 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 problems, the present inventors have improved the characteristics of plating peel strength, water absorption, and dielectric loss tangent in a laminated board for printed wiring boards by using a specific active ester resin. As a result, the present invention has been completed.

That is, the present invention is as follows.
[1]
A resin composition containing an active ester resin (A) represented by the following general formula (1) and an epoxy resin (B).

  Here, in General Formula (1), X represents a hydrogen atom, a benzoyl naphthyl group, or Z each independently. Y is represented by the following general formula (2). Z is independently selected from the group represented by the hydrogen atom or the following general formulas (3) and (4). n and k are each independently an integer of 1 to 10.

  Here, in the general formula (2), * represents a binding site in the general formula (1).

  Here, in General Formula (3), * represents the binding site in General Formula (1). l is an integer of 1-10.

  Here, in General Formula (4), * represents the binding site in General Formula (1). m is an integer of 1-10.

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

[3]
The resin composition according to [1] or [2], further containing a cyanate ester compound (C).

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

[5]
Any one of [1] to [4], which further contains any one or more of a group selected from 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 one item.

[6]
The resin composition according to [4] or [5], wherein the content of the filler (D) in the resin composition is 50 to 1600 parts by mass with respect to 100 parts by mass of the resin solid content.

[7]
The prepreg which has a base material and the resin composition as described in any one of [1]-[6] impregnated or apply | coated to this base material.

[8]
A metal foil-clad laminate comprising at least one prepreg as described in [7] and a metal foil disposed on one or both sides of the prepreg.

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

[10]
The printed wiring board which has an insulating layer and the conductor layer formed in the surface of this insulating layer, and this insulating layer contains the resin composition as described in any one of [1]-[6].

  According to the present invention, among various properties required for a laminate for a printed wiring board, a resin composition excellent in plating peel strength, low water absorption, and low dielectric loss tangent, and a prepreg using the resin composition, A metal 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 (D), unless otherwise specified, and “resin solid content of 100 parts by mass”. Means that the total of the components excluding the solvent and the filler (D) in the resin composition is 100 parts by mass.

(Resin composition)
The resin composition of this embodiment contains an active ester resin (A) and an epoxy resin (B).

[Active ester resin (A)]
The active ester resin (A) used in the present embodiment is represented by the following general formula (1).

  Here, in General Formula (1), X represents a hydrogen atom, a benzoyl naphthyl group, or Z each independently. Y is represented by the following general formula (2). Z is independently selected from the group represented by the hydrogen atom or the following general formulas (3) and (4). n and k are each independently an integer of 1 to 10.

  Here, in the general formula (2), * represents a binding site in the general formula (1).

  Here, in General Formula (3), * represents the binding site in General Formula (1). l is an integer of 1-10.

  Here, in General Formula (4), * represents the binding site in General Formula (1). m is an integer of 1-10.

  Specific examples of the active ester resin (A) represented by the general formula (1) include those represented by the following formulas (5) to (7) and the following formulas (5) to (7). And those having a part of the structure represented by the following formulas (5) to (7) (all satisfying the general formula (1)). It is done. In other words, specific examples of the active ester resin (A) represented by the general formula (1) include those represented by the following formulas (5) to (7) and the following formula (5). ) To (7) having a part or all of the structure as a partial structure (both compounds satisfying the general formula (1)) (however, in such exemplified compounds, “formula (5) ) To (7) “a part or all of the structure represented by (7) need not be included as a unit structure.”

  Moreover, as another specific example of active ester resin (A) represented by the said General formula (1), what is represented, for example by following formula (8)-(10) is mentioned.

  Such an active ester resin (A) may be a commercially available product or may be synthesized by a conventional method. Examples of the active ester resin (A) include EPICLON EXB-8200-65T manufactured by DIC Corporation or EPICLON HPC-8100-65T manufactured by DIC Corporation.

  The content of the active ester resin (A) is preferably 1 to 90 parts by mass, more preferably 10 to 80 parts by mass, and still more preferably 15 to 70 parts by mass with respect to 100 parts by mass of the resin solid content. And particularly preferably 20 to 60 parts by mass. When the content of the active ester resin (A) is within the above range, the plating peel strength of the resulting cured product is improved, and the water absorption rate and dielectric loss tangent tend to be reduced.

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

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

  The content of the epoxy resin (B) is preferably 1 to 90 parts by mass, more preferably 20 to 70 parts by mass, and further preferably 40 to 60 parts by mass with respect to 100 parts by mass of the resin solid content. is there. When 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, chemical resistance, and desmear resistance to improve more.

[Cyanate ester compound (C)]
The resin composition of this embodiment may further contain a cyanate ester compound (C). The cyanate ester compound (C) 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).

  Examples of the cyanate ester compound (C) include those represented by the general formula (11).

Here, in the general formula (11), 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 6 to 12 carbon atoms. A group to which the aryl group is bonded. 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, each independently, an integer of 1 to 3. q represents the number of Ra bonded to Ar ₁ , 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. is there. t represents an average number of repetitions and is an integer of 0 to 50, and the other cyanate compound (C) may be a mixture of compounds having different t. When there are a plurality of Ws, each independently represents a single bond, a divalent organic group having 1 to 50 carbon atoms (a hydrogen atom may be substituted with a hetero atom), or a divalent group having 1 to 10 nitrogen atoms. An organic group (for example, —N—R—N— (wherein R represents an organic group)), a carbonyl group (—CO—), a carboxy group (—C (═O) O—), a carbonyl dioxide group ( —OC (═O) O—), a sulfonyl group (—SO ₂ —), a divalent sulfur atom, or a divalent oxygen atom.

  The alkyl group in Ra of the general formula (11) may have any of a linear or branched chain structure and a cyclic structure (for example, a cycloalkyl group).

  In addition, the hydrogen atom in the alkyl group in the general formula (11) and the aryl group in Ra is substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, or a cyano group. Also good.

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

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

  Specific examples of the divalent organic group having 1 to 50 carbon atoms in W of the general formula (11) include a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, a trimethylcyclohexylene group, and biphenylyl. Examples include a methylene group, dimethylmethylene-phenylene-dimethylmethylene group, fluorenediyl group, and phthalidodiyl group. The hydrogen atom in the divalent organic group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, a cyano group, or the like.

  Examples of the divalent organic group having 1 to 10 nitrogen atoms in W of the general formula (11) include an imino group and a polyimide group.

  Moreover, as an organic group of W in General formula (11), what is a structure represented by the following general formula (12) or the following general formula (13) is mentioned, for example.

Here, in the general formula (12), 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. Is done. u represents an integer of 0 to 5.

Here, in the general formula (13), 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 as 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, or a trifluoromethyl group. Or 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 General formula (11), the bivalent group represented by a following formula is mentioned.

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

Specific examples of Ar _{2 in the} general formula (12) and Ar _{3 in} the general formula (13) include two carbon atoms represented by the general formula (12) or two oxygen atoms represented by the general formula (13). A benzenetetrayl group bonded to the 1,4-position or the 1,3-position, the two carbon atoms or the two oxygen atoms are in the 4,4′-position, 2,4′-position, 2,2′-position, 2 , 3′-position, 3,3′-position, or 3,4′-position, and the above two carbon atoms or two oxygen atoms are in the 2,6-position, 1,5-position , 1,6-position, 1,8-position, 1,3-position, 1,4-position, or 2,7-position.

  Rb, Rc, Rd, Re, Rf and Rg in the general formula (12), and the alkyl group and aryl group in Ri and Rj in the general formula (13) have the same meanings as those in the general formula (11).

  Specific examples of the cyanato-substituted aromatic compound represented by the general formula (11) include cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methylbenzene, 1 -Cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methoxybenzene, 1-cyanato-2,3-, 1-cyanato-2,4-, 1-cyanato-2,5-, 1-cyanato-2,6-, 1-cyanato-3,4- or 1-cyanato-3,5-dimethylbenzene, cyanatoethylbenzene, cyanatobutylbenzene, cyanatooctylbenzene, cyanatononylbenzene, 2- (4-cyanaphenyl) -2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylben 1-cyanato-2- or 1-cyanato-3-chlorobenzene, 1-cyanato-2,6-dichlorobenzene, 1-cyanato-2-methyl-3-chlorobenzene, cyanatonitrobenzene, 1-cyanato-4- Nitro-2-ethylbenzene, 1-cyanato-2-methoxy-4-allylbenzene (eugenol cyanate), methyl (4-cyanatophenyl) sulfide, 1-cyanato-3-trifluoromethylbenzene, 4-cyanatobiphenyl 1-cyanato-2- or 1-cyanato-4-acetylbenzene, 4-cyanatobenzaldehyde, 4-cyanatobenzoic acid methyl ester, 4-cyanatobenzoic acid phenyl ester, 1-cyanato-4-acetaminobenzene, 4 -Cyanatobenzophenone, 1-cyanato-2,6-di-ter t-butylbenzene, 1,2-dicyanatobenzene, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,4-dicyanato-2-tert-butylbenzene, 1,4-dicyanato-2, 4-dimethylbenzene, 1,4-dicyanato-2,3,4-dimethylbenzene, 1,3-dicyanato-2,4,6-trimethylbenzene, 1,3-dicyanato-5-methylbenzene, 1-cyanato or 2-cyanatonaphthalene, 1-cyanato-4-methoxynaphthalene, 2-cyanato-6-methylnaphthalene, 2-cyanato-7-methoxynaphthalene, 2,2′-dicyanato-1,1′-binaphthyl, 1,3- , 1,4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,6- or 2,7-dicyanatosinaphthalene, 2,2'- or 4,4 ' - Anatobiphenyl, 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-bis (4-cyanato) Enyl) 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-shear Natophenyl) -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, screw ( -Cyanatophenyl) biphenylmethane, 1,1-bis (4-cyanatophenyl) cyclopentane, 1,1-bis (4-cyanatophenyl) cyclohexane, 2,2-bis (4-cyanato-3-isopropyl) Phenyl) 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-si Anatophenyl) -3,3,5-trimethylcyclohexane, 4- [bis (4-cyanatophenyl) methyl] biphenyl, 4,4-dicyanato Nzophenone, 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-cresol phthalate) Rain's cyanate), 9,9'-bis (4-cyanatophenyl) fluorene, 9,9-bis (4-cyanato-3-methylphenyl) fluorene, 9,9-bis (2-cyanato-5-biphenyl) Yl) 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-methylaniline) ) -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'-(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.

Other specific examples of the compound represented by the general formula (11) include phenol novolak resins and cresol novolak resins (phenol, alkyl-substituted phenol or halogen-substituted phenol, formalin, paraformaldehyde, etc. by a known method). Of formaldehyde compound in an acidic solution), trisphenol novolak resin (reacted hydroxybenzaldehyde and phenol in the presence of an acidic catalyst), fluorene novolak resin (fluorenone compound and 9,9-). bis (hydroxyaryl) fluorenes those reacted in the presence of an acid catalyst), phenol aralkyl resins, cresol aralkyl resin, a naphthol aralkyl resin and a biphenyl aralkyl resin (a known method, Ar ₄ - CH ₂ Y) ₂ (Ar ₄ represents a phenyl group, Y represents a halogen atom. Hereinafter, the same in this paragraph.) Represented by such bishalogenomethyl compound and a phenol compound and an acidic catalyst or unsubstituted A reaction with a catalyst, a reaction between a bis (alkoxymethyl) compound represented by Ar ₄ — (CH ₂ OR) ₂ and a phenol compound in the presence of an acidic catalyst, or Ar ₄ — ( A reaction product of a bis (hydroxymethyl) compound and a phenol compound represented by CH ₂ OH) ₂ in the presence of an acidic catalyst, or a polycondensation of an aromatic aldehyde compound, an aralkyl compound and a phenol compound. ), Phenol-modified xylene formaldehyde resin (by known methods, acid contact between xylene formaldehyde resin and phenol compound) ), 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, poly Phenols such as phenolic resins having a naphthylene ether structure (polyhydric hydroxynaphthalene compounds having two or more phenolic hydroxy groups in one molecule by dehydration condensation in the presence of a basic catalyst) Examples include those obtained by cyanating a resin by the same method as described above, and prepolymers thereof. These are not particularly limited. These other cyanate ester compounds (C) can be used alone or in combination.

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

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

  The method for producing these cyanate ester compounds (C) is not particularly limited, and known methods 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 (C) is preferably 1 to 90 parts by weight, more preferably 15 to 70 parts by weight, and still more preferably 20 to 60 parts by weight with respect to 100 parts by weight of the resin solid content. Part. When the content of the cyanate ester compound (C) is within the above range, heat resistance and chemical resistance tend to be further improved.

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

  Examples of the inorganic filler include, but are not limited to, silicas such as natural silica, fused silica, synthetic silica, amorphous silica, aerosil, and hollow silica; silicon compounds such as white carbon; titanium white, zinc oxide, magnesium oxide, Metal oxides such as zirconium oxide; nitrides such as boron nitride, 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 Mica, E glass, A glass, NE glass, C glass, L glass, D glass, S glass, M glass G20, short glass fiber (glass fine powder such as E glass, T glass, D glass, S glass, Q glass) 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 (D), the thermal expansion coefficient of the cured product of the resin composition tends to be further reduced.

  The content of the filler (D) 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 (D) is 50 parts by mass or more, the thermal expansion coefficient tends to be further reduced.

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

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

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

[Other ingredients]
The resin composition of the present embodiment may contain other components as necessary in addition to the above components. The other component is not particularly limited, but for example, any one or more selected from the group selected from a maleimide compound, a phenol resin, an oxetane resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group. Can be mentioned.

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

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

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

(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 alone 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.

(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 alone or in combination.

[Curing accelerator]
The resin composition of this embodiment may further contain a curing accelerator. Although it does not specifically limit as a hardening accelerator, For example, imidazoles, such as a 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, 2-N-ethylanilino Tertiary amines such as ethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine; phenol, xylenol, cresol, resorcin, cateco Phenols such as lead; organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetone; these organic metal salts Inorganic metal salts such as tin chloride, zinc chloride, aluminum chloride; organic tin compounds such as dioctyl tin oxide, other alkyl tins, alkyl tin oxides, etc. It is done. Among these, triphenylimidazole promotes the curing reaction and is particularly preferable because it tends to have excellent glass transition temperature and coefficient of thermal expansion.

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

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

[Method for producing resin composition]
Although the manufacturing method of the resin composition of this embodiment is not specifically limited, For example, the method of mix | blending each component mentioned above in a solvent one by one and fully stirring is mentioned. At this time, in order to uniformly dissolve or disperse each component, known processes such as stirring, mixing, and kneading can be performed. Specifically, the dispersibility of the filler (D) 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 can be performed according to a conventional method, and is not specifically limited. For example, after impregnating or applying the resin component in the present embodiment to the base material, by semi-curing (B stage) by heating in a dryer at 100 to 200 ° C. for 1 to 30 minutes, The prepreg of this embodiment can be produced.

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

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

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

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

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

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

(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 can be performed according to a conventional method, and is not specifically limited. 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.

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

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

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

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

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

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

  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 the present embodiment is particularly effective as a printed wiring board for a semiconductor package because the above-mentioned insulating layer has excellent properties in plating peel strength, low water absorption, and low dielectric loss tangent. it can.

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

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

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

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

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

Example 1
Active ester resin represented by the following general formula (1) (DIC Corporation, EPICLON EXB-8200-65T, ester equivalent: 223 g / eq.) 25 parts by mass, biphenylaralkyl type epoxy resin (Nippon Kayaku Co., Ltd.) ), NC-3000-FH, epoxy equivalent: 320 g / eq.) 50 parts by mass, SNCN (cyanate equivalent: 256 g / eq.) Obtained by Synthesis Example 1, 25 parts by mass, fused silica (Admatechs Co., Ltd.) Manufactured, SC2050MB) 100 parts by mass, 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd.) 0.10 parts by mass, and zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.) 0.13 parts by mass Were mixed to obtain a varnish.

  Here, in General Formula (1), X represents a hydrogen atom, a benzoyl naphthyl group, or Z each independently. Y is represented by the following general formula (2). Z is independently selected from the group represented by the hydrogen atom or the following general formulas (3) and (4). n and k are each independently an integer of 1 to 10.

  Here, in the general formula (2), * represents a binding site in the general formula (1).

  Here, in General Formula (3), * represents the binding site in General Formula (1). l is an integer of 1-10.

  Here, in General Formula (4), * represents the binding site in General Formula (1). m is an integer of 1-10.

(Example 2)
50 mass parts of an active ester resin (manufactured by DIC Corporation, EPICLON EXB-8200-65T, ester equivalent: 223 g / eq.), Blended with SNCN (cyanate equivalent: 256 g / eq.) Obtained in Synthesis Example 1. A varnish was obtained in the same manner as in Example 1 except that the amount of zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.) was changed to 0.10 parts by mass.

(Comparative Example 1)
The SNCN obtained in Synthesis Example 1 (cyanate equivalent: 256 g / eq.) Was not blended with an active ester resin (manufactured by DIC Corporation, EPICLON EXB-8200-65T, ester equivalent: 223 g / eq.). A varnish was obtained in the same manner as in Example 1 except that the content was 50 parts by mass and that the zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.) was 0.10 parts by mass.

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

(Characteristic evaluation)
(Plating peel strength)
The copper foil in the surface layer of the copper clad laminate having an insulating layer thickness of 0.2 mm obtained above was removed by etching, and an electroless copper plating process (name of chemical used: MCD-PL, manufactured by Uemura Kogyo Co., Ltd.) MDP-2, MAT-SP, MAB-4-C, MEL-3-APEA ver. 2) About 0.5 μm of electroless copper plating is applied to the insulating layer and dried at 130 ° C. for 1 hour. went. Subsequently, electrolytic copper plating was performed so that the thickness of the plated copper was 20 μm, and drying was performed at 180 ° C. for 1 hour. In this manner, a test piece of a printed wiring board in which a conductor layer (plated copper) having a thickness of 20 μm was formed on an insulating layer having a thickness of 0.8 mm was produced.

  As a test piece of the copper-clad laminate obtained as described above, a plating peel was used in accordance with JIS C6481, using a desmear-treated one (without desmear) and a desmear-treated one (with desmear). The strength (adhesive force) was measured three times, and the average value was determined. Here, the “desmear treatment” was performed by immersing the insulating layer obtained above in an alkaline aqueous solution (1N sodium hydroxide aqueous solution) at 40 ° C. for 5 minutes. Moreover, about the test piece swollen by drying after electrolytic copper plating, it evaluated using the part which is not swollen.

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

(Dielectric loss tangent (Df))
Using the test piece obtained by removing the copper foil of the copper-clad laminate with an insulating layer thickness of 0.8 mm obtained as described above by etching, using the cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies), The measurement of 10 GHz dielectric loss tangent was performed 3 times, 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)

An active ester resin (A) represented by the following general formula (1);
Epoxy resin (B);
Containing a resin composition.
(In general formula (1), each X independently represents a hydrogen atom, a benzoylnaphthyl group or Z. Y is represented by the following general formula (2). Z is each independently a hydrogen atom or (Selected from the group represented by the general formulas (3) and (4), n and k are each independently an integer of 1 to 10).
(In general formula (2), * represents a binding site in general formula (1).)
(In General Formula (3), * represents a binding site in General Formula (1). L is an integer of 1 to 10.)
(In General Formula (4), * represents a binding site in General Formula (1). M is an integer of 1 to 10.) Content in the resin composition of the said active ester resin (A) is 1-90 mass parts with respect to 100 mass parts of resin solid content,
The resin composition according to claim 1. Further containing a cyanate ester compound (C),
The resin composition according to claim 1 or 2. Further containing a filler (D),
The resin composition as described in any one of Claims 1-3. A maleimide compound, a phenol resin, an oxetane resin, a benzoxazine compound, and a group selected from a compound having a polymerizable unsaturated group, further containing any one or more kinds;
The resin composition as described in any one of Claims 1-4. Content in the resin composition of the said filler (D) 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.