JP2019089929A - Resin composition, prepreg, metal foil-clad laminate, resin sheet and printed wiring board - Google Patents

Abstract

To provide a resin composition exhibiting excellent physical property balance in electric characteristics, heat resistance and thermal conductivity, and to provide a prepreg, a metal foil-clad laminate, a resin sheet and a printed wiring board using the same.SOLUTION: A resin composition contains at least a cyanate ester compound (A), and a bismaleimide compound (B) represented by the following formula (I). In formula (I), Rto Reach independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.SELECTED DRAWING: None

Description

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

  In recent years, high integration and miniaturization of semiconductors widely used in electronic devices, communication devices, personal computers, etc. are accelerating. Along with this, various characteristics required for a laminate for a semiconductor package used for a printed wiring board are becoming increasingly severe. Examples of the required properties include properties such as low water absorption, hygroscopic heat resistance, flame retardancy, low dielectric constant, low dielectric loss tangent, low thermal expansion coefficient, heat resistance, chemical resistance, high plating peel strength and the like.

  Conventionally, cyanate ester compounds are known as resins for printed wiring boards having excellent heat resistance and electrical properties, and in recent years, resin compositions in which an epoxy resin, a bismaleimide compound, etc. are used in combination with a cyanate ester compound are semiconductor plastic packages It is widely used for high-performance printed wiring board materials etc.

  For example, in Patent Document 1, a curable resin composition composed of a cyanate ester compound having a specific structure and other components suppresses the generation of cracks during curing while achieving both a low coefficient of thermal expansion and a low water absorption. It is described that it can give a cured product.

  Further, Patent Document 2 discloses a thermosetting type containing a polyfunctional unsaturated imide of a specific structure, a thermoplastic polyimide of a specific structure having a compatible region with a polyfunctional unsaturated imide of this specific structure, and other components. It is described that the polyimide resin composition is excellent also in mechanical properties such as toughness, flexibility and adhesiveness while maintaining excellent properties such as high heat resistance.

  Furthermore, Patent Document 3 discloses a ketone-based thermosetting resin composition containing a thermosetting resin containing an epoxy resin and a bismaleimide compound, and a filler containing 60 to 85% by mass of the solid content. Resin varnish contained in a solvent is excellent in dielectric properties, adhesion with a conductor layer, adhesion to a non-smooth surface (circuit embedding property) to which circuit processing is applied, etc., no void is generated, and streak-like It is described that an insulating layer free from appearance defects such as unevenness can be produced.

WO 2012/105547 Japanese Patent Application Publication No. 06-157905 JP, 2012-116941, A

  However, although the curable resin composition described in Patent Document 1 has good properties such as low water absorption and low coefficient of thermal expansion, there is still room for improvement from the viewpoint of the balance between dielectric properties, heat resistance and thermal conductivity. The

  Moreover, although the thermosetting polyimide resin composition of the specific structure described in Patent Document 2 is excellent in heat resistance, and further in mechanical properties such as toughness, flexibility, adhesiveness, etc., it has dielectric properties, heat resistance and heat. There is still room for improvement in terms of conductivity balance.

  Furthermore, although the resin composition of the specific structure described in Patent Document 3 is excellent in dielectric properties and circuit embedding, and can produce an insulating layer without appearance defects, it has a balance of dielectric properties, heat resistance and thermal conductivity. From the point of view, there is still room for improvement.

  The present invention has been made in view of the above-mentioned problems, and a resin composition which exhibits excellent physical property balance in electrical characteristics, heat resistance and thermal conductivity, and a prepreg using the same, and a metal foil-clad laminate , A resin sheet, a printed wiring board, and the like.

  The present inventors diligently studied to solve the above problems. As a result, they have found that the above-mentioned problems can be achieved by using the cyanate ester compound (A) and the bismaleimide compound (B) having a specific structure in combination, and the present invention has been completed.

That is, the present invention includes the following aspects.
[1] A resin composition containing at least a cyanate ester compound (A) and a bismaleimide compound (B) represented by the following formula (I).
(Wherein, R _{1 to} R ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
[2] The resin composition according to [1], wherein the content of the bismaleimide compound (B) is 1 to 60 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
[3] The content ratio of the cyanate ester compound (A) and the bismaleimide compound (B) is the ratio of the unsaturated imide group of the bismaleimide compound (B) and the cyanate group of the cyanate ester compound (A) The resin composition as described in [1] or [2] which is 0.05 or more and 0.99 or less in equivalent ratio (equivalent of unsaturated imide group / equivalent of cyanate group).
[4] From the group consisting of maleimide compounds other than bismaleimide compounds (B) represented by the above formula (I), epoxy resins, phenol resins, oxacene resins, benzoxazine compounds, and compounds having a polymerizable unsaturated group The resin composition as described in any one of [1]-[3] which further contains 1 or more types selected.
[5] A maleimide compound other than the bismaleimide compound (B) represented by the above formula (I) is further contained, and the content ratio of the cyanate ester compound (A) and the maleimide compound is the unsaturation of the maleimide compound The equivalent ratio of the imide group to the cyanate group of the cyanate ester compound (A) (equivalent of unsaturated imide group / equivalent of cyanate group) is 0.1 or more and 1.5 or less [1] to [3] The resin composition as described in any one of these.
[6] The resin composition according to any one of [1] to [5], which further contains a filler (C).
[7] The resin composition according to [6], 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 in the resin composition.

[8] A prepreg comprising at least a substrate, and the resin composition according to any one of [1] to [7] impregnated or applied to the substrate.
[9] A metal foil-clad laminate, comprising at least one or more of the prepregs according to [8] and a metal foil disposed on one side or both sides of the prepreg.
[10] A resin sheet comprising at least a support, and the resin composition according to any one of [1] to [7] provided on the surface of the support.
[11] A printed wiring comprising at least an insulating layer, and a conductor layer provided on the surface of the insulating layer, wherein the insulating layer comprises the resin composition according to any one of [1] to [7]. Board.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which expresses the physical property balance excellent in the glass transition temperature (Tg), an electrical property, heat resistance, and thermal conductivity, a prepreg using the same, a metal foil tension laminate sheet, a resin sheet And a printed wiring board etc. can be provided. Further, according to the preferred embodiment of the present invention, the productivity of such a prepreg, a metal foil-clad laminate, a resin sheet, a printed wiring board and the like can be enhanced, which leads to cost reduction.

  Hereinafter, although a mode for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail, the present invention is not limited to this, and various modifications can be made within the scope of the present invention. Is possible.

[Resin composition]
The resin composition of the present embodiment at least contains a cyanate ester compound (A) and a bismaleimide compound (B) represented by the following formula (I). Since it is comprised in this way, the resin composition of this embodiment can express the physical property balance excellent in the electrical property, heat resistance, and heat conductivity.

(Wherein, R _{1 to} R ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

(Cyanate ester compound (A))
The cyanate ester compound contained in the resin composition in this embodiment is not particularly limited as long as it is a compound having an aromatic moiety substituted by at least one cyanato group (cyanate group) in the molecule. The resin composition using a cyanate ester compound has excellent properties of glass transition temperature, low thermal expansion, plating adhesion and the like when it is a cured product.

  Examples of cyanate ester compounds include, but are not limited to, those represented by the following formula (1).

In the above formula (1), Ar ₁ represents a benzene ring, a naphthalene ring or a single benzene ring. When there are a plurality of Ar _{1 's} , they may be the same or different. Ra each independently represents 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 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 represents the number of cyanato groups bonded to Ar ₁ and each is independently an integer of 1 to 3. q represents the number of Ra bound to Ar ₁ , 4-p when Ar ₁ is a benzene ring, 6-p when naphthalene ring, and 8-p when two benzene rings are singly bonded . t represents an average repeat number and is in the range of 0 to 50, and the cyanate ester compound may be a mixture of compounds different in t. In the case where there are a plurality of X's, each independently has 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 nitrogen having 1 to 10 carbons. Organic group (eg, -N-R-N- (wherein R represents an organic group)), carbonyl group (-CO-), carboxy group (-C (= O) O-), carbonyl dioxide group ( -OC (= O) O-), a sulfonyl group (-SO ₂ -), represents any divalent sulfur atom or a divalent oxygen atom.

The alkyl group at Ra in the above formula (1) may have any of a linear or branched chain structure and a cyclic structure (for example, a cycloalkyl group etc.).
The hydrogen atom in the alkyl group in Formula (1) 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, A 2, 2- dimethyl propyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a trifluoromethyl group etc. are mentioned.

  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 A phenyl group, a trifluorophenyl group, a methoxyphenyl group, o-, m- or p-tolyl group etc. are mentioned.

  As an alkoxyl group, although it is not limited to the following, for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group and the like can be mentioned.

  Specific examples of the divalent organic group having 1 to 50 carbon atoms in X in the above formula (1) include, but are not limited to, methylene group, ethylene group, trimethylene group, cyclopentylene group, cyclohexylene group, trimethyl Examples thereof include a cyclohexylene group, a biphenylyl methylene group, a dimethyl methylene-phenylene-dimethyl methylene group, a fluorenediyl group, and a phthalide diyl group. The hydrogen atom in the divalent organic group may be substituted by 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 in the formula (1) include, but are not limited to, imino groups and polyimide groups.

  Moreover, as an organic group of X in said Formula (1), what is a structure represented by following formula (2) or following formula (3) is mentioned, for example.

(In the above formula (2), Ar ₂ represents a benzenetetrayl group, a naphthalenetetrayl group or a biphenyltetrayl group, and when u is 2 or more, they may be identical to or different from each other. Rb, Rc , Rf and Rg each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryl group having at least one trifluoromethyl group, or a phenolic hydroxy group Each of Rd and Re is independently selected from any one kind 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, or a hydroxy group U is an integer of 0 to 5)

(In the formula (3), 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 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 benzyl group, an alkoxyl group having 1 to 4 carbon atoms, a hydroxy group, a trifluoromethyl group or a cyanato group And at least one substituted aryl group, wherein v represents an integer of 0 to 5, but may be a mixture of compounds different in v).

  Furthermore, as X in Formula (1), the bivalent group represented by a following formula is mentioned.

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

As specific examples of Ar ₂ of Formula ( ₂ ) and Ar ₃ of Formula (3), two carbon atoms shown in Formula (2) or two oxygen atoms shown in Formula (3) are 1,4 Benzenetetrayl group bonded to the position or 1, 3 position, the above two carbon atoms or two oxygen atoms are 4, 4 ', 2, 4', 2, 2 ', 2, 3' And the biphenyltetrayl group bonded to the 3,3'-position or the 3,4'-position, and the above two carbon atoms or two oxygen atoms are 2,6, 1,5,1,6 And a naphthalenetetrayl group bonded to the 1, 8, 1, 3, 1, 4, or 2,7 position.

  The alkyl group and the aryl group in Rb, Rc, Rd, Re, Rf and Rg in Formula (2), and Ri and Rj in Formula (3) have the same meanings as in Formula (1) above.

  Specific examples of cyanato-substituted aromatic compounds represented by the above formula (1) include, but are not limited to, cyanatobenzene, 1-cyanato-2-1, 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-cyanaphenyl) -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 (cyanide of eugenol), methyl (4-cyanatophenyl) sulfide, 1-cyanato-3-trifluoromethylbenzene, 4- 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-dicyanathosinaphthalene, 2, 2'- Or 4,4'-dicyanatobiphenyl, 4,4'-dicyanatooctafluorobiphenyl, 2,4'- or 4,4'-dicyanatodiphenylmethane, bis (4-cyanato-3,5-dimethylphenyl) methane, 1 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-cyano) Natophenyl) 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 ( -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-cyanatophenyl)- 1-phenylethane, 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-dicyl Natobenzophenone, 1,3-bis (4-cyanatophenyl) -2-propen-1-one, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) sulfide, bis (4-cyanato) Phenyl) sulfone, 4-cyanatobenzoic acid-4-cyanatophenyl ester (4-cyanatophenyl-4-cyanatobenzoate), bis- (4-cyanatophenyl) carbonate, 1,3-bis (4-cyano) Anatophenyl) 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-creso) Cyanate of ruphthalein), 9,9'-bis (4-cyanatophenyl) fluorene, 9,9-bis (4-cyanato-3-methylphenyl) fluorene, 9,9-bis (2-cyanato-5-biphenyl) (I) fluorene, tris (4-cyanatophenyl) methane, 1,1,1-tris (4-cyanatophenyl) ethane, 1,1,3-tris (4-cyanatophenyl) propane, α, α, α, 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-methyl) Lino) -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 '-(hexafluoroisopropyl) Phenyl) 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- Scan (4-cyanatophenyl) indolin-2-one, and 2-phenyl-3,3-bis (4-cyanatophenyl) include indolin-2-one.

Further, other specific examples of the compound represented by the above formula (1) include, but are not limited to, phenol novolac resin and cresol novolac resin (phenol, alkyl substituted phenol or halogen substituted phenol by a known method; Formaldehyde compounds such as formalin and paraformaldehyde are reacted in an acidic solution), trisphenol novolak resin (hydroxybenzaldehyde and phenol reacted in the presence of an acidic catalyst), fluorene novolac resin (fluorenone compound) And 9,9-bis (hydroxyaryl) fluorenes in the presence of an acidic catalyst), phenolaralkyl resin, cresolaralkyl resin, naphtholaralkyl resin and biphenylaralkyl resin (known methods) _{Ri, 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, Ar ₄ - (CH ₂ OH) bis (hydroxymethyl) as represented by _two things compound and a phenol compound is reacted in the presence of an acidic catalyst, or an aromatic aldehyde compound and aralkyl compound with a phenol compound Polycondensed), phenol-modified xylene formaldehyde resin (xylene formaldehyde resin and phenol compound by a known method) (In the presence of an acidic catalyst), a modified naphthalene formaldehyde resin (a reaction of a naphthalene formaldehyde resin and a hydroxy-substituted aromatic compound in the presence of an acidic catalyst by a known method), a phenol-modified dicyclopentadiene Resin, Phenolic resin having a polynaphthylene ether structure (in which a multivalent hydroxynaphthalene compound having two or more phenolic hydroxy groups in one molecule is dehydrated and condensed by a known method in the presence of a basic catalyst) And the like, and those obtained by cyanating the phenolic resin by the same method as described above, and prepolymers of these.

  The above-mentioned cyanate ester compounds can be used singly or in combination of two or more.

  Among the above-mentioned cyanate ester compounds, bisphenol A type cyanate ester compounds, bisphenol E type cyanate ester compounds, bisphenol F type cyanate ester compounds such as bisphenol F type cyanate ester compounds, naphthol aralkyl type cyanate ester compounds, and Phenolic novolac type cyanate ester compounds are preferred. That is, in the present embodiment, the cyanate ester compound includes at least one selected from the group consisting of a bisphenol-type cyanate ester compound, a naphthol aralkyl-type cyanate ester compound, and a phenol novolac-type cyanate ester compound. preferable. More preferably, the cyanate ester compound contains a naphthol aralkyl type cyanate ester compound.

  The content of the cyanate ester compound can be appropriately set according to the desired characteristics, and is not particularly limited, but from the viewpoint of further improving the physical property balance of the electrical characteristics, heat resistance and thermal conductivity, the resin solid content 100 30-100 mass parts is preferable with respect to a mass part, More preferably, it is 35-80 mass parts, More preferably, it is 40-70 mass parts.

  In the present embodiment, “resin solid content” refers to components excluding the solvent and the filler in the resin composition of the present embodiment, unless otherwise noted, and “100 parts by mass of resin solid content” The term "S" means that the total of components excluding the solvent and the filler in the resin composition of the present embodiment is 100 parts by mass.

(Bismaleimide compound (B))
The bismaleimide compound (B) contained in the resin composition in the present embodiment is a bismaleimide compound represented by the following formula (I). The resin composition using a cyanate ester compound has excellent properties of glass transition temperature, low thermal expansion, plating adhesion and the like when it is a cured product.

In the above formula (I), R ₁ ~R ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The alkyl group in the above formula (I) may have any of linear or branched chain structure. Further, the alkyl group in the formula (I) may be substituted by a halogen atom such as a fluorine atom or a chlorine atom.

  A methyl group, an ethyl group, a propyl group, an isopropyl group is mentioned as a specific example of the alkyl group in the said Formula (I). In addition, the substitution position of the maleimide group to the benzene ring in the above formula (I) is not particularly limited and is arbitrary, for example, 2,2 'position, 2,3' position, 2,4 'position, 3,3 The 'position 3, 4' or 4, 4 'is preferred, more preferably the 3, 4' or 4, 4 '.

  The bismaleimide compound (B) represented by the above-mentioned formula (I) can be synthesized by a conventionally known synthetic method, and the production method thereof is not particularly limited. For example, it can be obtained by reacting maleic anhydride with diaminodiphenyl ether to prepare maleamic acid and then dehydrating cyclizing maleamic acid.

  The content of the bismaleimide compound (B) in the present embodiment can be appropriately set according to the desired characteristics, and is not particularly limited, but from the viewpoint of further improving the physical property balance of electrical characteristics, heat resistance and thermal conductivity. Therefore, 1 part by weight or more and 60 parts by weight or less is preferable, more preferably 1 part by weight or more and less than 34 parts by weight, and still more preferably 2 parts by weight or more and less than 30 parts by weight. When the content of the bismaleimide compound (B) is in the above range, the electrical properties and heat resistance of the resulting cured product tend to be further improved.

  Further, the content ratio of the cyanate ester compound (A) and the bismaleimide compound (B) in the present embodiment can be appropriately set according to the desired characteristics, and is not particularly limited, but the electrical characteristics, heat resistance and From the viewpoint of further improving the physical property balance of thermal conductivity, the equivalent ratio of the unsaturated imide group of the bismaleimide compound (B) to the cyanate group of the cyanate ester compound (A) (equivalent of unsaturated imide group / cyanate group) The equivalent weight is preferably 0.05 or more and less than 0.99, more preferably 0.1 or more and 0.75 or less, and still more preferably 0.15 or more and 0.6 or less.

  The above-described bismaleimide compounds (B) can be used singly or in combination of two or more.

  The resin composition of the present embodiment further includes a maleimide compound other than the maleimide compound (B) represented by the above-mentioned formula (I) (hereinafter may be simply referred to as a "maleimide compound"), an epoxy resin, It is preferable to further contain one or more selected from the group consisting of a phenol resin, an oxacene resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group. Each of these components will be described below.

[Maleimide compound]
The maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule, and examples thereof include N-phenyl maleimide, N-hydroxyphenyl maleimide, bis (4-maleimidophenyl) methane, and 2,2 -Bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis ( Examples include 3,5-diethyl-4-maleimidophenyl) methane, maleimide compounds represented by the following formula (4), prepolymers of these maleimide compounds, and prepolymers of maleimide compounds and amine compounds. Among these, 2,2′-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and the following formula (4) At least one selected from the group consisting of maleimide compounds is preferred. By containing such a maleimide compound, the balance of physical properties of the resulting cured product tends to be more excellent. From the same viewpoint, the maleimide compound more preferably contains at least one selected from the group consisting of maleimide compounds represented by the following formula (4).

Here, in Formula (4), each R ₅ independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In the formula (4), n ₁ represents an integer of 1 or more, preferably 10 or less, and more preferably 7 or less.

  The content of the maleimide compound in the present embodiment can be appropriately set according to the desired characteristics, and is not particularly limited, but from the viewpoint of further improving the physical property balance of the electrical characteristics, heat resistance and thermal conductivity, Preferably it is 10-70 mass parts with respect to 100 mass parts of components, More preferably, it is 20-60 mass parts, More preferably, it is 25-50 mass parts. When the content of the maleimide compound is in the above range, the thermal expansion coefficient of the obtained cured product is further reduced, and the heat resistance tends to be further improved.

  The maleimide compounds described above can be used singly or in combination of two or more.

(Epoxy resin)
As an epoxy resin, if it is an epoxy resin which has 2 or more epoxy groups in 1 molecule, a well-known thing can be used suitably, The kind in particular is not limited. Specifically, bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, bisphenol A novolac epoxy resin, glycidyl ester epoxy resin, aralkyl novolac Epoxy resin, biphenylaralkyl epoxy resin, naphthalene ether epoxy resin, cresol novolak epoxy resin, polyfunctional phenol epoxy resin, naphthalene epoxy resin, anthracene epoxy resin, naphthalene skeleton modified novolak epoxy resin, phenolaralkyl Type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, alicyclic type Carboxy resin, a polyol type epoxy resins, phosphorus-containing epoxy resin, glycidyl amine, glycidyl ester, compounds of the double bonds epoxidized butadiene, etc., a compound obtained by a reaction of a hydroxyl-group-containing silicon resin with epichlorohydrin. Among these epoxy resins, biphenylaralkyl type epoxy resins, naphthylene ether type epoxy resins, polyfunctional phenol type epoxy resins, and naphthalene type epoxy resins are preferable in view of flame retardancy and heat resistance. These epoxy resins can be used singly or in combination of two or more.

(Phenol resin)
As the phenol resin, generally known phenol resins can be used as long as they have 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, biphenylaralkyl type phenol resin, cresol novolac type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolak resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolac type phenol resin, phenolaralkyl type phenol resin Naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol 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, biphenylaralkyl type phenol resins, naphtholaralkyl type phenol resins, phosphorus-containing phenol resins, and hydroxyl group-containing silicone resins are preferable in view of flame retardancy. These phenol resins can be used singly or in combination of two or more.

(Oxetane resin)
As the oxetane resin, those generally known can be used. For example, alkyl oxetanes such as oxetane, 2-methyl oxetane, 2,2-dimethyl oxetane, 3-methyl oxetane, 3, 3-dimethyl oxetane, 3-methyl-3-methoxymethyl oxetane, 3, 3-di (trifluoro) Methyl) perfluoxetane, 2-chloromethyl oxetane, 3, 3-bis (chloromethyl) oxetane, biphenyl type oxetane, OXT-101 (trade name of Toho Gosei Co., Ltd.), OXT-121 (trade name of Toho Gosei Co., Ltd.), etc. Although it may be mentioned, it is not particularly limited. 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 are compounds having two or more dihydrobenzoxazine rings in one molecule. For example, bisphenol A type benzoxazine BA-BXZ (trade name of Konishi Chemical) bisphenol F type benzooxazine BF-BXZ (trade name of Konishi Chemical), bisphenol S type benzooxazine BS-BXZ (trade name of Konishi Chemical), P Examples thereof include d-type benzoxazine (trade name of Shikoku Kasei Kogyo Co., Ltd.) and F-a type benzoxazine (trade name of Shikoku Kasei Kogyo Co., Ltd.), but are not particularly limited. These benzoxazine compounds can be used singly or in combination of two or more.

(Compound having a polymerizable unsaturated group)
As compounds having a polymerizable unsaturated group, generally known compounds can be used. For example, vinyl compounds such as ethylene, propylene, styrene, divinylbenzene and divinylbiphenyl, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polypropylene glycol di (meth) acrylate, (Meth) acrylates of monohydric or polyhydric alcohols such as trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol Epoxy (meth) acrylates such as A-type epoxy (meth) acrylate, bisphenol F-type epoxy (meth) acrylate and the like, and benzocyclobutene resin But it is not particularly limited. In addition, the said "(meth) acrylate" is the concept containing an acrylate and the methacrylate corresponding to it. The compound which has these unsaturated groups can be used 1 type or in mixture of 2 or more types.

  The content of one or more components selected from the group consisting of the maleimide compound, the epoxy resin, the phenol resin, the oxacene resin, the benzoxazine compound, and the compound having a polymerizable unsaturated group depends on the desired characteristics. It can be set appropriately and is not particularly limited. For example, in the case of using a maleimide compound other than the bismaleimide compound (B) represented by the above formula (I), a cyanate ester compound (from the viewpoint of further improving the physical property balance of electric characteristics, heat resistance and heat conductivity) The content ratio of A) to the maleimide compound is 0.1 by the equivalent ratio of the unsaturated imide group of the maleimide compound to the cyanate group of the cyanate ester compound (A) (equivalent of unsaturated imide group / equivalent of cyanate group). It is preferable that it is 1.5 or more, More preferably, it is 0.1 or more and 1.2 or less, More preferably, it is 0.2 or more and 1.0 or less.

(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. A well-known thing can be used suitably as a filler (C), The kind is not specifically limited. In particular, fillers generally used in laminate applications can be suitably used as the filler (C). Specific examples of the filler (C) include, but are not limited to, natural silica, fused silica, synthetic silica, amorphous silica, aerosils, silicas such as hollow silica, white carbon, titanium white, zinc oxide, magnesium oxide, Oxides such as zirconium oxide, boron nitride, agglomerated boron nitride, silicon nitride, aluminum nitride, barium sulfate, aluminum hydroxide, aluminum hydroxide heat-treated products (aluminum hydroxide is heat-treated to reduce part of crystal water ), Metal hydrates such as boehmite and magnesium hydroxide, 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-gala , L-glass, D-glass, S-glass, M-glass G20, short glass fibers (including glass fine powders such as E glass, T glass, D glass, S glass, Q glass, etc.), hollow glass, In addition to spherical glass and other inorganic fillers (C), organic powders such as styrene-, butadiene- and acrylic-type rubber powders, core-shell rubber powders, silicone resin powders, silicone rubber powders and silicone composite powders. Materials (C) etc. may be mentioned. Among these, one or more selected from the group consisting of silica, aluminum hydroxide, boehmite, magnesium oxide and magnesium hydroxide are preferable. These fillers (C) can be used individually by 1 type or in combination of 2 or more types.

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

  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, The kind in particular is not limited. Specific examples of the silane coupling agent include, but are not limited to, aminosilanes such as, but not limited to, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycide Epoxysilanes such as xylpropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinylsilanes such as γ-methacryloxypropyltrimethoxysilane, vinyl-tri (β-methoxyethoxy) silane, N Cationic silanes such as -β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride and the like, as well as silane coupling agents based on phenylsilanes. The silane coupling agent can be used singly or in combination of two or more.

  Moreover, as a wetting and dispersing agent, what is generally used for paints can be used suitably, The kind in particular is not 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 the commercially available product include, but are not limited to, Disperbyk-110, 111, 161, 180, BYK-W 996, BYK-W 9010, BYK-W 903, BYK-W 940 and the like manufactured by Big Chemie Japan Ltd. Be The wetting and dispersing agents can be used alone or in combination of two or more.

(Hardening accelerator)
Moreover, the resin composition of this embodiment may contain the hardening accelerator for adjusting a hardening speed 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 acetylacetonate, nickel octylate, organic acid salts such as manganese octylate, phenol, xylenol, cresol, resorcinol, 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 the like; Derivatives such as carboxylic acids of imidazoles or adducts of acid anhydrides thereof, amines such as dicyandiamide, benzyldimethylamine, 4-methyl-N, N-dimethylbenzylamine, phosphine compounds, phosphine oxide compounds, Phosphorus compounds such as phosphonium salt compounds and diphosphine compounds, epoxy-imidazole adduct compounds, benzoyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropyl peroxy carbonate, di-2-ethylhexyl Peroxides such as peroxy carbonate, or azo compounds such as azobisisobutyronitrile, N, N-dimethylaminopyridine and the like can be mentioned. The curing accelerator can be used singly or in combination of two or more.

(Other additives)
Furthermore, the resin composition of the present embodiment can be used in various polymer compounds such as other thermosetting resins, thermoplastic resins and their oligomers, elastomers, and flame retardant compounds as long as the desired properties are not impaired. And various additives etc. 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, phosphate esters, melamine phosphates, phosphorus-containing epoxy resins, nitrogen compounds such as melamine and benzoguanamine, oxazines Examples thereof include ring-containing compounds and silicone compounds. Moreover, as various additives, although it is not limited to the following, for example, an ultraviolet light absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitening agent, a photosensitizer, a dye, a pigment, a thickener, a flow control agent Lubricants, antifoaming agents, dispersants, leveling agents, brighteners, polymerization inhibitors and the like. These can be used singly or in combination of two or more, as desired.

(Organic solvent)
In addition, the resin composition of this embodiment can contain the 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 part, preferably all, of the various resin components described above are dissolved or compatible with the organic solvent. As the organic solvent, known solvents can be appropriately used so long as at least a part, preferably all of the various resin components described above can be dissolved or compatible, and the type thereof is not particularly limited. . Specific examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, methyl lactate, methyl acetate, ethyl acetate, butyl acetate and isoamyl acetate And ester solvents such as ethyl lactate, 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. Be Among these, non-cyclic aliphatic ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone are preferable from the viewpoint of relatively low boiling point and small processing load at the time of drying and high productivity. These organic solvents can be used singly or in combination of two or more.

  The content ratio of the organic solvent in the resin composition may be appropriately set in consideration of the above-described solubility or dispersibility of the resin solid content, the handleability of the obtained resin composition or varnish, and the like, and is not particularly limited. The content of the organic solvent in the resin composition is preferably 10 to 99% by mass, more preferably 20 to 95% by mass, in view of handleability in impregnation or application to a substrate, etc. It is desirable for the concentration to be preferably 99 to 10% by mass, more preferably 95 to 20% by mass.

  The resin composition of the present embodiment can be prepared according to a conventional method, and is a resin uniformly containing the cyanate ester compound (A) and the bismaleimide compound (B) in the present embodiment and the other optional components described above. The method of preparation is not particularly limited as long as the composition is obtained. For example, the resin composition of the present embodiment can be easily obtained by sequentially blending the cyanate ester compound (A) and the bismaleimide compound (B) in the present embodiment and the other optional components described above in a solvent and sufficiently stirring. It can be prepared.

  In addition, at the time of preparation of a resin composition, the well-known process (stirring, mixing, kneading process etc.) for dissolving or disperse | distributing each component uniformly 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-mentioned stirring, mixing, and kneading processing can be appropriately performed using, for example, a device intended for mixing such as a ball mill and a bead mill, or a known device such as a rotation and rotation type mixing device.

  The resin composition of the present embodiment can be used as a constituent material of a prepreg, a metal foil-clad laminate, a printed wiring board, and a semiconductor package. For example, a prepreg can be obtained by impregnating or coating a base material with a solution in which the resin composition of the present embodiment is dissolved in a solvent, and drying.

  In addition, a film obtained by dissolving the resin composition of the present embodiment in a solvent is applied to the plastic film and dried using the peelable plastic film as a substrate to obtain a build-up film or 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 unhardened state which dried the solvent, and can also be used in the state of semi-hardening (B stage formation) as needed.

  Hereinafter, the prepreg of the present embodiment will be described in detail. The prepreg of the present embodiment has a substrate and the above-described resin composition impregnated or coated on the substrate. The method for producing the prepreg of the present embodiment is not particularly limited as long as it is a method of producing a prepreg by combining the resin composition of the present embodiment and a substrate. Specifically, after impregnating or applying the resin composition of the present embodiment to a substrate, the resin composition is semi-cured by a method such as drying in a dryer at 120 to 220 ° C. for about 2 to 15 minutes, etc. The prepreg of the embodiment can be manufactured. At this time, the adhesion amount of the resin composition to the substrate, that is, the content of the resin composition (including the filler (C)) with respect to the total amount of the semi-cured prepreg 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. As such a substrate, for example, glass fibers such as E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass, spherical glass, 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 fabrics, non-woven fabrics, rovings, chopped strand mats, surfacing mats 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, in particular, woven fabrics which have been subjected to super-opening treatment and filling treatment are preferable from the viewpoint of dimensional stability. Furthermore, a glass woven fabric surface-treated with a silane coupling agent such as epoxysilane treatment or aminosilane treatment is preferable from the viewpoint of moisture absorption heat resistance. In addition, 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 in the case of laminated plate applications, the range of 0.01 to 0.2 mm is preferable.

The metal foil-clad laminate of this embodiment has the above-described prepreg on which at least one or more sheets are laminated, and a metal foil disposed on one side or both sides of the prepreg. Specifically, a metal foil such as copper or aluminum is disposed on one side or both sides of one prepreg or a laminate of a plurality of prepregs, and the laminate is formed by molding. be able to. The metal foil used here is not particularly limited as long as it is used for a printed wiring board material, but a copper foil such as a rolled copper foil and a copper foil is preferable. The thickness of the metal foil is not particularly limited, but is preferably 2 to 70 μm, and more preferably 3 to 35 μm. As a molding condition, a method used at the time of producing a laminate for a general printed wiring board and a multilayer board can be adopted. For example, using a multi-stage press, multi-stage vacuum press, continuous molding machine, autoclave molding machine, etc., laminate molding is carried out under conditions of temperature 180 to 350 ° C., heating time 100 to 300 minutes, and surface pressure 20 to 100 kg / cm ² Thus, the metal foil-clad laminate of the present embodiment can be manufactured. A multilayer board can also be produced by laminating and molding the above-mentioned prepreg and a wiring board for the inner layer prepared separately. As a method of manufacturing a multilayer board, for example, copper foils of 35 μm are disposed on both sides of one of the prepregs described above, and laminated under the above conditions, an inner layer circuit is formed, and the circuit is blackened. Forming an inner layer circuit board. Further, the inner layer circuit board and the above-mentioned prepreg are alternately arranged one by one, and a copper foil is further arranged as the outermost layer, and laminated and formed preferably under vacuum under the above conditions. Thus, 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, the surface of the metal foil-clad laminate is subjected to etching to form an inner circuit, whereby an inner substrate is produced. If necessary, the inner layer circuit surface of the inner layer substrate is subjected to a surface treatment to increase the adhesive strength, and then, the required number of the above-described prepregs is superimposed on the inner layer circuit surface. Furthermore, a metal foil for the outer layer circuit is laminated on the outer side, and heat and pressure are integrally molded. In this manner, a multilayer laminate is produced in which an insulating layer composed of a cured product of the base material and the resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit. Then, after drilling the through holes and via holes in the multilayer laminate, a plated metal film is formed on the wall surfaces of the holes so that the inner layer circuit and the outer layer circuit metal foil are conducted. Furthermore, the printed wiring board is manufactured by etching the metal foil for the outer layer circuit to form the outer layer circuit.

  The printed wiring board obtained in the above-mentioned production example has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer contains the resin composition of the present embodiment described above. That is, the prepreg (the base material and the resin composition of the present embodiment impregnated or coated with the same) of the present embodiment described above, the layer of the resin composition of the metal foil-clad laminate of the present embodiment described above (the present embodiment The layer consisting of the resin composition of (1) is comprised from the insulating layer containing the resin composition of this embodiment.

  The resin sheet of the present embodiment includes a support and the above-mentioned resin composition layer (laminated sheet) disposed on the surface of the support. The resin sheet of the present embodiment can be used as a laminated sheet, and can also be used only as a resin composition layer from which a support has been removed (a single-layer sheet). That is, the resin sheet of this embodiment has at least the resin composition of this embodiment. The laminated sheet can be obtained by applying a solution obtained by dissolving the above resin composition in a solvent to a support and drying. The support used herein is not particularly limited. For example, a polyethylene film, a polypropylene film, a polycarbonate film, a polyethylene terephthalate film, an ethylene tetrafluoroethylene copolymer film, and a surface of these films are coated with a release agent. An organic film substrate such as a mold release film and a polyimide film, a conductor foil such as copper foil and aluminum foil, a glass plate, a SUS plate, and a plate-like inorganic film such as FRP. As a coating method, for example, a solution obtained by dissolving the above resin composition in a solvent is coated on a support by a bar coater, a die coater, a doctor blade, a baker applicator or the like to obtain a support and a resin composition layer. There is a method of producing a laminated sheet in which Moreover, a single layer sheet can also be obtained by peeling or etching a support body from the resin sheet obtained by drying after application | coating. Incidentally, a 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 forming a 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, although the drying conditions at the time of removing a solvent are not specifically limited, It is preferable to make it dry at the temperature of 20 degreeC-200 degreeC for 1 to 90 minutes. When the temperature is 20 ° C. or more, the remaining of the solvent in the resin composition can be further prevented, and when the temperature is 200 ° C. or less, 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 of the solution of the resin composition of this embodiment, and application | coating thickness, and it does not specifically limit. 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 at the time of drying.

  Hereinafter, the present embodiment will be more specifically described using examples and comparative examples. However, the present invention is not limited at all by these. The values of various manufacturing conditions and evaluation results in the following examples have meanings as preferable upper limit values or preferable lower limit values in the embodiment of the present invention, and the preferable range is the value of the upper limit or the lower limit described above. And a range defined by a combination of the values of the following examples or the values of the examples.

Synthesis Example 1 Synthesis of Naphthol Aralkyl Type Cyanate Ester Resin (SNCN) 300 g (1.28 mol in terms of OH group) of 1-naphthol aralkyl resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and 194.6 g (1.92 mol) of triethylamine (1.5 mol per 1 mol of hydroxy group) was 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 to 1 mol of hydroxy group), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol to 1 mol of hydroxy group) The solution 1 was poured over 30 minutes, keeping 1205.9 g of water under stirring, at a solution temperature of -2 to -0.5 ° C. After completion of 1 injection of solution, after stirring for 30 minutes at the same temperature, 10 minutes of a solution (solution 2) in which 65 g (0.64 mol) of triethylamine (0.5 mol per 1 hydroxyl group) is dissolved in dichloromethane I poured it over. After completion of solution 2 injection, the reaction was completed by stirring for 30 minutes at the same temperature.
Thereafter, the reaction solution was allowed to stand to separate the organic phase and the aqueous phase. The resulting organic phase was washed five times with 1300 g of water. The electric conductivity of the fifth washing with water was 5 μS / cm, and it was confirmed that washing with water sufficiently removed the removable ionic compound.
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 material). The mass average molecular weight Mw of the obtained SNCN was 600. In addition, the IR spectrum of SNCN showed an absorption of 2250 cm ^-1 (cyanate group) and no absorption of a hydroxy group.

Synthesis Example 2 Synthesis of Bismaleimide Compound (BMI-4,4'-BPE) 10.01 g (50.0 mmol) of a flask equipped with a stirrer, a nitrogen inlet tube, Dean Stark, a condenser and a thermometer was used. 4,4'-diaminodiphenyl ether manufactured by Tokyo Chemical Industry Co., Ltd. and 120.0 g of N, N-dimethylformamide as a solvent were charged, and dissolved by stirring under nitrogen gas. To this solution was added 10.8 g (110 mmol) of maleic anhydride and stirred overnight at room temperature. Thereafter, 0.951 g (5.00 mmol) of p-toluenesulfonic acid monohydrate as a catalyst and 60 g of toluene as a dehydrated azeotropic solvent were charged, and the azeotropic stirring was carried out for 6 hours. At this time, evaporation of toluene and water occurred, and a part of them was condensed by the cooler. After water and toluene trapped in Dean Stark were separated, only toluene was refluxed into the system, and a part was distilled out of the system from the upper part of the cooling pipe by flowing nitrogen gas.
After cooling the reaction mixture, toluene was distilled off with an evaporator. Thereafter, the resulting solution was poured into 1% aqueous sodium bicarbonate solution to remove excess used maleic anhydride and p-toluenesulfonic acid. The obtained crude product was dissolved in N, N-dimethylformamide, methanol was added to reprecipitate, and the precipitate was collected by filtration and dried. This operation was repeated three times to obtain 4,4'-bismaleimide diphenyl ether (yield 70%).

Synthesis Example 3 Synthesis of Bismaleimide Compound (BMI-3,4′-BPE) Synthesis Example except that 3,4′-diaminodiphenyl ether manufactured by Tokyo Chemical Industry Co., Ltd. is used instead of 4,4′-diaminodiphenyl ether Operated in the same manner as 2 to give 3,4'-bismaleimide diphenyl ether (yield 70%).

Example 1
50.0 parts by mass of naphthol aralkyl type cyanate ester resin (SNCN, cyanate group equivalent 256 g / eq.) Of Synthesis Example 1, novolac type bismaleimide compound (manufactured by Daiwa Kasei Kogyo, BMI-2300, unsaturated imido group equivalent 186 g / Eq. 35.0 parts by mass, bismaleimide compound of Synthesis Example 2 (BMI-4, 4'-BPE, unsaturated imide group equivalent 180 g / eq.) 15.0 parts by mass, epoxysilane-treated fused silica 100.0 parts by mass (ADMATEX SC 30, 50 MB), 0.5 parts by mass of 2,4,5-Triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.125 zinc octoate (manufactured by Nippon Kagaku Sangyo Co., Ltd.) Parts by mass were mixed with methyl ethyl ketone to obtain the varnish of Example 1.
The obtained varnish of Example 1 is impregnated and coated on an E glass cloth having a thickness of 0.1 mm, and the temperature is 165 ° C. for 4 minutes using a drier (a flameproof steam dryer, manufactured by Takasugi Mfg. Co., Ltd.). It heat-dried and the prepreg of Example 1 of 46 mass% of resin compositions was obtained. Eight prepregs are stacked, 12 μm copper foil (3EC-M3-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd.) is placed on both sides, and vacuum pressing is performed at a pressure of 40 kg / cm ² and a temperature of 220 ° C. for 80 minutes. A 12 μm copper-clad laminate of Example 1 of 0.8 mm was obtained.

(Example 2)
50.0 parts by mass of naphthol aralkyl type cyanate ester resin (SNCN, cyanate group equivalent 256 g / eq.) Of Synthesis Example 1, novolac type bismaleimide compound (manufactured by Daiwa Kasei Kogyo, BMI-2300, unsaturated imido group equivalent 186 g / Eq. 35.0 parts by mass, bismaleimide compound of Synthesis Example 3 (BMI-3, 4′-BPE, unsaturated imide group equivalent 180 g / eq.) 15.0 parts by mass, epoxysilane-treated fused silica 100.0 parts by mass (ADMATEX SC 30, 50 MB), 0.5 parts by mass of 2,4,5-Triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.150 zinc octoate (manufactured by Nippon Kagaku Sangyo Co., Ltd.) Parts by weight were mixed with methyl ethyl ketone to obtain the varnish of Example 2.
The obtained varnish of Example 2 is impregnated and coated on an E glass cloth having a thickness of 0.1 mm, and the temperature is 165 ° C. for 4 minutes using a drier (a flameproof steam dryer, manufactured by Takasugi Mfg. Co., Ltd.). It heat-dried and the prepreg of Example 2 of 46 mass% of resin compositions was obtained. Eight prepregs are stacked, 12 μm copper foil (3EC-M3-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd.) is placed on both sides, and vacuum pressing is performed at a pressure of 40 kg / cm ² and a temperature of 220 ° C. for 80 minutes. A 12 μm copper-clad laminate of Example 2 of 0.8 mm was obtained.

(Comparative example 1)
Example 1 except that the amount of BMI-2300 used is changed to 50.0 parts by mass and the amount of zinc octylate used is changed to 0.150 parts by mass without using BMI-4, 4'-BPE The varnish of Comparative Example 1 was obtained in the same manner as in the above.
The varnish of Comparative Example 1 thus obtained is impregnated and coated on an E glass cloth having a thickness of 0.1 mm, and then dried at 165 ° C. for 10 minutes using a dryer (explosion-proof steam dryer, Takasugi Seisakusho Co., Ltd.). It heat-dried and the prepreg of the comparative example 1 of 46 mass% of resin compositions was obtained. Eight prepregs of Comparative Example 1 are stacked, and 12 μm copper foil (3EC-M3-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd.) is placed on both sides, and vacuum pressing is performed for 80 minutes at a pressure of 40 kg / cm ² and a temperature of 220 ° C. Thus, a 12 μm copper-clad laminate of Comparative Example 1 having a thickness of 0.8 mm was obtained.

[Evaluation of copper-clad laminates]
The following evaluation was performed using the obtained copper-clad laminate.

(1) Electrical characteristics <dielectric constant (Dk)>
The dielectric constant of 2 GHz and 10 GHz was measured by the cavity resonator perturbation method (Agilent 8722 ES, manufactured by Agilent Technologies) using the test piece (n = 3) from which the copper foil of the copper-clad laminate was removed, three times each. The average value was calculated.
<Dielectric loss tangent (Df)>
Measure the dielectric loss tangent of 2 GHz and 10 GHz with cavity resonator perturbation method (Agilent 8722 ES, Agilent Technologies) using the test piece (n = 3) from which copper foil of copper clad laminate was removed, and 3 times each The average value was calculated.

(2) Heat resistance evaluation The obtained copper foil-clad laminate having an insulation layer thickness of 0.8 mm is cut to a size of 12.7 × 30 mm with a dicing saw, and then the copper foil on the surface is removed by etching to obtain a measurement sample. Obtained. Using this sample for measurement, the storage elastic modulus E ′ and the loss elastic modulus E ′ ′ are measured by the DMA method according to JIS C6481 with a dynamic viscoelastic analyzer (manufactured by TA Instruments), E ′ ′ The heat resistance was evaluated by setting the peak value of and tan δ (= E ′ ′ / E ′) as Tg.

(3) Thermal conductivity The copper foil on the surface of the obtained copper foil-clad laminate having an insulating layer thickness of 0.8 mm was removed by etching to obtain a measurement sample. The density of the obtained sample was measured, the specific heat was measured by DSC (TA Instrumen Q100), and the thermal diffusivity was measured by a xenon flash analyzer (Bruker: LFA 447 Nanoflash). Next, the thermal conductivity in the thickness direction was calculated from the following equation.
Thermal conductivity (W / m · K) = density (kg / m ³ ) × specific heat (kJ / kg · K) × thermal diffusivity (m ² / s) × 1000

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

Claims (11)

Cyanate ester compound (A), and bismaleimide compound (B) represented by the following formula (I)
A resin composition containing at least
(Wherein, R _{1 to} R ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) The resin composition according to claim 1, wherein a content of the bismaleimide compound (B) is 1 to 60 parts by mass with respect to 100 parts by mass of a resin solid content in the resin composition. The content ratio of the cyanate ester compound (A) and the bismaleimide compound (B) is the equivalent ratio of the unsaturated imide group of the bismaleimide compound (B) to the cyanate group of the cyanate ester compound (A) ( The resin composition according to claim 1 or 2, which is 0.05 or more and 0.99 or less in terms of equivalent of unsaturated imide group / equivalent of cyanate group). It is selected from the group consisting of maleimide compounds other than the bismaleimide compound (B) represented by the above formula (I), epoxy resins, phenol resins, oxacene resins, benzoxazine compounds, and compounds having a polymerizable unsaturated group. The resin composition as described in any one of Claims 1-3 which further contains 1 or more types. The maleimide compound other than the bismaleimide compound (B) represented by the formula (I) is further contained, and the content ratio of the cyanate ester compound (A) and the maleimide compound is the unsaturated imide group of the maleimide compound and The equivalent ratio of the cyanate ester compound (A) to a cyanate group (equivalent of unsaturated imide group / equivalent of cyanate group) is 0.1 or more and 1.5 or less. The resin composition as described in. The resin composition according to any one of claims 1 to 5, further comprising a filler (C). The resin composition according to claim 6, 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 in the resin composition. A prepreg, comprising: a substrate; and the resin composition according to any one of claims 1 to 7, which is impregnated or applied to the substrate. A prepreg according to claim 8, at least one sheet, and a metal foil disposed on one side or both sides of the prepreg,
A metal foil-clad laminate, comprising at least: A resin sheet comprising at least the resin composition according to any one of claims 1 to 7, provided on a support and a surface of the support. At least an insulating layer, and a conductor layer provided on the surface of the insulating layer,
The said insulating layer contains the resin composition as described in any one of Claims 1-7,
Printed wiring board.