JP2019077759A - Resin composition, prepreg, metal foil-clad laminate, resin sheet and printed wiring board - Google Patents

Abstract

To provide a resin composition which exhibits excellent physical property not only in heat resistance but also in thermal conductivity, and 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) represented by formula (I), and a maleimide compound (B). In the formula (I), Rto Reach independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 0 or more.SELECTED DRAWING: Figure 1

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. In particular, a heat dissipation technique for printed wiring boards against heat generation is required. This is because the amount of heat generated from the semiconductor increases as the semiconductor becomes higher functional, and the heat is easily accumulated inside due to the influence of high integration and high density mounting.

  The thermosetting resin itself such as epoxy resin used for the insulating layer of the printed wiring board has a relatively low thermal conductivity. Therefore, in order to improve the thermal conductivity of the printed wiring board, the thermal conductivity of the cured product can be obtained by blending 80 to 95% by weight of the mixed filler (inorganic filler) having a predetermined particle size distribution into the thermosetting resin. A thermally conductive resin composition to be 3 to 10 W / mK has been proposed (see Patent Document 1).

  However, when the inorganic filler is highly filled as in Patent Document 1 described above, although the thermal conductivity can be improved, the volume ratio of the thermosetting resin decreases, so the formability deteriorates, and the resin and the inorganic filler Cause problems such as cracking and void formation. Therefore, improvement of the resin itself is required.

  Conventionally, cyanate ester compounds have been 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 maleimide compound, etc. are used in combination with a cyanate ester compound are for semiconductor plastic packages Etc. are widely used for high performance printed wiring board materials etc.

  As a cyanate ester compound widely used for printed wiring board materials etc., the resin composition which used the bisphenol A type cyanate ester compound and other thermosetting resins etc. is mentioned, for example. Bisphenol A type cyanate ester compounds have excellent properties such as electrical properties, mechanical properties, and chemical resistance, but are insufficient in heat resistance, low water absorption, hygroscopic heat resistance, and flame retardancy May be Therefore, studies of various cyanate ester compounds having different structures are being conducted for the purpose of further improving the properties.

  As a resin having a structure different from that of the bisphenol A type cyanate ester compound, for example, a novolac type cyanate ester compound is often used (see Patent Document 2). In addition, prepolymerization of a novolac type cyanate ester compound and a bisphenol A type cyanate ester compound has been proposed (see Patent Document 3). Further, as a modification of these, a cyanate ether compound obtained by cyanating a phenol resin having a polynaphthylene ether structure has been proposed (see Patent Document 4).

JP 2001-348488 A Unexamined-Japanese-Patent No. 11-124433 gazette JP 2000-191776 A International Publication No. 2014/065422

  However, although the improvement of heat resistance etc. is anticipated, the further improvement is calculated | required from the viewpoint of the improvement of heat conductivity of the cyanate Ertel compound of patent documents 2-4.

  The present invention has been made in view of the above-mentioned problems, and a resin composition which exhibits excellent physical properties not only in heat resistance but also in heat conductivity, as well as a prepreg using the same, a metal foil-clad laminate, It aims at providing a resin sheet, a printed wiring board, etc.

  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 together the cyanate ester compound (A) having a specific structure having a repeating skeleton of phenylene ether and the maleimide compound (B), and have completed the present invention.

That is, the present invention includes the following aspects.
[1] A resin composition containing at least a cyanate ester compound (A) represented by the following formula (I) and a maleimide compound (B).
(Wherein, R _{1 to} R ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 0 or more.)

[2] The resin composition according to [1], wherein the content of the cyanate ester compound (A) is 1 to 90 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
[3] The resin composition according to [1] or [2], further containing a filler (C).
[4] The resin composition according to [3], 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.
[5] From a cyanate ester compound other than the cyanate ester compound (A) represented by the above formula (I), an epoxy resin, a phenol resin, an oxetane resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group The resin composition as described in any one of [1]-[4] which further contains 1 or more types selected from the group which consists of.

[6] A prepreg comprising at least a substrate, and the resin composition according to any one of [1] to [5] impregnated or applied to the substrate.
[7] A metal foil-clad laminate, comprising at least one or more of the prepregs according to [6] and a metal foil disposed on one side or both sides of the prepreg.
[8] A resin sheet comprising at least a resin composition according to any one of [1] to [5], provided on a support and the surface of the support.
[9] 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 includes the resin composition according to any one of [1] to [5]. Board.

  According to the present invention, it is possible to provide a resin composition that exhibits excellent physical property balance in heat resistance and thermal conductivity, and a prepreg, a metal foil-clad laminate, a resin sheet, a printed wiring board and the like using the same. it can.

It is a chart which shows IR spectrum of the cyanate ester compound (A) of the synthesis example 1.

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

(Wherein, R _{1 to} R ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 0 or more.)

[Cyanate ester compound (A)]
The cyanate ester compound (A) contained in the resin composition in the present embodiment is a cyanate ester compound represented by the above formula (I). The resin composition using a cyanate ester compound has excellent properties of glass transition temperature, thermal conductivity, 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 may have either a linear or branched chain structure. 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). The alkyl group in the formula (I) 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, or a cyano group.

  In said formula (I), n represents an integer greater than or equal to 0, Preferably it is an integer of 1-6. The compound represented by the said Formula (I) may be contained in the resin composition of this embodiment as a mixture of several compounds in which n differs.

The OCN group and R _{1 to} R ₄ in the above formula (I) can be selected at any position. For example, a benzenetriyl group in which two oxygen atoms shown in the formula (I) are bonded to the 1,4 or 1,3 position and an OCN group is bonded to the 2, 5, or 6 position can be mentioned.

  The above-mentioned cyanate ester compounds (A) represented by the formula (I) can be used singly or in combination of two or more.

  The cyanate ester compound (A) represented by the above-mentioned formula (I) can be synthesized by applying a conventionally known synthesis method, and the production method thereof is not particularly limited. For example, a cyanate compound (A) can be obtained by reacting a phenol resin having a repeating skeleton of phenylene ether with cyanogen chloride in the presence of a base such as an amine to cyanate a hydroxy group. The degree of progress of the reaction in cyanation can be analyzed by liquid chromatography or IR spectroscopy. The obtained cyanate ester compound (A) can be identified by a known method such as NMR, and its purity can be analyzed by liquid chromatography or IR spectroscopy. Furthermore, byproducts such as dicyan and dialkyl cyanoamide and volatile components such as residual solvent can be quantitatively analyzed by gas chromatography.

  The content of the cyanate ester compound (A) represented by the above formula (I) in the present embodiment can be appropriately set according to the desired characteristics, and is not particularly limited, but it is heat resistant and thermally conductive. From the viewpoint of further improving the physical property balance, it is preferably 1 to 90 parts by mass, more preferably 10 to 85 parts by mass, and still more preferably 20 to 80 parts by mass with respect to 100 parts by mass of resin solid content. . When the content of the cyanate ester compound (A) is in the above range, the heat resistance and the thermal conductivity of the obtained cured product tend to be further improved.

  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.

[Maleimide compound (B)]
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 ( 3,5-Diethyl-4-maleimidophenyl) methane, a maleimide compound represented by the following formula (1), a maleimide compound represented by the following formula (2), a maleimide compound represented by the following formula (3), and the like There may be mentioned prepolymers of maleimide compounds, or 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 (1) At least one selected from the group consisting of a maleimide compound, a maleimide compound represented by the following formula (2), and a maleimide compound represented by the following formula (3) is preferable. By containing such a maleimide compound (B), the physical property balance of the obtained cured product tends to be more excellent. From the same viewpoint, the maleimide compound (B) contains at least one selected from the group consisting of a maleimide compound represented by the following formula (1) and a maleimide compound represented by the following formula (2) Is more preferred.

Here, in Formula (1), each R ₅ independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In the formula (1), n ₁ represents an integer of 1 or more, preferably 10 or less, and more preferably 7 or less. Maleimide compound represented by the above formula (1), as a mixture of compounds n ₁ are different, it may be included in the resin composition of the present embodiment.

In the above formula (2), n ₂ represents an integer of 1 or more, preferably 5 or less, more preferably 4 or less, and still more preferably 3 or less. The maleimide compound represented by 2) may be contained in the resin composition of this embodiment as a mixture of several compounds in which n ₂ differs.)

(In the above formula (3), n ₃ represents an integer of 1 or more, preferably an integer of 30 or less, more preferably an integer of 20 or less, and still more preferably an integer of 15 or less. The maleimide compound represented by 3) may be contained in the resin composition of this embodiment as a mixture of several compounds in which n ₃ differs.)

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

  The content of the maleimide 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 heat conductivity. The amount is preferably 1 to 90 parts by mass, more preferably 10 to 85 parts by mass, and still more preferably 20 to 80 parts by mass with respect to 100 parts by mass of the resin solid content. When the content of the maleimide compound (B) 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 resin composition of the present embodiment is a cyanate ester compound other than the cyanate ester compound (A) represented by the above-mentioned formula (I) (hereinafter sometimes simply referred to as "cyanate ester compound"), It may further contain one or more selected from the group consisting of an epoxy resin, 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.

  As a cyanate ester compound which may be contained in the resin composition of the present embodiment, a compound having an aromatic moiety substituted by at least one cyanato group (cyanate group) in the molecule is particularly limited. I will not. 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 addition, the thing applicable to the cyanate ester compound (A) represented by said Formula (I) is not contained in the cyanate ester compound which can be used together demonstrated here.

  Examples of cyanate ester compounds include, but are not limited to, those represented by the following formula (4).

In the above formula (4), Ar ₁ represents a benzene ring, a naphthalene ring, or a single bond of two benzene rings. 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 the number of repetitions, and is an integer in the range of 0 to 50. The cyanate ester compound represented by the above formula (4) is a mixture of a plurality of compounds different in t in the resin composition of the present embodiment. It may be included. 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 (4) may have any of a linear or branched chain structure and a cyclic structure (for example, a cycloalkyl group etc.).
Furthermore, even if the hydrogen atom in the alkyl group in Formula (4) and the aryl group in Ra is substituted with a halogen atom such as a fluorine atom or 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 (4) 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 above formula (4) include, but are not limited to, an imino group, a polyimide group, and the like.

  Moreover, as an organic group of X in said Formula (4), what is a structure represented by following formula (5) or following formula (6) is mentioned, for example.

(In the above formula (5), Ar ₂ represents a benzenetetrayl group, a naphthalenetetrayl group or a biphenyltetrayl group, and when u is 2 or more, they may be the same or different from each other. Rb and 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 (6), 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 (4), 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 (5) and Ar ₃ of Formula (6), two carbon atoms shown in Formula (5) or two oxygen atoms shown in Formula (6) 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 aryl group in Rb, Rc, Rd, Re, Rf and Rg in Formula (5), and Ri and Rj in Formula (6) have the same meanings as in Formula (4) above.

  Specific examples of cyanato-substituted aromatic compounds represented by the above formula (4) 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.

In addition, other specific examples of the compound represented by the above formula (4) 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. Furthermore, it is more preferable that the cyanate ester compound includes at least one selected from the group consisting of naphthol aralkyl type cyanate ester compounds and diallyl bisphenol A type cyanate ester. In particular, a naphthol aralkyl type cyanate ester compound represented by the following formula (7) or a diallyl bisphenol A type cyanate ester compound represented by the following formula (8) is preferably used.

(In formula (7), R respectively independently shows a hydrogen atom or a methyl group. N shows an integer of 1 or more and 50 or less. The naphthol aralkyl type cyanate ester compound represented by the said formula (7) is It may be contained in the resin composition of this embodiment as a mixture of a plurality of compounds in which n is different.)

(In formula (8), R _{1 to} R ₃ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

(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 novolac 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.

  A group comprising a cyanate ester compound other than the cyanate ester compound (A) represented by the above-mentioned formula (I), an epoxy resin, a phenol resin, an oxacene resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group The content of one or more components selected from the above can be appropriately set according to the desired characteristics, and is not particularly limited. For example, the total of 1 to 50 parts by mass is preferable, more preferably 2 to 30 parts by mass, and still more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the resin solid content.

[Filler (C)]
The resin composition of the present embodiment preferably further contains a filler (C) from the viewpoint of thermal expansion characteristics, dimensional stability, flame retardancy, thermal conductivity, electrical 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 These organic solvents can be used singly or in combination of two or more.

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

  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 an electrolytic 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 Cyanate Ester Compound (A) (NOCN) Having a Phenylene Ether Skeleton 300 g of a phenol resin having a phenylene ether skeleton (manufactured by DIC Corporation, EXB-9600) (3.75 mol in terms of OH group), And 580.8 g (5.74 mol, 1.53 mol with respect to 1 mol of the hydroxy group) of triethylamine were dissolved in 1800 g of dichloromethane, and this was used as a solution 1.
380.4 g (6.19 mol, 1.65 mol relative to 1 mol of the hydroxy group) of cyanogen chloride, 887.5 g of dichloromethane, 569.7 g (5.63 mol, 36 mol of hydrochloric acid), 1.5 mol per 1 mol of the hydroxy group And a solution of 2800 g of water were poured over 100 minutes while maintaining the solution temperature -2 to -0.5 ° C under stirring. After completion of the pouring of Solution 1, after stirring for 30 minutes at the same temperature, a solution in which 227.7 g (2.25 mol, 0.6 mol per 1 mol of the hydroxy group) of triethylamine was dissolved in 230 g of dichloromethane (solution 2) Was poured over 40 minutes. After completion of pouring of solution 2, 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 obtained organic phase was washed with 2 L of 0.1 N hydrochloric acid and then washed seven times with 2000 g of water. The electric conductivity of the seventh washing with water was 50 μS / cm, and washing with water confirmed that the removable ionic compounds were sufficiently removed.
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 197 g of the objective cyanate ester compound NOCN (black-purple viscous substance). The IR spectrum of the obtained NOCN showed absorption of a cyanate ester group at 2250 cm ^-1 and no absorption of a hydroxy group. The IR chart of the obtained NOCN and the IR chart of EXB-9600 used as a raw material are shown in FIG.

Example 1
50.0 parts by mass of cyanate ester compound (A) (NOCN, cyanate group equivalent 108 g / eq.) Of Synthesis Example 1, novolac type maleimide compound (manufactured by Daiwa Kasei Kogyo Co., Ltd., BMI-2300, unsaturated imide group equivalent 186 g /) eq.) 50.0 parts by mass, 100.0 parts by mass of fused silica treated with epoxysilane (manufactured by Admatex, SC2050MB), 0.5 parts by mass of 2,4,5-Triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.10 parts by mass of zinc octylate (manufactured by Nippon Chemical Industrial Co., Ltd.) was 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 5 minutes using a dryer (explosion-proof steam dryer, manufactured by Takasugi Seisakusho 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.

(Comparative example 1)
Example 1 except using a novolak type cyanate ester compound (Primaset PT-30, manufactured by Lonza Japan Co., Ltd., cyanate group equivalent 124 g / eq.) In place of the cyanate ester compound (A) of Synthesis Example 1 The varnish of Comparative Example 1 was obtained in the same manner as in the above.
The varnish of Comparative Example 1 obtained is impregnated and coated on an E glass cloth having a thickness of 0.1 mm, and the temperature is 165 ° C. for 5 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 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 Comparative Example 1 of 0.8 mm was obtained.

[Evaluation of copper-clad laminates]
The following evaluation was performed using the obtained copper-clad laminate.
(1) 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 the copper foil on the surface is removed by etching to obtain a sample for measurement. 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 tanδ (= E ′ ′ / E ′) as the glass transition temperature.

(2) 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 (9)

Cyanate ester compound (A) represented by the following formula (I), and maleimide compound (B)
The 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, and n represents an integer of 0 or more.) The resin composition according to claim 1, wherein the content of the cyanate ester compound (A) is 1 to 90 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. The resin composition according to claim 1, further comprising a filler (C). The resin composition according to claim 3, 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. From the group consisting of a cyanate ester compound other than the cyanate ester compound (A) represented by the formula (I), an epoxy resin, a phenol resin, an oxetane resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group The resin composition according to any one of claims 1 to 4, further comprising one or more selected. A prepreg, comprising: a substrate; and the resin composition according to any one of claims 1 to 5, which is impregnated or applied to the substrate. A prepreg according to claim 6, 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 a resin composition according to any one of claims 1 to 5, provided on a support and the 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 1-5,
Printed wiring board.