JPH0625504A - Curing resin composition - Google Patents

Abstract

PURPOSE:To provide a curing resin composition excellent in mechanical strength, resistance to heat and moisture, electrical properties, etc., comprising specific block copolymer(s), a thermosetting resin and/or vinyl monomer and specific organopolysiloxane. CONSTITUTION:This composition comprises (A) copolymer(s) of formula I and/or formula II (X is conjugated diene polymer block; Y is N-substituted maleimide polymer block; (m) is a positive number of 0-2; (n) is a positive number of 1-5) 500-100000 in number-average molecular weight with the weight ratio X/Y of (20:80) to (90:10), (B) a thermosetting resin (pref. epoxy resin, polybutadiene resin, maleimide compound or cyanic ester) and/or vinyl monomer, and (C) an organopolysiloxane >=1000 in number-average molecular weight bearing functional group(s) selected from COOH, OH, NH2, and groups of ester, mercapto, epoxy, polyoxyalkylene, vinyl and (meth) arcylic.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable resin composition, and more specifically to a specific copolymer comprising a conjugated diene polymer block and an N-substituted maleimide polymer block, a thermosetting resin and / or a thermosetting resin. Alternatively, it relates to a curable resin composition containing a vinyl monomer and a specific organopolysiloxane. INDUSTRIAL APPLICABILITY The curable resin composition of the present invention provides a cured product having excellent mechanical strength, heat resistance, moisture resistance, electrical characteristics, and the like, and has an extremely small coefficient of thermal expansion. Effectively applied in the field.

[0002]

2. Description of the Related Art In the field of electric and electronic materials, thermosetting resins such as epoxy resins, phenol resins and unsaturated polyester resins have been widely used. For example, as a resin for impregnating a laminated board for a printed wiring board, an epoxy resin, a phenol resin, a polyimide resin, or the like, and a semiconductor element, a diode, a capacitor, a relay, an epoxy resin for sealing electric / electronic parts such as a switch, A low-pressure molding material such as a silicone resin material, a thermosetting or photocurable liquid material such as an epoxy resin material, an acrylic resin material, or a silicon resin material is used.

Further, it is known that a cured product obtained by radical-curing a conjugated diene resin represented by a polybutadiene resin is extremely excellent in electrical characteristics, water resistance, moisture resistance and the like. For example, a method for producing a laminate and a molding material using a resin composition comprising a 1,2-polybutadiene resin which is liquid at room temperature and has a number average molecular weight of about 1,000 to 5,000 and a radical polymerization initiator (Japanese Patent Publication No. 47-051952). Gazette, Japanese Patent Publication No. Sho 48-0144
No. 28, etc.), the number average molecular weight is 50,000 to 200,000.
Method for producing a laminate using a resin composition comprising a 1,2-polybutadiene resin which is solid at room temperature and a radical polymerization initiator (see Japanese Patent Publication No. 58-021925, Japanese Patent Publication No. 02-1926, etc.) , And a curable resin composition comprising a butadiene-vinyl aromatic compound copolymer and a cyanate ester resin composition (see JP-A-61-233060, etc.) and the like.

Further, the present inventors have already proposed a curable resin composition containing the above-mentioned specific copolymer and thermosetting resins and / or vinyl monomers as essential components (JP-A-2- 255855, JP-A-3-2690.
47, JP-A-3-281650, etc.).

[0005]

In recent years, the miniaturization of electronic devices has made rapid progress, but along with this, high performance and high reliability of electric and electronic parts are required. For example, a substrate (laminated plate) for a printed wiring board used in a high-speed arithmetic circuit or a high-frequency circuit is required to have a material that has excellent dielectric properties such as a low dielectric constant and a low dielectric loss tangent and is flame retardant. Further, as a sealing material for electric / electronic circuit parts, a material having a well-balanced adhesiveness, moisture resistance, heat resistance, thermal shock resistance, electrical characteristics, flame retardancy, etc. is required. In response to these requirements, the laminated board using the general-purpose resin does not satisfy the required dielectric characteristics, and the sealing material also has various required characteristics, particularly both thermal shock resistance and electrical characteristics. There is nothing to be satisfied.

On the other hand, a laminated board using a polybutadiene resin has extremely excellent dielectric properties, but in the method for producing a laminated board using a liquid polybutadiene resin, a prepreg obtained by impregnating a base material and drying it is tacky. Since it has the property, it was difficult to laminate-mold it. Further, in the method for producing a laminated plate using a solid polybutadiene resin, the solubility in a general-purpose solvent is poor and the viscosity of the impregnating varnish is extremely high, which also results in extremely poor workability in producing a laminated plate. Furthermore, since the adhesiveness to metal foil such as copper foil is poor in common to both, it is the current situation that it has not been put to practical use industrially.

Further, when a polybutadiene resin is used for electric and electronic parts, it is possible to obtain extremely excellent heat resistance, moisture resistance and electric characteristics, but the contraction rate upon curing is extremely large and the adhesiveness is poor, so that it is liquid. It is not used as a sealing material except for some special purposes. Further, the polybutadiene resin has extremely poor compatibility with other thermosetting fats, and a method using the butadiene-vinyl aromatic compound copolymer has been proposed as a method for improving it, but sufficient compatibility is obtained. Therefore, it is necessary to increase the copolymerization ratio of the vinyl aromatic compound, and in that case, the heat resistance decreases. On the other hand, according to the method previously proposed by the present inventors, a cured product having extremely excellent mechanical strength, heat resistance, moisture resistance, electrical characteristics and the like can be obtained. However, although it depends on the composition, the thermal expansion coefficient is around 10 × 10 ^-5 / ° C, which is slightly larger than that of general epoxy resin or polyimide resin, and especially for the purpose of increasing the chip size and packaging density in recent semiconductors. However, there is a problem when it is used as a sealing agent that meets the demand for smaller and thinner products, and as an impregnating agent for ultra-high density printed wiring boards. The present invention has been made in view of such an actual situation, and a cured product having excellent mechanical strength, heat resistance, moisture resistance, flame retardancy, thermal shock resistance, electrical characteristics, and the like, and having a small thermal expansion coefficient can be obtained. It is intended to provide a curable resin composition.

[0008]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, have found that a specific copolymer consisting of a conjugated diene polymer block and an N-substituted maleimide polymer block ( A curable resin composition comprising a thermosetting resin and / or a vinyl monomer and a specific organopolysiloxane is excellent in mechanical strength, heat resistance, resistance, electrical characteristics, etc., The present invention has been completed by finding that a cured product having a small coefficient of thermal expansion is provided.

The present invention relates to a curable resin composition comprising the following components A, B and C: Component A: the following general formula [1] and / or [2] X (Y) m ... [1] X (O—Y) n ... [2] (where X is a conjugated diene polymer. Block, Y is N-
Shows a substituted maleimide polymer block, m is 1-2, n
Is a positive number of 1 to 5), and the weight ratio of X and Y is 20 /
80 / ≦ X / Y ≦ 90/10, number average molecular weight of 500-
Copolymer which is 100,000 Component B: Thermosetting resin and / or vinyl monomer Component C: Carboxyl group, hydroxyl group, amino group in the molecule,
An organopolysiloxane having at least one functional group selected from an ester group, a mercapto group, an epoxy group, a polyoxyalkylene group, a vinyl group, and a (meth) acryl group, and having a number average molecular weight of 1,000 or more.

The present invention will be described in detail below. The component A used in the present invention is a copolymer of the above general formula [1] and 2 or [2], and X (Y) of the general formula [1] is used.
The copolymer represented by m is a conjugated diene-based polymer block or a conjugated diene-based polymer block which is a copolymer of a conjugated diene and a vinyl monomer, and Y in the formula
Is the following general formula [3]

[0011]

[Chemical 1] (Wherein R represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or a substituted aryl group), and is at least one polymer block of N-substituted maleimide, Y Is a copolymer bonded in the molecule of X.

The conjugated diene is generally a conjugated diene having 4 to 12 carbon atoms, such as 1,3-butadiene,
Isoprene, 2,3-dimethyl-1,3-butadiene, 1,3
-Pentadiene, 2-methyl-1,3-pentadiene, 1,
Examples thereof include 3-hexadiene, 4,5-diethyl-1,3-octadiene, and 3-butyl-1,3-octadiene, with 1,3-butadiene and isoprene being particularly preferable.

As the vinyl monomer, styrene, o-methylstyrene, p-methylstyrene, α-methylstyrene, p-tert-butylstyrene, 1,3-
Vinyl aromatic compounds such as dibutylstyrene, vinylnaphthalene, divinylbenzene, and 1,1-diphenylethylene; (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate Esters; (meth) acrylates having a hydroxyl group in the molecule such as 2-hydroxyethyl methacrylate; (meth) acrylates having a glycidyl group in the molecule such as glycidyl methacrylate; acrylonitrile and the like, and one or two of these. Used in seeds and above. Of these, vinyl aromatic compounds are preferably used, more preferably styrene and α-methylstyrene.
The microstructure of the conjugated diene unit in the conjugated diene polymer block is not particularly limited.

On the other hand, as the N-substituted maleimide monomer,
For example, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-n-hexylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (1-naphthyl) maleimide, N- Benzylmaleimide, N-
(2-fluorenyl) maleimide, N-1- (4-acetoxynaphthyl) maleimide, N-2-methylphenylmaleimide and the like can be mentioned, and these monomers are 1 type or 2 types.
Used in seeds and above.

The copolymer of the general formula [1] as the component A can be easily synthesized by a known anionic polymerization method.
Conjugated diene alone or conjugated diene and vinyl monomer under an inert gas atmosphere such as nitrogen and argon in an organic solvent, using an alkali metal or an organic alkali metal compound as a polymerization initiator, -100 to 150 ° C, preferably -80 ~
Polymerization is carried out at a temperature of 70 ° C., and then N-substituted maleimide is added to continue the polymerization reaction, whereby a copolymer composed of a conjugated diene polymer block and an N-substituted maleimide polymer block is synthesized.

As the alkali metal of the polymerization initiator, lithium, sodium, potassium and the like are used, and as the organic alkali metal compound, alkyl compounds, allylic compounds and aryl compounds of the above alkali metals are used. Specific examples of the organic alkali metal compound include ethyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, ethyl sodium, butadienyl dilithium, butadienyl disodium, lithium biphenyl, lithium naphthalene, lithium trioxide. Examples thereof include phenyl, lithium fluorene, sodium biphenyl, sodium naphthalene, sodium triphenyl, sodium fluorene, and α-methylstyrene sodium dianion, and these are used as one kind or as a mixture of two or more kinds.

As reaction solvents, aliphatic hydrocarbons such as n-hexane and n-heptane; alicyclic hydrocarbons such as cyclohexane and cyclopentane; aromatic hydrocarbons such as benzene and toluene; diethyl ether, dioxane The organic solvent usually used in anionic polymerization, such as ethers such as tetrahydrofuran and tetrahydrofuran, is a single solvent or 2
It is used as a mixed solvent of one or more kinds.

In the above reaction, by using a conjugated diene polymer having a carbon-alkali metal bond at one end of the molecular chain, the following general formula [4] XY ... [4] (where X is And Y have the same meanings as described above) to give an AB type block copolymer. Further, by using a conjugated diene-based polymer having a carbon-alkali metal bond at both ends of the molecular chain, the following general formula [5] Y-XY ... [5] (where X and Y are , Having the same meanings as described above) is obtained.

In the above copolymer, a conjugated diene polymer block: X and an N-substituted maleimide polymer block:
The ratio with Y = X / Y (weight basis) is 20/80 ≦ X /
Y ≦ 90/10 is preferable, and when this X / Y ratio is too small, the electrical properties of the cured product deteriorate, and when it is too large, the compatibility with different resins decreases. Further, the number average molecular weight of the copolymer is preferably in the range of 500 to 100,000, and when it is too small, the thermal shock resistance of the cured product decreases, and when it is too large, the compatibility with different resins decreases.

The copolymer of the general formula [2] as the component A can be easily synthesized by the following method. (I) A conjugated diene or a conjugated diene and a vinyl monomer are polymerized by the anionic polymerization method described above to synthesize a conjugated diene-based polymer having an alkali metal bonded to at least one polymer end, and then the following general formula [6]

[0021]

[Chemical 2] (Wherein R ′ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), for example, ethylene oxide,
A cyclic ether compound such as propylene oxide is added to form an oxygen-alkali metal bond at the polymer terminal, and then N-
A method in which a substituted maleimide monomer is added and copolymerized.

(Ii) Oxygen-alkali in the molecule is produced by reacting a conjugated diene polymer having 1 to 5 hydroxyl groups and / or epoxy groups in the molecular chain and at the terminal of the molecular chain with an alkali metal or an organic alkali metal. A method in which a metal bond is introduced and then N-substituted maleimide monomers are added and copolymerized. The conjugated diene polymer having 1 to 5 hydroxyl groups and / or epoxy groups in the molecular chain and / or at the terminal of the molecular chain in the above synthesis method (ii) can be synthesized by the following method or the like. Even if it is synthesized by a method other than the above, any conjugated diene polymer having a hydroxyl group and / or an epoxy group in the molecular chain and / or at the molecular end can be used in the present invention. (a) The reaction product of a conjugated diene polymer having an alkali metal bonded to at least one terminal synthesized by the method of the above (I) and a cyclic ether compound is treated with water, alcohol, Lewis acid or the like. And a method of introducing a hydroxyl group into at least one terminal.

As a commercial product manufactured by this method, NISS
O PBG-1000, same -2000, same -3000 (manufactured by Nippon Soda Co., Ltd.)
Etc. (b) In the method (I), a halogenated cyclic ether such as epichlorohydrin is used in place of the cyclic ether compound to introduce an epoxy group into at least one polymer terminal. (c) Compounds having a hydroxyl group in the molecule such as hydrogen peroxide and azobis-4-cyanopentanol, or azo compounds such as azobisisobutyronitrile and azobis-2,4-dimethylvaleronitrile and mercaptoethanol A method in which a conjugated diene or a conjugated diene and a vinyl monomer are radical-polymerized by using a hydroxyl group-containing mercaptan such as the above in combination as a polymerization initiator to obtain a conjugated diene polymer having a hydroxyl group in the molecular chain. (d) A method of radically copolymerizing a compound having a hydroxyl group or an epoxy group in a part or all of a vinyl monomer and a conjugated diene. (e) Epoxylation of a part of the conjugated diene unit of the conjugated diene homopolymer or copolymer having or not having a functional group in the molecule by using a known reagent such as peracetic acid to introduce an epoxy group into the molecular chain. how to.

As the alkoxidizing agent for introducing an oxygen-alkali metal bond into the conjugated diene polymer having a hydroxyl group and / or an epoxy group in the molecule, the general formula [1] copolymer of the component A is used. The polymerization initiator used in the above synthesis can be used, and more preferably an alkyllithium compound such as n-butyllithium or sec-butyllithium is used. The reaction of introducing an oxygen-alkali metal bond into the conjugated diene-based polymer having a hydroxyl group and / or an epoxy group in the molecule is carried out by reacting the conjugated diene-based polymer and an organic alkali metal compound with each other in an organic solvent at −10.
While stirring at a temperature of 0 to + 100 ° C, preferably -7 to 0 to + 50 ° C, 1 second to 5 hours, preferably 1 minute to 3
The reaction can be carried out over time.

As reaction solvents, aromatic hydrocarbon solvents such as benzene and toluene; alicyclic hydrocarbon solvents such as pentane and cyclohexane; ether solvents such as dimethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane and anisole; methylal ,
Acetal solvents such as dimethoxyethane; amine solvents such as trimethylamine and N-methylmorpholine can be used, and these can be used as a single solvent or a mixed solvent of two or more kinds.

The copolymerization reaction of the conjugated diene polymer having an oxygen-alkali metal bond in the molecule obtained by the method (i) or (ii) and the N-substituted maleimide monomer is
In the organic solvent exemplified above, the reaction temperature is from -100 to
The reaction can be carried out for 1 minute to 100 hours, preferably 1 to 50 hours while stirring at a temperature of + 100 ° C, preferably -70 to + 50 ° C. In the above reaction, by using a conjugated diene polymer having an oxygen-alkali metal bond at one end of the molecular chain, an N-substituted maleimide polymer block is attached to one end of the conjugated diene polymer block through an ether bond. An AB block copolymer represented by the general formula [7] X-O-Y ... [7] (where X and Y have the same meanings as described above) is obtained.

Further, by using a conjugated diene-based polymer having oxygen-alkali metal bonds at both ends of the molecular chain, an N-substituted maleimide polymer block is formed at both ends of the conjugated diene-based polymer block via ether bonds. An ABA type block represented by the following general formula [8] Y-O-X-O-Y ... [8] (where X and Y have the same meanings as described above). A copolymer was obtained, and by using a conjugated diene-based polymer having an oxygen-alkali metal bond in the molecular chain, an N-substituted maleimide polymer block was branched from the molecular chain of the conjugated diene-based polymer block. The following general formula

[9]

[0028]

[Chemical 3] (Here, X, Y and n have the same meanings as described above) to obtain a graft copolymer.

Further, by using a conjugated diene-based polymer having an oxygen-alkali metal bond in the molecular chain terminal and in the molecular chain, N is bonded through an ether bond at the molecular chain terminal and in the molecular chain of the conjugated diene polymer block. -The following general formula [10] having a substituted maleimide polymer block

[0030]

[Chemical 4] (Here, X, Y and n have the same meanings as described above) to obtain a block-graft copolymer.

In the copolymer, the conjugated diene polymer block is the same as the copolymer of the general formula [1] of the component A:
Ratio of X to N-substituted maleimide polymer block: Y =
X / Y (weight basis) is 20/80 ≦ X / Y ≦ 90/1
0 is preferable, and when this X / Y ratio is too small, the electrical properties of the cured product deteriorate, and when it is too large, the compatibility with different resins decreases. Further, the number average molecular weight of the copolymer is preferably in the range of 500 to 100,000, and when it is too large, the thermal shock resistance of the cured product decreases, and when it is too large, the compatibility with different resins decreases.

As the thermosetting resin which is the component B of the present invention, it is preferable to use a resin having excellent heat resistance, but the kind thereof is not particularly limited. Preferred thermosetting resins include, for example, epoxy resins, polybutadiene resins, the following general formula [11]

[0033]

[Chemical 5] (Wherein A represents a p-valent aromatic, alicyclic or aliphatic organic group, and p represents an integer of 1 to 6), and a maleic acid compound represented by To be

As the epoxy resin, a bifunctional or higher functional polyfunctional epoxy resin is preferably used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, glycidyl ester type epoxy resin, polyglycol type epoxy resin, alicyclic epoxy resin , Glycidyl amine type epoxy resin, isocyanuric acid type epoxy resin, halogenated bisphenol A type epoxy resin, halogenated phenol novolac type epoxy resin,
Examples thereof include polybutadiene epoxy resins (see Japanese Patent Publication No. 027093), and urethane modified epoxy resins, acrylic modified epoxy resins, and the like, which are modified products thereof. These can be blended alone or as a mixture.

As the polybutadiene resin, homopolymers and copolymers of diene in which 50% or more of the butadiene units in the polymer chain are 1,2-bonds and their derivatives can be blended as the component B without particular limitation. For example, NISSO PB B-1000, B-20 sold by Nippon Soda Co., Ltd.
00, same B-3000, same G-1000, same G-2000, same G-3000, same C-10
00 etc. and their derivatives TE-2000 (modified acrylate), GM-1000 (modified maleic anhydride half ester), GQ-1000 (modified boiled), TP-1001 (modified urethane) ), BF-1000 (epoxidized modified product), GI-1000, GI
-3000 (hydrogenated modified product), BN-1010 (mine modified product), etc. are used in combination. The maleimide compound represented by the general formula [11] is usually obtained by reacting maleic anhydride or a derivative thereof with an amine having one or more amino groups to synthesize maleamic acid, and then converting maleic acid into a dehydrated ring. It is synthesized by a publicly known method such as a method of converting the compound into

As the maleimide compound, N-ethylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-phenylmaleimide, N-o, m- or p-methoxyphenylmaleimide, N-2-nitrophenylmaleimide, N-3 , 5-Dichlorophenylmaleimide, N-
o, m or p-hydroxyphenyl maleimide, N-
o, m or p-carboxyphenyl maleimide, Np
-Allylphenyl maleimide, Np-fluorophenyl maleimide, N-4-pyridyl maleimide, N-
(2-Methyl-4-pyridyl) maleimide, N-pentachlorophenylmaleimide, N-o, m or p-acetoxyphenylmaleimide, Np- [1-methyl-1-
(P'-Hydroxyphenyl) ethyl] phenylmaleimide, N-2-methyl-4- [1'-methyl-1 '-(3 "-methyl-4" -hydroxyphenyl) ethyl] phenylmaleimide, N-benzylmaleimide , N-4-quinolylmaleimide, N-1 (or 2) -naphthylmaleimide and other monomaleimides; N, N'-ethylene bismaleimide, N,
N'-o, m or p-phenylene bismaleimide, N, N '
-Hexamethylene bismaleimide, N, N '-(methylene-
Di-p-phenylene) bismaleimide, N, N '-(oxy-di-p-phenylene) bismaleimide, N, N'-(thio-di-pphenylene) bismaleimide, N, N '-(sulfonyl- Di-p-phenylene) bismaleimide, N, N'-
(Sulfinyl-di-p-phenylene) bismaleimide, N, N '-(methylene-di-1,4-cyclohexylene) bismaleimide, N, N'-(isopropylidene-di-
p-phenylene) bismaleimide, N, N'-m-xylylenebismaleimide, N, N'-p-xylylenebismaleimide, N, N '-(imino-di-p-phenylene) bismaleimide, N, N'-2,4-tolylene bismaleimide, N, N'-
(Methylene-di-3-chloro-p-phenylene) bismaleimide N, N '-(methylene-di-3-methyl-1,4-phenylene) bismaleimide, N, N'-(vinylene-di-p
-Phenylene) bismaleimide, 4-methyl-2,4-bis (p-N-maleimidophenyl) pentane, N, N'-1,
4-naphthylene bismaleimide N, N'-2,4-pyridine bismaleimide, tris (4-N-maleimidophenyl)
Phosphate, tris (4-N-maleimidophenyl)
Thiophosphate, 2,4,6-tris (4'-N-maleimidophenoxy) -s-triazine, 5 (or 6) -N-
Maleimide-1- (4'-N-maleimidophenyl) -1,
Examples thereof include polymaleimides such as 3,3-trimethylindane, poly (phenylenemethylene) polymaleimide, poly (cyclohexylenemethylene) polymaleimide, and the hydrogen atom bonded to the unsaturated carbon in the maleimide group of these maleimide compounds is , Chlorine atom, bromine atom,
A compound substituted with a methyl group, an ethyl group, a phenyl group or the like can also be used. As the component B, these maleimide compounds are also used alone or as a mixture of two or more kinds.

The cyanate ester is a polyfunctional cyanate ester having a cyanato group in the molecule or a prepolymer thereof alone or a resin composition containing these components as an essential component. For example, cyanate resin (Japanese Patent Publication No. 41-
1928, Japanese Patent Publication No. 45-011712, Japanese Patent Publication No. 41222
JP, DE-1,190,184, etc.), cyanate ester-maleimide resin, cyanate ester-maleimide-epoxy resin (Japanese Patent Publication No. 54-030440, Japanese Examined Patent Publication)
52-031279, USP-4,110,364, etc.), cyanate ester-epoxy resin (Japanese Patent Publication No. 46-04)
1112 gazette, etc.).

As the above polyfunctional cyanate ester,
Represented by the following general formula [12] R "'(OCN) q ... [12] (where R"' represents an aromatic organic group, q is an integer of 5 or less), and cyanato A compound in which the group is bonded to the aromatic ring is preferably used. For example, 1,3- or
1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2,
7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis (4-cyanatophenyl) methane, 2,2-bis (3,5-dichloro-)
4-Cyanatophenyl) propane, 2,2-bis (3,5-
Dibromo-4-cyanatophenyl) propane, bis (4
-Cyanatophenyl) ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl)
Cyanate ester (U obtained by reacting sulfone, tris (4-cyanatophenyl) phosphite, tris (4-cyanatophenyl) phosphate, etc. and a terminal-OH-containing polycarbonate oligomer with cyanogen halide
SP-4,026,913) and cyanate ester obtained by reaction of novolac with cyanogen halide (see USP-4,022,755, USP-3,448,079 etc.) and the like. In addition, Japanese Patent Publication No. 41-1928 and Japanese Patent Publication 43
-18468, Japanese Patent Publication No. 444791, Japanese Patent Publication No. 45-011712,
Japanese Patent Publication No. 46-041112, Japanese Patent Publication No. 47-026853, Japanese Patent Publication No. 51-
Publications such as 063149, USP-3,553,244, USP-3,75
5,402, USP-3,740,348, USP-3,595,900,
Cyanate esters described in USP-3,694,410, USP-4,116,946 and the like can also be used.

Further, the cyanate ester is converted into a mineral acid,
Lewis acids, salts such as sodium carbonate or lithium chloride,
A prepolymer obtained by polymerization in the presence or absence of a catalyst such as a phosphoric acid ester such as tributylphosphine can also be used. These prepolymers generally have a sym-triazine ring formed by trimerizing the cyan group in the cyanate ester in the molecule.

The polyfunctional cyanates are also used in the form of prepolymers with amines. Suitable amines include, for example, m- or p-phenylenediamine,
m- or p-xylylenediamine, 1,4- or 1,3-cyclohexanediamine, hexahydroxylylenediamine, 4,4'-diaminobiphenyl, bis (4-aminophenyl) methane, bis (4-aminophenyl) ) Ete
, Bis (4-aminophenyl) sulfone, bis (4-
Amino-3-methylphenyl) methane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4-aminophenyl) cyclohexane, 2,2-bis (4-aminophenyl) propane, 2,2- Bis (4-amino-3-methylphenyl) propane, 2,2-bis (4-amino-3)
-Chlorophenyl) propane, 2,2-bis (4-amino-3-chlorophenyl) methane, 2,2-bis (4-amino-3,5-dibromophenyl) propane, bis (4-aminophenyl) phenylmethane, 1,1-bis (4-aminophenyl) -1-phenylethane and the like can be mentioned.

The polyfunctional cyanate ester, the prepolymer thereof and the prepolymer with amine can be used in the form of a mixture, and the number average molecular weight of the individual and the mixture is 300 to 6,000.
, Preferably 1,500 or less, more preferably 300 to 1,000
Used in the range of. As a maleimide used as a component of a cyanate ester-based resin composition represented by a cyanate ester-maleimide resin and a cyanate ester-maleimide-epoxy resin, a maleimide compound represented by the general formula [11] is preferable. Used for.

As the vinyl monomer as the component B, aromatic vinyl monomers such as styrene and divinylbenzene;
(Meth) acrylic acid esters such as ethyl acrylate, methyl methacrylate and trimethylolpropane trimethacrylate; phthalic acid esters such as dimethyl fumarate; maleic acid esters such as dimethyl maleate; allyl compounds such as diallyl phthalate A radically polymerizable monomer such as triallyl isocyanurate is used.

The organopolysiloxane of component C is a dimethylsiloxane unit as a basic repeating unit, and the terminal and / or side chain in this molecule has a carboxyl group, a hydroxyl group,
It has at least one functional group selected from an amino group, an ester group, a mercapto group, an epoxy group, a polyoxyalkylene group, a vinyl group and a (meth) acryl group, and has a number average molecular weight of 1,000 or more. In addition, a part of the methyl group in the repeating unit may be substituted with an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. As commercially available products, SF-8418, BY having a carboxyl group is used.
-16-750 (all manufactured by Toray Dow Corning Silicone Co., Ltd.), XF42-411 (manufactured by Toshiba Silicone Co., Ltd.), SF-842 as having a hydroxyl group
7, SF-8428, SH-3771, BX16-19
0, BY16-752 (all manufactured by Toray Dow Corning Silicone Co., Ltd.), XF42-220, XF42-4
14 (all manufactured by Toshiba Silicone Co., Ltd.), SF-8417, BX16-859, BY having an amino group.
16-853 (all manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF4700, TSF4701, TSF
4702 (manufactured by Toshiba Silicone Co., Ltd.), SF-8422 (manufactured by Toray Dow Corning Silicone Co., Ltd.) as having an ester group, BX16-838A (Toray Dow Corning Silicone as having mercapto group) Co., Ltd.), SF8411, SF8413, BY16-861, B having an epoxy group
Y16-855 (all manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4730, YF3965 (all manufactured by Toshiba Silicone Co., Ltd.), SH3749, SH8400, SF8 having a polyoxyalkylene group.
419 (above Toray Dow Corning Silicone Co., Ltd.)
Manufactured), TSF4440, TSF4445, TSF445
0 (all manufactured by Toshiba Silicone Co., Ltd.), SF8421 having an epoxy group and a polyoxyalkylene group
EG, BY16-845, BX16-866 (all manufactured by Toray Dow Corning Silicone Co., Ltd.), BX16-867 (manufactured by Toray Dow Corning Silicone Co., Ltd.) having a vinyl group, (meth) acrylic group BX16-192 (manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like are exemplified, and these are used alone or as a mixture of two or more kinds.

The curable resin composition of the present invention comprises the above component A
It is prepared by mixing the copolymer (1) with the thermosetting resin of component B and / or the vinyl monomer and the organopolysiloxane of component C, or preliminarily reacting component A and / or component B with component C. As a preparation method, (a) a method of simply mixing without solvent at room temperature or under heating, (b) a method of heating without solvent to perform a preliminary reaction, (c) acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, etc. Of the above, or a method of dissolving in a mixed solvent of two or more kinds and mixing as a solution, (d) a method of mixing as a solution in the solvent and preliminarily reacting, (e) a mixture of those preliminarily reacted in the solvent A method etc. can be adopted.

The composition ratio of the component A, the component B and the component C varies depending on the purpose of use and is not particularly limited, but is usually 90/10 ≧ A / A + B ≧ 5/95, preferably 8 by weight ratio.
0/20 ≧ A / A + B ≧ 10/90, and the component C is 0.01 to 10 relative to the total amount of the components A and B.
A weight% range is preferred. The curable resin composition of the present invention can be cured as it is depending on the combination, but a known compound is used as a curing catalyst of the component B as a curing reaction accelerator. Examples of these curing accelerators include epoxy resin curing agents, organic metal salts, and organic peroxides.

As a curing agent for epoxy resin, for example, tertiary amines such as benzyldimethylamine, imidazoles such as 2-ethylimidazole, quaternary ammonium salts such as choline chloride, fats such as triethylenediamine and triethylenetetramine. Group polyamines, aromatic polyamines such as diaminophenylmethane and diaminodiphenyl sulfone, alicyclic polyamines such as N-aminoethylpiperazine and menthanediamine, phthalic anhydride, 4-methylhexahydrophthalic anhydride, trimellitic anhydride Acids, acid anhydrides such as pyromellitic dianhydride, benzophenonetetracarboxylic anhydride, etc., dicyandiamide, phenol novolac resins, aniline / formaldehyde resins, polyamide resins, triphenylphosphine, etc., and these may be used alone or Two or more kinds are used in combination.

As the organic metal salts, zinc naphthenate, lead stearate, lead naphthenate, zinc octylate, tin oleate, tin octylate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetone, manganese acetylacetone, etc. These are also used alone or in combination of two or more.

As the organic peroxide, benzoyl peroxide,
2,4-Dichlorobenzoyl peroxide, octanoyl peroxide, lauroyl peroxide and other diacyl peroxides, di-t-butyl peroxide, 2,5-
Diallyl peroxides such as dimethyl-2,5-di (t-butylperoxy) hexyne-3 and dicumyl peroxide; t-butyl perbenzoate, t-butyl peracetate, di-t-butyl perphthalate, 2 Peroxyesters such as 5,5-dimethyl-2,5-di (benzoylperoxy) hexane; ketone peroxides such as methylethylketone peroxide and cyclohexanone peroxide; di-t-butylhydroperoxide, cumene hydroperoxide , Α-phenylethylhydroperoxide, cyclohexenyl hydroperoxide and other hydroperoxides; 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3, Peroxyke such as 3,5-trimethylcyclohexane And the like, and the amount of them used is generally within the range of the amount of catalyst in a general sense. For example, 10% by weight or less, preferably 5% by weight or less is used with respect to the amount of the preceding resin. It

To the curable resin composition of the present invention, components other than the above can be added and blended within a range that does not impair the characteristics thereof. As these compounding components, thermosetting resins other than those exemplified above, thermoplastic resins, polyallyl compounds, liquid rubbers, solvents, fillers, flame retardants, plasticizers, photopolymerization initiators, polymerization inhibitors, coupling agents, Examples include pigments and the like.

As the thermosetting resin, an unsaturated polyester resin, a diallyl phthalate resin, a urethane acrylate resin or the like can be added within a range that does not impair the performance.

As the thermoplastic resin, aromatic or aliphatic petroleum resin, rosin resin, terpene resin, coumarone resin, xylene resin, ketone resin and the like are blended.

The polyallyl compound is not particularly limited as long as it has at least two or more allyl groups in one molecule. For example, triallyl isocyanurate, o, o
Bisphenols such as ′ -diallylbisphenol A, o, o′-diallylbisphenol F, 1,1,1,3,3,3-hexafluoro-2,2-bis (p-hydroxy-o-allylphenyl) propane Allylated phenol novolac, allylated 1,1,3-tris- (4-hydroxyphenyl) propane, allylated 1,1,2,2-tetra (4-hydroxyphenyl) ethane; α, α, α ', α'-
One or a mixture of two or more of an allylated product of tetra (4-hydroxyphenyl) -p-xylene and an allylated product of a dehydration condensation product of phenols and hydroxybenzaldehyde can be used.

As liquid rubber, 1,4-polybutadiene, such as polyoil 110, 130, manufactured by Nippon Zeon Co., Ltd.,
160, Idemitsu Arco (Poly BDR-45HT, R-45MA,
Polyisoprene, R-45EPT, etc., Polyisoprene, R-45EPT, polyisoprene, such as Kuraprene LTR-290 manufactured by Kuraray Co., Ltd.,
-390, Same-310, Same-30, Same-50, Same-403, Same-410, Same-50
3, 506, etc. Nitrile rubber such as BF Goodrich Hiker CTBN-1300 × 8, VTBN-1300 × 14,
ATBN-1300 × 16, CTB-2000 × 162, etc., chloroprene rubber such as Denka LCRX-10 manufactured by Denki Kagaku Kogyo Co., Ltd.
0, X-050, C-type, CE-type, H-type, XA-type, etc. can be used.

As the solvent, in addition to the reaction solvent used in the synthesis of the copolymer, a ketone solvent such as acetone, methyl ethyl ketone and methyl isobutyl ketone, an ester solvent such as ethyl acetate and butyl acetate, carbon tetrachloride and monochlorobenzene. The chlorinated hydrocarbon solvent can be used.

As the filler, fused silica, silica powder such as crystalline silica, inorganic filler such as alumina, magnesium oxide (magnesia), wollastonite, mica, calcium carbonate, talc and the like are preferably blended. These fillers may be used as they are as powdery, particulate, flake or fibrous fillers, or may be surface-treated with the above coupling agent.

As the flame retardant, a known inorganic or organic flame retardant, for example, aluminum hydroxide, antimony oxide,
Perchloropentacyclodecane, tetrabromobisphenol A, pentabromophenol methacrylate, halogenated epoxy resin, 4-bromophenylmaleimide, 2,4-dibromophenylmaleimide, 2,4,6
-Tribromophenylmaleimide and the like are used.

Examples of the plasticizer include phthalic acid esters such as dibutyl phthalate and dioctyl phthalate; phosphoric acid esters such as tricresyl phosphate and diphenyl octyl phosphate; dibutyl sebacate, dioctyl sebacate and di-2-ethylhexyl adipate. And dibasic acid esters thereof are used.

As the photopolymerization initiator, a photoradical polymerization initiator such as benzoin, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxyphenylacetophenone, 2-ethylanthraquinone is used. it can.

As a polymerization inhibitor, 4,4'-thiobis (6-
t-butyl-3-methylphenol), 3,5-di-t-
Butylhydroxytoluene, 2,2'-methylenebis (4-
Alkylphenols such as methyl-6-t-butylphenol) and 4,4′-butylidenebis (6-t-butyl-3-cresol); phenyl-C-naphthylamine, N, N ′
-Arylamines such as di-β-naphthyl-p-phenylenediamine; catechols such as pt-butylcatechol; hydroquinones such as hydroquinone and hydroquinone monomethyl ether are used.

As the coupling agent, a compound represented by the general formula ESiF ₃ (wherein E is a non-hydrolyzable organic group such as a vinyl group, a methacryloxypropyl group, an aminoalkyl group, a mercaptoalkyl group and an epoxyalkyl group, F is a halogen) , A hydrolyzable organic group such as an alkoxy group), for example, a silane coupling agent such as γ-glycidoxypropyltrimethoxysilane and α-aminopropyltriethoxysilane, in the above general formula A titanium coupling agent in which Si is replaced with Ti can be used.

The curable resin composition of the present invention comprises Component A
A copolymer of (1), a thermosetting resin and / or a vinyl monomer of component B, and an organopolysiloxane of component C, if desired, with a curing accelerator, various additives, and the like,
It is prepared and used as a composition for paints, adhesion, casting, etc. These curable resin compositions can be cured at room temperature and can be cured using various energies such as hot air, electric heat, infrared rays, far infrared rays, high frequencies, and microwaves. Further, the curable resin composition is dissolved in an appropriate solvent to prepare an impregnated varnish. A B-stage prepreg can be prepared by impregnating or applying this varnish on a sheet-shaped base material, air-drying it if necessary, and then drying it in constant temperature air at 60 to 150 ° C.

As the sheet-shaped substrate, woven fabrics, non-woven fabrics, mats, papers obtained by various weaving of inorganic fibers such as quartz, glass, carbon and asbestos, organic fibers such as polyester, polyacryl and polyamide, and combinations thereof A base material or the like is used. It is preferable that these base materials are subjected to a surface treatment using a coupling agent similarly to the filler and used. Using one or more of this prepreg,
If necessary, a metal foil such as an electrolytic copper foil is laminated, and the molding pressure is usually 3 to 100 kg / cm ² , and the temperature is 130 to 3
By pressurizing and heating under a condition of 00 ° C. for a certain period of time and molding, it is possible to manufacture a laminated board for a printed wiring board, which has excellent adhesiveness to a metal foil and excellent heat resistance and dielectric properties.

Further, the curable resin composition is heated and melted, and if necessary, additives such as a filler and a curing agent are added and sufficiently kneaded to prepare a curable resin composition for molding. be able to. The molding conditions of the resin composition for molding are usually molding pressure of 0.1 to 1,000 Kg / cm ² , preferably 3 to 500 Kg / cm ² , temperature of 100 to 300 ° C., preferably 150 to 240 ° C. and molding time. 30 seconds to 30 hours.

[0064]

The curable resin composition of the present invention comprises a copolymer (component A) comprising a conjugated diene polymer block and an N-substituted maleimide polymer block as described above, a thermosetting resin and / or a thermosetting resin. It is characterized by containing a vinyl monomer (component B) and an organopolysiloxane (component C) having a specific functional group in the molecule and having a number average molecular weight of 1,000 or more. In the present invention, the copolymer of component A is essentially composed of a non-polar segment and a polar segment. Therefore, the composition ratio of those segments,
That is, by selecting the copolymerization ratio of the conjugated diene polymer block and the N-substituted maleimide polymer block, it is compatibilized with both nonpolar polymers such as polybutadiene resin and polar polymers such as epoxy resin and polyimide resin. Therefore, it acts as a compatibilizing agent between the non-polar polymer and the polar polymer, which could not be conventionally compatibilized, and as a result, it becomes possible to prepare a novel curable resin composition.

In the cured product of the curable resin composition having the above-mentioned constitution, not only the phase separation structure is formed and the toughness and heat resistance of the cured product are remarkably improved, but also the conjugated diene polymer has The original excellent electrical characteristics, water resistance, moisture resistance, etc. are also imparted. Further, it is presumed that the organopolysiloxane as the component C acts as a regulator of the dispersion form in the phase-separated structure and makes the dispersed particles more fine, thereby lowering the thermal expansion coefficient. As a result, the curable resin composition of the present invention can be prepared as a resin composition of various aspects such as casting, molding, lamination, impregnation, adhesion, and coating, and by curing them, Mechanical strength,
A cured product having excellent water resistance, moisture resistance, heat resistance, electrical characteristics, thermal shock resistance, and a small thermal expansion coefficient can be obtained.

[0066]

EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples. However, the scope of the present invention is not limited by these examples. In the following examples, "part" and "%" are based on weight unless otherwise specified.

<Synthesis of Copolymer> (a) Sample A-1 A reaction vessel sealed with nitrogen was charged with 2500 g of a solution prepared by dissolving a sodium-kerosene dispersion containing 0.2 mol of sodium in tetrahydrofuran (hereinafter referred to as THF). -60 ° C
1500 g of a THF solution of 6.29 mol of butadiene and 1.34 mol of α-methylstyrene, which had been cooled to −60 ° C. in advance, was added dropwise over 4 hours, and the mixture was kept for 1 hour, and 0.5 mol of ethylene oxide was added. By the treatment, a solution of a butadiene-based polymer having oxygen-sodium bonds at both ends of the molecular chain was obtained. Table 1 shows the characteristics of the butadiene-based polymer obtained by removing a part of the reaction solution from the system, treating it with water, and distilling the solvent off under reduced pressure. Next, N-phenylmaleimide (hereinafter referred to as PMI) was added to the reaction system.
1500 g of a solution in which 1.45 mol was dissolved in THF was added dropwise over 4 hours, and the mixture was kept for 1 hour, and then the reaction was stopped by adding a hydrochloric acid-methanol solution. Then, the reaction solution was poured into a large amount of methanol to precipitate a polymer, which was filtered, washed, and then dried at 60 ° C for 24 hours to give a yellowish white powdery copolymer.
(Sample A-1) was obtained. The polymerization yield was 99.0%. The characteristics of Sample A-1 are shown in Table 1.

(B) Sample A-2 A commercially available hydroxyl group-containing 1,2-polybutadiene (number average molecular weight 3100, 1,2-bond content 91.0
%, Hydroxyl content per molecule 1.82, trade name NISSO PB
G-3000, manufactured by Nippon Soda Co., Ltd.) 500g solution in THF
Charge 3300 g, hold at 0 ° C, and stir to add 0.29 mol of n-butyllithium (OH / Li (molar ratio) = 1.0) dropwise to the butadiene-based polymer having oxygen-lithium bonds at both ends of the molecular chain. A combined solution was obtained. Next, while keeping the reaction system of this polymer solution at -60 ° C and stirring, 3300 g of a solution in which 2.67 mol of o-methylphenylmaleimide was dissolved in THF was added dropwise over 4 hours, and after further holding for 1 hour, The reaction was stopped and the post-treatment was performed in the same manner as in Sample A-1, to give a yellowish white powdery copolymer.
(Sample A-2) was obtained. The polymerization yield was 99.5%. The characteristics of Sample A-2 are shown in Table 1.

(C) Sample A-3 In a reaction vessel sealed with nitrogen, a commercially available hydroxyl group-containing 1,4-polybutadiene (number average molecular weight 2800, 1,4-bond content 80%,
Hydroxyl content of 2.35 per molecule, trade name poly-BD R-45
HT, manufactured by Idemitsu Arco Ltd.) 300g in THF 20
Charge 00 g, hold at 0 ° C, and stir to add 0.251 mol of n-butyllithium (OH / Li (molar ratio) = 1.0) dropwise to have oxygen-lithium bonds at both ends of the molecular chain and in the molecule. A butadiene-based polymer solution was obtained. Then, the reaction system of this polymer solution was kept at -60 ° C, 2000 g of a solution of 1.73 mol of PMI in THF was added dropwise over 4 hours with stirring, and the mixture was kept for 1 hour, and then sample A-1 was used. The reaction was stopped and the post-treatment was carried out in the same manner as in 1. to obtain a yellowish white powdery copolymer (Sample A-3). The polymerization yield was 98.8%. The characteristics of Sample A-3 are shown in Table 1.

(D) Sample A-4 A reaction vessel sealed with nitrogen was charged with 3300 g of a THF solution containing 0.25 mol of n-butyllithium, and the mixture was kept at -40 ° C under stirring for 9.26 mol of butadiene over 4 hours. After being introduced and held for 1 hour, 0.5 mol of ethylene oxide was added and treated to obtain a solution of a butadiene-based polymer having an oxygen-lithium bond at one end of the molecular chain. Table 1 shows the characteristics of the butadiene-based polymer obtained by removing a part of the reaction solution from the system, treating it with water, and removing the solvent under reduced pressure. Then, the reaction system of this polymer solution was kept at -60 ° C, and a solution of 0.72 mol of PMI in THF was stirred while stirring.
After 830 g was added dropwise over 4 hours and the mixture was kept for 1 hour, a hydrochloric acid-methanol solution was added to stop the reaction. Then
Water was added to the reaction solution to separate it, and then the solvent was distilled off from the polymer solution in the upper layer under reduced pressure to obtain a brown elastomeric copolymer.
(Sample A-4) was obtained. The polymerization yield was 98.7%. The characteristics of Sample A-4 are shown in Table 1.

[0071]

[Table 1]

Examples 1 to 6 and Comparative Examples 1 to 4 -Curable resin composition (impregnating varnish)-(a) Preparation of impregnating varnish (W-1 to W-6, CW for comparison)
-1 to CW-4) Component A; the copolymer synthesized above (Samples A-1 to A-
4) Component B: The following thermosetting resin CNE: Cresol novolac type epoxy resin (trade name YDCN-701, manufactured by Toto Kasei Co., Ltd.) SGM: Maleic anhydride half-esterified 1,2-polybutadiene (trade name PBSG-2050M) , Nippon Soda Co., Ltd.
M20: polyphenylene methylene bismaleimide (trade name: bismaleimide M-20, manufactured by Mitsui Toatsu Chemicals, Inc.) MB: 4,4′-bismaleimide-di- (3-ethyl-5-methylphenyl) methane ( Product name NB-700
0, manufactured by Mitsubishi Petrochemical Co., Ltd. Component C; Organopolysiloxane below SF: Epoxy / polyether modified polysiloxane (trade name SF8421EG, manufactured by Toray Dow Corning Silicone Co., Ltd.) BYE: Polysiloxane containing carboxyl group ( Product name B
Y16-750, manufactured by Toray Dow Corning Silicone Co., Ltd. and bisphenol A type epoxy resin (trade name YD-128, manufactured by Toto Kasei Co., Ltd.) as 50/100 (weight ratio) at 150 ° C. for 2 hours. Reacted substances Other components: TB: 2,4,6-tribromophenylmaleimide LR: Maleated 1,4-polybutadiene 1,4-polybutadiene (trade name Polyoil 110, manufactured by Nippon Zeon Co., Ltd.) (Addition amount of maleic anhydride = 10%)

The components A, B, and C are blended appropriately, and if necessary, the other components, dicumyl peroxide (referred to as DCP) or 2-undecylimidazole (epoxy curing agent, trade name as a curing accelerator. C ₁₁ Z, manufactured by Shikoku Fine Chemicals Co., Ltd., referred to as 2UI) was added and dissolved in cyclohexanone under heating to impregnate varnish having a resin content of 50%:
W-1 to W-6 were prepared. In addition, as a comparative sample, a curing accelerator was added to the composition comprising the components A and B, and the mixture was dissolved in cyclohexanone under heating to impregnate a varnish with a resin content of 50%:
Comparative samples CW-1 to CW-4 were prepared. The compounding composition of the prepared sample is shown in Table 2.

[0074]

[Table 2]

(B) Preparation and Evaluation of Laminated Plate Each of the impregnated varnish samples W-1 to W-6 and the comparative samples CW-1 to CW-4 prepared in the above item (a) had a thickness of 0.1.
mm glass fiber woven fabric was impregnated and dried by heating to prepare a B-stage prepreg. 1 for the obtained prepreg
Four layers are stacked, 35 μm thick electrolytic copper foil is stacked on both sides, pressure molding is performed under the conditions of 180 ° C. × 50 kg / cm ² × 120 minutes, and further cured at 200 ° C. for 24 hours to form a copper clad laminate. It was made.

The following characteristics of the copper-clad laminate prepared above were measured. Dielectric constant (ε) and electric tangent (tan δ): 1MHz, 25
Measured under conditions of ℃ Copper foil adhesion: kg / cm ² Solder heat resistance: Treated with solder bath at 300 ℃ for 120 seconds ○: No abnormality ×: Blistering Water absorption rate: Hold for 2 hours in boiling water (%) Thermal expansion coefficient ( α): Measured in the Z direction by the TMA method (ppm / ° C.). The measurement results are shown in Table 3. As shown in Table 3, the laminated board using the impregnated varnish made of the curable resin composition of the present invention has not only a low dielectric constant but also excellent copper foil adhesion, solder heat resistance, water resistance, and heat resistance. The expansion coefficient is small and each property is well balanced.

[0077]

[Table 3]

Example 7-Curable Resin Composition (Molding Material) -Copolymer (Sample A-2) 5 Synthesized above as Component A
0 part, M20 (the above) as the component B, 20 parts as the component C, SF (above) 5 parts, and TB as the other components (above)
After mixing 25 parts and 1 part of DCP (described above) as a curing accelerator, 250 parts of crystalline silica powder surface-treated with a silane coupling agent was added and kneaded at a temperature of 100 to 110 ° C. The granulated curable resin composition: G-1 was prepared by cooling and pulverizing. Prepared sample G-1 is 1
Compression molding was carried out under the conditions of 70 ° C. × 30 kg / cm ² × 3 minutes, and the molded product was held at 230 ° C. for 2 hours to cure. The obtained molded product had the following properties. Bending strength: 12.0 kg / cm ² (20 ° C) 9.8 kg / cm ² (200 ° C) Dielectric constant: 3.3 (1MHz, 20 ° C) Water absorption rate: 0.1% (holding in boiling water for 2 hours) Heating loss: 0.1% (180 (Holding at 24 ℃ for 24 hours) Thermal expansion coefficient: 8.5PPM / ℃ Flame retardance: UL94V-0

Example 8-Curable Resin Composition (Casting Resin) -Copolymer (Sample A-4) 4 Synthesized above as Component A
0 parts, 25 parts of MB as the component B (supra) and 20 parts of triallyl isocyanurate, BYE as the component C (supra)
After dissolving 15 parts by heating at 100 ° C. to form a uniform solution, 1 part of DCP (previously mentioned), 8 parts of 4-methylhexahydrophthalic anhydride and 2 UI (previously described) of 0.02 part were added as a curing accelerator. A light brown transparent liquid curable resin composition: Sample T-1 was obtained. The prepared curable resin composition for casting T-1 was heated to 130 ° C.
Cured for 3 hours and then at 150 ° C. for 8 hours. The obtained cured product had the following properties.

Curing shrinkage (Vs): 1.5% Vs = (solid specific gravity-liquid specific gravity) / solid specific gravity x 100 Bending strength: 8.9 kg / cm ² (20 ° C) 7.2 kg / cm ² (200 ° C) Dielectric constant: 2.6 (1MHz, 20 ℃) Water absorption: 0.2% (holding in boiling water for 2 hours) Thermal shock resistance: 120 ℃ ~ -30 ℃ × 10 cycles or more 100 ml poly cup, using 30 g of test resin, outer diameter
After embedding a 40 mmΦ spring washer and hardening by heating, 120 ° C × 1 hour → -30 ° C × 1 hour was set as one cycle, and repeated tests were conducted until cracks occurred. Thermal expansion coefficient: 55ppm / ℃

[0081]

The curable resin composition of the present invention comprises a copolymer composed of a conjugated diene polymer block and an N-substituted maleimide polymer block, a thermosetting resin and / or a vinyl monomer. It is characterized by comprising a specific organopolysiloxane. As is clear from the examples, the curable resin composition of the present invention is excellent in solubility and compatibility, and has a small curing shrinkage upon curing, and the cured product has mechanical strength, heat resistance and water resistance. It has excellent properties, adhesiveness, thermal shock resistance, and electrical characteristics, and has a small coefficient of thermal expansion. Therefore, it can be used for a wide range of applications such as casting materials, molding materials, sealing materials, impregnating varnishes for laminated plates, coil impregnating varnishes, paints and adhesives.

In particular, the prepreg using the impregnated varnish according to one embodiment of the present invention has good workability, and the laminate produced using the prepreg has excellent adhesiveness to the metal foil and excellent dielectric properties. Since it has heat resistance and flame retardancy and has a small coefficient of thermal expansion, it is extremely useful as a substrate material for a printed wiring board such as a high frequency circuit requiring a low dielectric constant. The present invention provides a curable resin composition that has both the original characteristics of a thermosetting resin that has been widely used in various fields in the past and the original characteristics of a conjugated diene polymer, and that has a very small coefficient of thermal expansion. However, its industrial significance including the electric and electronic fields is extremely significant.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C08L 101/00 LTA 7242-4J // C08G 59/20 NKB 8416-4J

Claims (2)

[Claims] 1. A curable resin composition comprising the following components A, B, and C: Component A: the following general formula [1] and / or [2] X (Y) m ... [1] X (O-Y) n ... [2] (where X is a conjugated diene-based compound). Combined block, Y is
N-substituted maleimide polymer block is shown, and m is 0 to
2, n is a positive number of 1 to 5), and the weight ratio of X and Y is 20/80 / ≤X / Y≤90 / 10 and the number average molecular weight is 500 to 100,000. Component B: Thermosetting resin and / or vinyl monomer Component C: Carboxyl group, hydroxyl group, amino group in the molecule,
An organopolysiloxane having at least one functional group selected from an ester group, a mercapto group, an epoxy group, a polyoxyalkylene group, a vinyl group, and a (meth) acryl group, and having a number average molecular weight of 1,000 or more. 2. The thermosetting resin of component B is an epoxy resin,
The curable resin composition according to claim 1, which is at least one selected from the group consisting of a polybutadiene resin, a maleimide compound, and a cyanate ester.