JPH0455457A - Curable resin composition - Google Patents

Abstract

PURPOSE:To provide the title composition of good workability, excellent in mechanical strength, resistance to heat, moisture and heat shock and electrical properties, and low in the shrinkage in its thermosetting, comprising a specific block copolymer, thermosetting resin and/or vinyl monomer and liquid rubber. CONSTITUTION:The objective composition comprising (A) a copolymer of formula X(O-Y)n (X is conjugated diene polymer block; Y is N-substituted maleimide polymer block; (n) is 1 - 5) having 500 - 100000 in number-average molecular weight with the weight ratio X/Y satisfying the relationship: (20:80) <= X/Y <=(90:10), (B) a thermosetting resin and/or vinyl monomer, selected from epoxy resins, polybutadiene resins, maleimide compounds and cyanic esters, and (C) a liquid rubber.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a curable resin composition, and more specifically, a curable resin composition in which a conjugated diene polymer block and an N-substituted maleimide polymer block are bonded via an ether bond. The present invention relates to a curable resin composition comprising a bonded copolymer, a thermosetting resin and/or a vinyl monomer, and a liquid rubber.

The curable resin composition of the present invention provides a cured product with excellent mechanical strength, heat resistance, moisture resistance, electrical properties, etc., and is therefore expected to be used in a wide range of fields including the field of electrical and electronic materials. .

[Conventional technology]

In the field of electrical and electronic materials, thermosetting resins such as epoxy resins, phenolic resins, and unsaturated polyester resins have been widely used. For example, epoxy resins, phenolic resins, polyimide resins, etc. are used as impregnating resins for laminated boards for printed wiring boards, and epoxy resins, silicone, etc. Low-pressure molding materials such as resin-based materials, heat or photocurable liquid materials such as epoxy resin-based, acrylic resin-based, and silicone resin-based materials are used.

On the other hand, cured products obtained by radically curing conjugated diene resins such as polybutadiene resins have excellent electrical properties, water resistance,
It is known to have excellent moisture resistance. For example, a method for manufacturing laminates and molding materials using a resin composition consisting of a 1,2-polybutadiene resin and a radical polymerization initiator that is liquid at room temperature and has a number average molecular weight of about 1,000 to 5,000 (Tokuko Showa) 47-051952, Japanese Patent Publication No. 48-014428, etc.), consisting of a 1,2-polybutadiene resin that is solid at room temperature and a radical polymerization initiator, with a number average molecular weight of 50,000 to 20o, about o o o. Method for manufacturing laminates using resin compositions
8-021925, Japanese Patent Publication No. 58-021926, etc.), a curable resin composition comprising a butadiene-vinyl aromatic compound copolymer and a cyanate ester resin composition (Japanese Patent Application Laid-Open No. 61-233060, etc.) reference)
etc. are disclosed.

[Problem that the invention seeks to solve]

BACKGROUND ART In recent years, the miniaturization of electronic devices has progressed dramatically, and along with this, higher performance and higher reliability of electrical and electronic components are required. For example, materials with excellent dielectric properties such as low dielectric constant and low dielectric loss tangent are required for substrates (laminates) for printed wiring boards used in high-speed arithmetic circuits and high-frequency circuits. In addition, materials for sealing electrical and electronic circuit components are required to have well-balanced adhesiveness, moisture resistance, heat resistance, thermal shock resistance, electrical properties, and the like.

In response to these demands, laminates using the aforementioned general-purpose resins do not satisfy the required dielectric properties, and sealing materials do not meet the required mechanical properties, especially both thermal shock resistance and electrical properties. There is nothing to be satisfied with.

On the other hand, laminates using polybutadiene resin have extremely excellent dielectric properties, but in the manufacturing method of laminates using liquid polybutadiene resin, the prepreg obtained by impregnating the base material and drying it has adhesive properties. Therefore, lamination molding was difficult.

Furthermore, in the method of manufacturing a laminate using solid polybutadiene resin, the solubility in general-purpose solvents is poor and the viscosity of the impregnating varnish is extremely high, so the workability of manufacturing the laminate is also extremely poor.

Furthermore, both have poor adhesion to metal foils such as copper foil, so they have not been put to practical use industrially yet.

In addition, when polybutadiene resin is used in electrical and electronic parts, extremely excellent heat resistance, moisture resistance, and electrical properties can be obtained, but the shrinkage rate during curing is extremely high and the adhesiveness is poor, so it is difficult to use liquid sealing materials. It is not used except for some special purposes.

Furthermore, polybutadiene resin has extremely poor compatibility with other thermosetting resins, and a method using the above-mentioned butadiene-vinyl aromatic compound copolymer has been proposed as a method to improve this, but it is difficult to obtain sufficient compatibility. In order to achieve this, it is necessary to increase the copolymerization ratio of the vinyl aromatic compound, in which case the heat resistance decreases.

The present invention has mechanical strength, heat resistance, moisture resistance, thermal shock resistance,
It is an object of the present invention to provide a curable resin composition that has excellent electrical properties, small shrinkage during heat curing, and excellent workability.

[Means for solving problems]

As a result of intensive research to achieve the above object, the present inventors have discovered that a specific copolymer consisting of a conjugated diene polymer block and an N-substituted maleimide polymer block can be used with other thermosetting resins. A curable resin composition consisting of this copolymer, a thermosetting resin and/or a vinyl monomer, and a liquid rubber has low shrinkage, mechanical strength, heat resistance, moisture resistance, and thermal shock resistance. , discovered that the cured product can improve electrical properties, etc., and completed the present invention.

That is, the present invention provides a curable resin composition component A characterized by consisting of the following components A, B and C; Here,
X represents a conjugated diene polymer block, Y represents an N-substituted maleimide polymer block, and n is a positive number from 1 to 5.

), and the weight ratio of X and Y is 20/80≦X/Y≦
90/10. Copolymer component B having a number average molecular weight of 500 to 100.000: thermosetting resin and/or vinyl monomer component C: liquid rubber.

In the present invention, component A is a conjugated diene polymer block in which X in the general formula (I) is a conjugated diene polymer block or a copolymer block of a conjugated diene and a vinyl monomer; Y is represented by the following general formula (I[
) At least one N-substituted maleimide represented by H-C-C-H (wherein R represents an alkyl group, cycloalkyl group, aryl group or substituted aryl group having 1 to 20 carbon atoms) It is a polymer block, and is a copolymer in which Y is bonded within the molecule of X via an ether bond.

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-butanene, 1,3-
Pentadiene, 2-methyl-1,3-pentadiene, 1
, 3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, etc., and these may be used alone or in combination. Among these, it is particularly preferable to use 1,3-butadiene and isoprene.

Further, as the vinyl monomer, styrene, 0-methylstyrene, p-methylstyrene, α-methylstyrene,
p-tert-butylstyrene, 1,3-dibutylstyrene, vinylnaphthalene, divinylbenzene, 1,1-
Vinyl aromatic compounds such as diphenylethylene; methyl (meth)acrylate, ethyl (meth)acrylate, (
(meth)acrylic acid esters such as butyl meth)acrylate; (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, etc., and one or more of these may be used. Among these, vinyl aromatic compounds are particularly preferably used, and styrene and α-methylstyrene are more preferably used.

Note that there are no particular limitations on the microstructure of the conjugated diene units in the conjugated diene polymer block.

N-substituted maleimide monomers include, for example, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide)', Nn-hexylmaleimide, N-cyclohexylmaleimide, N-
Phenylmaleimide, N-(1-naphthyl)maleimide, N-benzylmaleimide, N-(2-fluorenyl)
Maleimide F, N-1-(4-acetoxynaphthyl)maleimide, N-2-methylphenylmaleimide, and the like. These monomers may be used alone or in combination of two or more to obtain the N-substituted maleimide polymer block of Y.

The copolymer of component A used in the present invention can be easily synthesized by the method described below.

(i) A conjugated diene or a conjugated diene and a vinyl monomer are polymerized in an organic solvent under an inert gas atmosphere such as nitrogen or argon, using an alkali metal or an organic alkali metal compound as a polymerization initiator, at a temperature of -100 to +150°C. After polymerizing to synthesize a conjugated diene polymer with an alkali metal bonded to at least one polymer terminal, a cyclic ether compound is added to introduce an oxygen-alkali metal bond to the polymer terminal, and then N-substitution A method of copolymerization by adding maleimide monomer.

(ii) By reacting a conjugated diene polymer having 1 to 5 hydroxyl groups and/or epoxy groups in the molecular chain and/or at the end of the molecular chain with an alkali metal or an organic alkali metal compound, oxygen-alkali is added in the molecule. A method of introducing a metal bond and then adding an N-substituted maleimide monomer to copolymerize.

In the method of item (i) above, lithium, sodium, potassium, etc. are used as the alkali metal of the polymerization initiator, and alkylated products, allylated products, arylated products, etc. of the alkali metals are used as the organic alkali metal compound. Specific examples of organic alkali metal compounds include ethyllithium, n-butyllithium, 5ec-butyllithium,
t-butyl lithium, ethyl sodium, butadienyl dilithium, butadienyl disodium, lithium biphenyl, lithium naphthalene, lithium triphenyl,
Examples include lithium fluorene, sodium biphenyl, sodium naphthalene, sodium triphenyl, sodium fluorene, and α-methylstyrene sodium dianion, which may be used singly or as a mixture of two or more.

As a reaction solvent, aliphatic hydrocarbons such as n-hexane and n-heptane; ring hydrocarbons such as cyclohexane and cyclopentane; aromatic hydrocarbons such as benzene and toluene; Organic solvents commonly used in anionic polymerization, such as ethers, are used as a single solvent or a mixed solvent of two or more.

The cyclic ether compound used in the reaction with the conjugated diene polymer in which at least one alkali metal is bonded in the molecule synthesized by the above method is represented by the following general formula (DI) (where R' is a hydrogen atom or (representing an alkyl group having 1 to 4 carbon atoms), such as ethylene oxide, propylene oxide, and the like.

The reaction between a conjugated diene polymer to which at least one alkali metal is bonded and a cyclic ether compound is usually -70 to
It is carried out for 1 second to 3 hours while stirring at a temperature of +30°C. However, the reaction conditions are not limited to those described above, and can be adjusted within a wider range.

Furthermore, the synthesis of the conjugated diene polymer is not limited to the method described above, and for example, Japanese Patent Publication No. 43-027432, Japanese Patent Publication No. 47-019687, Japanese Patent Publication No. 47-03
Publication No. 3274, US Pat.
ion and physical properties J, P-193-195. ■Chemistry doujin,
(1970) and the like may be employed.

On the other hand, the conjugated diene polymer having 1 to 5 hydroxyl groups and/or epoxy groups in the molecular chain and/or at the end of the molecular chain in the synthesis method of item (ii) above can be synthesized by the following method, etc. Even if it is synthesized by a method other than the one described below, it can be used in the present invention as long as it has a hydroxyl group and/or an epoxy group in the molecular chain and/or at the end of the molecule. .

(a) The reaction product of the conjugated die polymer with an alkali metal bonded to at least one end synthesized by the method of item (i) above and a cyclic ether compound is treated with water, alcohol, Lewis acid, etc. A method of introducing a hydroxyl group into at least one terminal.

As a commercial product produced by this method, Nl5SOPBc
-tooo, same 2000. Same 3000 (all manufactured by Nippon Soda ■), etc.

(b) The conjugated diene polymer synthesized by the method of item (i) above and having an alkali metal bonded to at least one terminal is treated with a halogenated cyclic ether such as epichlorohydrin to form at least one polymer. A method of introducing an epoxy group to the joining 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 mercapto A method of radical polymerizing a conjugated diene or a conjugated diene and a vinyl monomer using a hydroxyl group-containing mercaptan such as ethanol as a polymerization initiator to obtain a conjugated diene polymer having a hydroxyl group in the molecular chain.

(d) hydroxyl group in part or all of the vinyl monomer,
A method of radical copolymerization of a compound having an epoxy group and a conjugated diene.

(e) Epoxidizing a part of the conjugated diene units of the conjugated diene homopolymer or copolymer with or without functional groups in the molecule using a known reagent such as peracetic acid,
A method of introducing epoxy groups into molecular chains. The polymerization initiator used in item (i) above can be used as an 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, Preferably, organic alkali metal compounds are used, and more preferably alkyllithium compounds such as n-butyllithium and 5ec-butyllithium are used.

In the reaction of introducing an oxygen-alkali metal bond into a conjugated diene polymer having a hydroxyl group and/or an epoxy group in the molecule, the conjugated diene polymer and an organic alkali metal compound are usually mixed in an organic solvent at a temperature of 100% ~+100
The reaction can be carried out for 1 second to 5 hours, preferably 1 minute to 3 hours while stirring at a temperature of -70 to +50°C.

As a reaction solvent, 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 and dimethoxyethane Acetal solvents such as trimethylamine, N-methylmorpholine, and other amine solvents can be used, and these may be used as a single solvent or a mixed solvent of two or more.

The copolymerization reaction between the conjugated diene polymer having an oxygen-alkali metal bond in the molecule obtained by the method (i) or (ii) above and the N-substituted maleimide monomer can be carried out using the above-mentioned organic In a solvent, reaction temperature -100 to +10
The reaction can be carried out for 1 minute to 100 hours, preferably 1 to 50 hours while stirring at a temperature of 0°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 formed at one end of the conjugated diene polymer block via an ether bond. General formula (iv) having X-0-Y
An AB type block copolymer represented by -·---(iv) (where X and Y have the same meanings as above) is obtained.

In addition, by using a conjugated diene copolymer that has oxygen-alkali metal bonds at both ends of the molecular chain, N
-The following general formula having a substituted maleimide polymer block (
v) y-o-x-o-y ・・・・・・・・・・・・ (
v) (herein, X and Y have the same meanings as above)
By using a conjugated diene polymer having an oxygen-alkali metal bond in the molecular chain, an A-B-A type block copolymer represented by The following general formula (where X, Y and n are branched N-substituted maleimide polymer blocks)
By using a conjugated diene polymer having an oxygen-alkali metal bond at the end of the molecular chain and in the molecular chain, The following general formula (distribution) Y-0-X-0-Y (herein, X, Y and n are A block-craft copolymer represented by (having the same meaning as above) is obtained.

In the copolymer, a conjugated diene polymer block:
Ratio of X to N-substituted maleimide polymer block Y -X
/Y (weight basis) is 20/80≦X/Y≦90/1
It is preferable that the X/Y ratio be 0. If the X/Y ratio is too small, the electrical properties of the cured product will deteriorate, and if it is too large, the compatibility with different resins will be reduced.

Further, the number average molecular weight of the copolymer is 500 to 100.
,000 is preferable; if it is too small, the thermal shock resistance of the cured product will decrease, and if it is too large, the compatibility with different resins will be reduced.

As the thermosetting resin of component B used in the present invention, it is preferable to use a resin having excellent heat resistance, but there is no particular restriction on the type thereof.

Preferred thermosetting resins include epoxy resins,
Polybutadiene resin, the following general formula (vi) (herein, A
represents a p-valent aromatic, alicyclic or aliphatic organic group, p is an integer of 1 to 6), cyanate esters and the like.

As the epoxy resin, a polyfunctional epoxy resin having two or more functionalities 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, ring type epoxy resin, Glycidylamine type epoxy resin, isocyanuric acid type epoxy resin,
Examples include halogenated bisphenol A type epoxy resin, halogenated phenol novolak type epoxy resin, polybutadiene epoxy resin (see Japanese Patent Publication No. 027093), and modified products of these, such as urethane-modified epoxy resin and acrylic-modified epoxy resin. Resin etc. are also used. These can be used alone or as a mixture.

As the polybutadiene resin, butadiene homopolymers and derivatives thereof in which 50% or more of the butadiene units in the polymer chain are 1,2-bonds can be blended as component B without particular limitation.

For example, Nl5SOP commercially available from Nippon Soda■
B B-1000, B-2000, B-3000,
G-1000, G-2000, G-3000, C-1000, etc., and their derivative TE-2
000 (acrylated modified product), M-1000 (maleic anhydride half ester modified product), GQ-1000 (boiled modified product), P-1001 (urethanized modified product),
BP-1000 (epoxidized modified product), G1-100
0, G1-3000 (hydrogenated modified product), etc. are used in combination.

The maleimide compound represented by the general formula (vi) is usually synthesized by reacting maleic anhydride or its derivatives with an amine having one or more amino groups to synthesize maleamic acid, and then dehydrating the maleamic acid into a ring. It is synthesized by a known method such as a method of converting into a compound.

As a maleimide compound, N-ethylmaleimide, N-
Butylmaleimide, N-hexylmaleimide, N-phenylmaleimide, N-o, m or p-methoxyphenylmaleimide, N-2-nitrophenylmaleimide, N-
-3,5-dichlorophenylmaleimide, No, m or p-hydroxyphenylmaleimide, No, m or p-carboxyphenylmaleimide, N-p-allylphenylmaleimide, N-p-fluorophenylmaleimide, N- 4-pyridylmaleimide, N-(2methyl-4-pyridyl)maleimide, N-pentachlorophenylmaleimide, N-o, m or p-acetoxyphenylmaleimide, N-p-(1-methyl-1-(p'- hydroxyphenyl)ethyl]phenylmaleimide, N-
2-Methyl-4-[1'-methyl-1'-(3''-methyl-4''-hydroxyphenyl)ethyl]phenylmaleimide, N-penzylmaleimide, N-4-quinolylmaleimide, N-1( or 2) monomaleimides such as -naphthylmaleimide, N,N'-ethylene bismaleimide F, N,N'-o, m* or p-phenylene bismaleimide, N,N'-hexamethylene bismaleimide,
N,N'-(methylene-di-p-phenylene)bismaleimide, N,N'-(oxy-di-p-)unishin)bismaleimide, N,N'-(thio-di-p-)unishin ) 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 -xylylene bismaleimide, N, N'-(imino-zyl-phenylene) bismaleimide, N, N' -2,4-tolylene bismaleimide, N, N'-(methylene-di-3-chloro-p- phenylene) bismaleimide, N,N'-(methylene-di3)
-methyl-1,4-)unishin)bismaleimide, N,
N'-(vinylene-p-)unisine) bismaleimide, 4-methyl-2,4-bis(p-N-maleimidophenyl)pentane, N,N'-1,4-naphthylene bismaleimide, N,N'-2,4-pyridine hismaleimide, tris(4-N-maleimidophenyl) phosphate, tris(4-N-maleimidophenyl) thiophosphate, 2,4.6-tris(4'-N-maleimide) phenoxy)-S-) riazine, 5 (or 6) N-maleimido-1-(4'-N-maleimidophenyl)-1
, 3,3-trimethylindane, poly(phenylenemethylene)polymaleimide, poly(cyclohexylenemethylene)polymaleimide, etc., and hydrogen bonded to the unsaturated carbon in the maleimide group of these maleimide compounds. Compounds in which atoms are appropriately substituted with chlorine atoms, bromine atoms, methyl groups, ethyl groups, phenyl groups, etc. can also be used. As component B, these maleimide compounds may be used singly or as a mixture of two or more.

Cyanate esters are polyfunctional cyanate esters having a cyanato group in the molecule, their prepolymers alone, or resin compositions containing these components as essential components.
Publication No. 45-011712, Special Publication No. 1973
-1222, DE-1,190,184, etc.), cyanate ester-maleimide resin, cyanate ester-maleimide-epoxy resin (Japanese Patent Publication No. 5
4-030440, Japanese Patent Publication No. 52-031279, US Pat. No. 4,110,364, etc.), cyanate ester-epoxy resin
041112, etc.).

As the above polyfunctional cyanate ester, the following general formula (
ix) R”'(OCN), ......--(ix)
(Here, R''° represents an aromatic organic group, and m is an integer of 5 or less), and a compound in which a cyanato group is bonded to an aromatic ring is preferably used.

For example, 1,3- or 1,4-dicyanatobenzene, 1.3.5-) lycyanatobenzene, 1.3-. 1°4-. 1.6-. 1.8-. 2,6- or 2,7-dicyanatonaphthalene, 1,3,6-dicyanatonaphthalene, 4,4°-dicyanatobiphenyl, bis(4cyanatophenyl)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) sulfone, tris(4-cyanatophenyl) phosphite, tris(4-cyanatophenyl) phosphate etc., and cyanic acid esters obtained by the reaction of terminal -OH-containing polycarbonate oligomers with cyanogen halides (see US Pat. No. 4,026,913, etc.), and cyanate esters obtained by the reaction of novolacs with cyanogen halides. Cyanate ester (USP-4,0
22°755, USP-3,448,079, etc.). In addition, the special public service
No. 28, Special Publication No. 18468, Special Publication No. 18468, Special Publication No. 44-47
No. 91, Special Publication No. 45-011712, Special Publication No. 46-0
No. 41112, Japanese Patent Publication No. 47-026853, Japanese Patent Publication No. 1977
Publications such as No. 1-063149, USP-3,55
No. 3,244, U.S.P. No. 3,755,402;
USP-3,740,348, USP-
No. 3,595,900, U.S.P.-3,694,4
Cyanic acid esters described in No. 10, USP-4,116,946, etc. can also be used.

Furthermore, the cyanate esters can be added to mineral acids, Lewis acids,
Prepolymers obtained by polymerization in the presence or absence of catalysts such as salts such as sodium carbonate or lithium chloride, and phosphoric esters such as tributylphosphine can also be used. These prepolymers are formed by trimerization of cyanide groups in the cyanate ester.
Generally has a ym-triazine ring in the molecule.

The polyfunctional cyanate esters are also used in the form of prepolymers with amines. Suitable amines include, for example, m- or p-funylenediamine, m- or p-xylylenediamine, 1,4- or 1,3-cyclohexanediamine, hexahydroxylylenediamine, 4,4'-diaminobiphenyl. , bis(4-aminophenyl)methane, bis(4-aminophenyl)ether, 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, l,1-
Bis(4-aminophenyl)-1-phenylethane and the like can be mentioned.

The polyfunctional cyanate esters, their prepolymers and prepolymers with amines can also be used in the form of mixtures,
Number average molecular weight of 300 to 6.000 individually and as a mixture;
Preferably 1.500 or less, more preferably 300-
Used in the range 1.000.

As the maleimide used as a component of a cyanate ester resin composition represented by cyanate ester-maleimide resin, cyanate ester-maleimide-epoxy resin, etc., a maleimide compound represented by the above general formula (vi) is suitable. used for.

As the vinyl monomer of 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; Radical polymerizable monomers such as triallyl isocyanurate.

The liquid rubber of component C used in the present invention is 1,4-polybutadiene, such as polyoil 1 manufactured by Nippon Zeon Co., Ltd.
10, 130, 160, PolyBD R-45HT, R-45MA, R-45E manufactured by Idemitsu Arco Co., Ltd.
PT, polyisoprene, such as Kuraprene LTR-290, Same 390, Same 310, Same 30, Same 50, Same 403, Same 410, Same 50 manufactured by Kuraray Co., Ltd.
3. Nitrile rubber such as 506, such as Hiker CTBN-1300X8 manufactured by BF Gutdrich, same v
TBN-1300x14, ATBN-1300x16
, CTB-2000x 162, etc., chloroprene rubber, such as Denka LCRX-1 manufactured by Denki Kagaku Kogyo Co., Ltd.
00, same x-oso, same C-type, same C-type,
The same C-type, the same C-type, etc. can be used.

The curable resin composition of the present invention is prepared by mixing or preliminarily reacting the copolymer of component A, the thermosetting resin and/or vinyl monomer of component B, and the liquid rubber of component C.

Preparation methods include (a) simply mixing without a solvent at room temperature or under heating, (b) heating and pre-reacting without a solvent, (C) acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, etc. (d) mixing as a solution in the solvent and pre-reacting; (e) mixing pre-reacted in the solvent. method etc. can be adopted.

The composition ratio of component A and component B varies depending on the purpose of use and is not particularly limited, but is usually 90/10≧A/
B≧10/90, preferably 70/30≧A/B≧30
/70, and component C is in a range of 50% by weight or less based on the total amount of components A and B.

The curable resin composition of the present invention can be cured as it is depending on the combination, but the above-mentioned component B can be used as a curing reaction accelerator.
A known compound is used as a curing catalyst.

Examples of these curing accelerators include curing agents for epoxy resins, 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, aliphatic polyamines such as triethylenediamine, triethylenetetramine, etc. , diaminophenylmethane,
Aromatic polyamines such as diaminodiphenylsulfone,
Ring polyamines such as N-aminoethylpiperazine and menthanediamine; acid anhydrides such as phthalic anhydride, 4-methylhexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic anhydride; dicyanamide, phenol novolak resin,
Examples include aniline formaldehyde resin, polyamide resin, etc., and these may be used alone or in combination of two or more.

As organic metal salts, zinc naphthenate, lead stearate, lead naphthenate, zinc octylate, tin oleate, tin octylate, dibutyltin malate, manganese naphthenate,
Examples include cobalt naphthenate, iron acetylacetone, manganese acetylacetone, and the like, and these may be used alone or in combination of two or more.

Organic peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, octanoyl peroxide,
Diacyl peroxides such as lauroyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,
Diallyl peroxides such as dicumyl peroxide; t-butyl perbenzoate, t-butyl peracetate, di-t-butyl perphthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, etc. Peroxy esters; Ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; di-t-butyl hydroperoxide,
Hydroperoxides such as cumene hydroperoxide, α-phenylethyl hydroperoxide, and cyclohexenyl hydroperoxide: 1,1-bis(
Examples include peroxyketals such as t-butylperoxy)cyclohexane and 1,1-bis(1-butylperoxy)-3,3,5-)limethylcyclohexane. A reasonable range of catalyst amounts is sufficient, for example up to 10% by weight, preferably up to 5% by weight, based on the amount of previous resin.

Components other than those mentioned above may be added to the curable resin composition of the present invention within a range that does not impair its properties.

These ingredients include thermosetting resins, thermoplastic resins, solvents, fillers, flame retardants, plasticizers,
Examples include photopolymerization initiators, polymerization inhibitors, coupling agents, pigments, and the like.

As the thermosetting resin, unsaturated polyester resin, diallyl phthalate resin, epoxy acrylate resin, urethane acrylate resin, etc. can be blended.

As the thermoplastic resin, aromatic or aliphatic petroleum resin, rosin resin, terpene resin, coumaron resin, xylene resin, ketone resin, etc. are blended.

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

As a coupling agent, general formula X5iYa (wherein, X
is a non-hydrolyzable organic group such as a vinyl group, methacryloxypropyl group, aminoalkyl group, mercaptoalkyl group, or epoxyalkyl group, and Y is a hydrolyzable organic group such as a halogen or alkoxy group). Silane coupling agents such as silane compounds such as γ-glycidoxypropyltrimethoxysilane and α-aminopropyltriethoxysilane, and titanium coupling agents in which Si in the above general formula is replaced with Ti can be used.

As the filler, silica powder such as fused silica and crystalline silica, and inorganic fillers such as alumina, magnesium oxide (magnesia), wollastonite, mica, calcium carbonate, and talc are suitably blended. These fillers can be used as they are in the form of powder, particles, flakes, or fibers, or can be used after surface treatment with the coupling agent.

As a flame retardant, known inorganic or organic flame retardants such as aluminum hydroxide, antimony oxide, perchloropentacyclodecane, tetrabromobisphenol A can be used.
1-pentabromophenol methacrylate, halogenated epoxy resin, etc. are used.

Examples of plasticizers include phthalic acid esters such as dibutyl phthalate and dioctyl phthalate; phosphoric acid esters such as tricresyl phosphate and diphenyloctyl phosphate; Basic acid esters and the like are used.

As a photopolymerization initiator, benzoin, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, 2,2-jethoxyacetophenone, 2,2
- Radical photopolymerization initiators such as dimethoxyphenylacetophenone and 2-ethylanthraquinone can be used.

As a polymerization inhibitor, 4,4'-thiobis(6-t-butyl-3-methylphenol), 3,5-di-t-butylhydroxytoluene, 2,2'-methylenebis(4-methyl-6-t-butylphenol) ), 4. Alkylphenols such as 4°-butylidenebis(6-t-butyl-3-cresol); phenyl-C-naphthylamine, N
, Allylamines such as N'-di-β-naphthyl-p-phenylenediamine; Catechols such as pt-butylcatechol; Hydroquinones such as hydroquinone and hydroquinone monomethyl ether; and the like.

The curable resin composition of the present invention comprises a copolymer of component A,
Component B thermosetting resin and/or vinyl monomer,
It is prepared by blending a curing accelerator, various additives, etc. with the liquid rubber of component C, if desired, and is prepared and used as a composition for paints, adhesives, casting, etc.

These curable resin compositions can be cured at room temperature, and can also be cured using various energies such as hot air, electric heat, infrared rays, far infrared rays, high frequency waves, and microwaves.

Further, the curable resin composition is dissolved in a suitable solvent,
An impregnating varnish is prepared. After impregnating or applying this varnish to a sheet-like base material and air-drying it as necessary,
A B-stage prepreg can be prepared by drying in air at a constant temperature of 50°C.

As a sheet-like base material, woven fabrics, non-woven fabrics made of various weavings of inorganic fibers such as quartz, glass, carbon, asbestos, and organic fibers such as polyester, polyacrylic, polyamide, etc.
Base materials such as mats, papers, and combinations of these are used. These base materials are preferably used after being subjected to surface treatment using a coupling agent in the same manner as the filler.

One or more sheets of this prepreg are used, and if necessary, metal foil such as electrolytic copper foil is layered, and the molding pressure is usually 3 to 100 kg/Crl and the temperature is 130 to 240.
By pressurizing and heating for a certain period of time to form the product under conditions of .degree. C., it is possible to produce a laminate for printed wiring boards that has excellent adhesion to metal foil, heat resistance, and dielectric properties.

Furthermore, a curable resin composition for molding can be prepared by heating and melting the curable resin composition, adding additives such as fillers and flame retardants as necessary, and sufficiently kneading the curable resin composition. .

The molding conditions for this resin composition for molding are usually molding pressure 0.
．． 1-1. OOOkg/cnr, preferably Ha 3-50
0 kg/crl, temperature 100-300°C, preferably 150-240°C, and molding time 30 seconds-30 hours.

(Left below) [Function] As described above, the curable resin composition of the present invention comprises a copolymer (component A) consisting of a conjugated diene polymer block and an N-substituted maleimide polymer block, and a thermosetting resin composition. It is characterized by containing a resin and/or a vinyl monomer (component B) and a liquid rubber (component C).

In the present invention, the copolymer of component A is essentially composed of nonpolar segments and polar segments. Therefore, by selecting the composition ratio of these segments, that is, the copolymerization ratio of the conjugated diene polymer block and the N-substituted maleimide polymer block, the composition of nonpolar polymers such as polybutadiene resin, epoxy resin, polyimide resin, etc. Because it is compatible with both polar polymers,
It acts as a compatibilizer between a nonpolar polymer and a polar polymer, which could not be made compatible in the past, and as a result, it becomes possible to prepare a new curable resin composition.

In addition, in the cured product of the curable resin composition having the above structure, a microphase separation structure is formed, and not only the toughness and heat resistance of the cured product are significantly improved, but also the original properties of the conjugated diene polymer. It also has excellent electrical properties, water resistance, moisture resistance, etc.

As a result, the curable resin composition of the present invention can be prepared as a resin composition for various uses such as casting, molding, lamination, impregnation, adhesion, and coating, and by curing them, A cured product with excellent mechanical strength, water resistance, moisture resistance, heat resistance, electrical properties, thermal shock resistance, etc. can be obtained.

〔Example〕

The present invention will be explained in more detail with reference to Examples and Comparative Examples. However, the scope of the present invention is not limited in any way by the following examples.

In addition, in the following examples, "parts" and "%" are based on weight unless otherwise specified.

Synthesis of copolymer> (a) Sample A-1 In a reaction vessel sealed with nitrogen, a sodium-kerosene dispersion containing 0.2 mol of sodium was added to tetrahydrofuran (
2,500 g of a solution dissolved in THF (hereinafter referred to as THF) was prepared, and the mixture was heated to -60°C in advance while being kept at -60°C and stirred.
1,500 g of a solution of 6.29 mol of butadiene and 1.34 mol of α-methylstyrene in THF cooled to A solution of a butadiene-based polymer having oxygen-sodium bonds at both ends of the chain was obtained.

A portion of this reaction solution was taken out of the system, treated with water, and then the solvent was distilled off under reduced pressure. Table 1 shows the properties of the butadiene-based polymer obtained.

Next, N-phenylmaleimide (hereinafter referred to as PMI) was added to the reaction system.
) A solution of 1°45 mole dissolved in THF 1500
g was added dropwise over 4 hours, and the mixture was maintained for an additional 1 hour. Then, a hydrochloric acid-methanol solution was added to stop the reaction. Then,
The reaction solution was poured into a large amount of methanol to precipitate a polymer, which was filtered and washed, and then dried at 60° C. for one day and night to obtain a yellow-white powdery copolymer (sample A-1). The polymerization yield was 99.0%.

The properties 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 group content per molecule 1°8
2. Pour 3300 g of a solution of 500 g of product name Nl5SOPBG-3000 (manufactured by Nippon Soda Co., Ltd.) in THF, maintain the temperature at 0°C, and add n-butyllithium 0.
．． 29 mol (OH/Li (molar ratio) 1.0) was added dropwise to obtain a solution of a butadiene-based polymer having oxygen-lithium bonds at both ends of the molecular chain.

Next, the reaction system of this polymer solution was maintained at -60°C,
While stirring, add 0-methylphenylmaleimide 2.67
3,300 g of a solution in THF was added dropwise over 4 hours, and after holding for another 1 hour, the reaction was stopped and post-treated in the same manner as in Sample A-1, resulting in a yellow-white powdery copolymer, Sample A. -2) was obtained.

The polymerization yield was 99.5%.

The properties of sample A-2 are shown in Table 1.

(c) Sample A-3 A commercially available hydroxyl group-containing 1.4-
Polybutadiene (number average molecular weight 2800.1.4-bond content 80%, hydroxyl group content per molecule 2.35,
Product name poly-BOR-45HT, Idemitsu Arco Co., Ltd.
2000 g of a solution prepared by dissolving 300 g of n-butyl lithium in THF were charged, and the mixture was kept at 0°C and stirred to dissolve 0.0.
251 mol (OH/Li (mole ratio).1.0) was added dropwise to obtain a solution of a butadiene-based polymer having oxygen-lithium bonds at both ends of the molecular chain and in the molecule.

Next, the reaction system of this polymer solution was maintained at -60°C,
While stirring, 2000 g of a solution of 1.73 moles of PMI dissolved in THF was added dropwise over 4 hours, and after holding for another 1 hour, the reaction was stopped and post-treated in the same manner as in Sample A-1, resulting in a yellowish white powder. A copolymer (sample A-3) was obtained. The polymerization yield was 98.8N.

The properties of sample A-3 are shown in Table 1.

(d) Sample A-4 0.2 n-butyllithium was added to a reaction vessel sealed with nitrogen.
Prepare 3300 g of THF solution containing 5 mol and heat at -40°C.
While stirring, 9.26 mol of butadiene was introduced over 4 hours and maintained for 1 hour.
．． A solution of a butadiene-based polymer having an oxygen-lithium bond at one end of the molecular chain was obtained.

A portion of this reaction solution was taken out of the system, treated with water, and then the solvent was removed under reduced pressure. Table 1 shows the properties of the butadiene polymer obtained.

Next, the reaction system of this polymer solution was maintained at -60°C, and while stirring, 830 g of a solution of 72 mol of PMI O dissolved in THF was added dropwise over 4 hours, and after an additional 1 hour, hydrochloric acid was added. - The reaction was stopped by adding methanol solution. Next, water was added to the reaction solution to separate the layers, and the solvent was distilled off from the upper polymer solution under reduced pressure to obtain a brown elastomer-like copolymer (sample A-4). The polymerization yield was 98.
It was 7X.

The properties of sample A-4 are shown in Table 1.

Examples 1 to 6, Comparative Examples 1 to 4, Monocuring resin composition (for impregnation varnish) (al Preparation of impregnation varnish (W-1 to W-6, Comparative CW-1 to CW-4) Component A ; Copolymers synthesized above (samples A-1 to A-3
) Component B: The following thermosetting resin EPL: Cresol novolak type epoxy resin (product name YDCN-701, manufactured by Tobu Kasei ■) EP2: Bisphenol A type epoxy resin (product name YD-128, manufactured by Tobu Kasei ■) TE Niacrylic modified 1.2-Polybutadiene resin (product name Nl5SOTE-2000, manufactured by Nippon Soda) BTI: Bismaleimide triazine resin (product name BT
-2170. Mitsubishi Gas Chemical (Structure) M2O: Polyphenylene methylene bismaleimide (trade name Bismaleimide M
-20, manufactured by Mitsui Toatsu Chemical ■) Component C: The following liquid rubber LRL: 1,4-polybutadiene (trade name polyBD
.

R-45HT, manufactured by Idemitsu Arco ■) LR2: Polyisoprene (product name: Claprene LTR-3
0, ■Kuraray) The above components A, B, and C are appropriately blended, and if necessary, dicumyl peroxide (D) is added as a curing accelerator.
CP) or 2-undecylimidazole (epoxy curing agent, brand name C,,l, Shikoku Fine Chemicals (
Impregnated varnish with a resin content of 50% by adding 2υI) and dissolving it in methyl ethyl ketone: Samples W-1 to W-6
was prepared.

In addition, as a comparative sample, the component B, or B and C
The curing accelerator was blended into a composition consisting of the following, and dissolved in methyl ethyl ketone to prepare an impregnated varnish with a resin content of 50% (comparative samples CW-1 to CW-4). Table 2 shows the composition of each sample prepared.

(b) Preparation and evaluation of laminates Impregnated varnish samples W-1 to W-6 prepared in section (a) above
and comparative samples CW-1 to CW-4 were impregnated into a glass fiber woven fabric with a thickness of 0.2 mm, and dried by heating.
- Prepreg for the stage was produced.

8 sheets of the obtained prepreg were stacked, and both sides were coated with a thickness of 35 mm.
Layer μm electrolytic copper foil at 18・0℃×50kg/crl
Pressure molded for 120 minutes, then further molded at 200℃ for 2
Curing was performed for 4 hours to produce a copper-clad laminate.

The following characteristics were measured for the copper-clad laminate produced above.

■ Dielectric constant (ε) and dielectric loss tangent (tanδ): IMH
z, measured at 25℃■ Copper foil adhesion (σ,) kg/car■ Soldering heat resistance: Processed in a solder bath at 300℃ for 120 seconds O: No abnormality ×: Blistering ■ Water absorption rate: 2 in boiling water Time retention (%) The measurement results are shown in Table 2.

As shown in Table 2, the laminate using the impregnated varnish made of the curable resin composition of the present invention not only has a low dielectric constant, but also has excellent copper foil adhesion, soldering heat resistance, and water resistance. Each characteristic is well balanced.

Example 7 Monocurable resin composition (for molding material) - copolymer synthesized above as component A (sample A-2) 5
0 parts, bismaleimide M-20 (supra) as component B 5
0 parts, 20 parts of liquid rubber LR-1 (mentioned above) as component C, and 1 part of DCP (mentioned above) as a curing accelerator, and further 250 parts of crystalline silica powder surface-treated with a silane coupling agent. After adding and kneading at a temperature of 100 to 110° C., the mixture was cooled and crushed to prepare a granular curable resin composition: Sample G-1.

The prepared sample G-1 was heated at 170°C
Compression molding was carried out under the conditions of 1 x 3 minutes, and the molded product was further heated to 230°C.
It was kept for 1 hour to harden.

The obtained molded article had the following characteristics.

Bending strength: 13.5kg/kaku! (20℃) Bending strength: 9.3kg/mm' (2000C
)Izotsu impact strength: 78kg/mm' (20℃)
Dielectric constant (ε): 3.5 (IMH2,206C) absorption
Water rate: 0.1% (kept in boiling water for 2 hours) Loss on heating
: 0.1% (held at 180°C for 24 hours) Example 8 Single-curing resin composition (for casting resin) - 40 parts of the copolymer (sample A4) synthesized previously as component A, epoxy as component B Resin YD-128 (mentioned above) 50
As component C, 10 parts of 1,4-polybutadiene LR-1 (mentioned above) were heated to 100°C and mixed to form a homogeneous solution, then allowed to cool to room temperature, and 4-methyl hexahydro was added as a curing accelerator. 40 parts of phthalic anhydride and 1 part of DCP (described above) were added to obtain a light brown transparent liquid curable resin composition T-1.

The prepared curable resin composition for casting T-1 was cured at 100°C for 3 hours and further at 150°C for 8 hours.

The obtained cured product had the following characteristics.

Bending strength: 10.5 kg/mm"
(20°C) Izot impact strength: 35 kg/c
m” (20°C) Dielectric constant (ε): 2.7
(IM) Iz, 20°C) Water absorption rate; 0.1
% (Kept in boiling water for 2 hours) Curing shrinkage rate (Vs):
2.0% Vs・(Solid specific gravity - Liquid specific gravity)/Solid specific gravity x 100 Shear adhesive strength (Ss): 158 kg/cm" (
208C) Compliant with JIS K 6850. Measurement of tensile shear adhesive strength between steel plates at 25°C.

Thermal shock resistance (HC): 1 at 120°C to -50°C
0 cycles or more After embedding a spring washer with an outer diameter of 40 mmΦ using 30 g of test resin in a 100 m poly cup and curing it by heating, heat at 120°C for 1 hour → -
One cycle was 50°C for 1 hour, and the test was repeated until cracks appeared.

〔Effect of the invention〕

The curable resin composition of the present invention contains a copolymer composed of a conjugated diene polymer block and an N-substituted maleimide polymer block, a thermosetting resin and/or a vinyl monomer, and a liquid rubber. It is characterized by

As shown in the examples above, the curable resin composition of the present invention has a high glass transition point, a low curing shrinkage rate during curing, and the cured product has good mechanical strength, water resistance, heat resistance, and heat resistance. It not only has excellent impact resistance, but also extremely excellent dielectric properties such as dielectric constant and dielectric loss tangent.

Therefore, it can be used in a wide range of applications such as casting materials, molding materials, sealing materials, impregnated varnishes for laminates, coil impregnated varnishes, paints, and adhesives.

In particular, prepreg using impregnated varnish, which is one aspect of the present invention, is non-adhesive and extremely easy to handle, and laminates manufactured using it have excellent adhesion to metal foil and excellent dielectric properties. Because it has heat resistance and water resistance,
It is extremely useful as a substrate material for printed wiring boards such as high-frequency circuits that require a low dielectric constant.

The present invention combines the characteristics of thermosetting resins that have been widely used in various fields and the characteristics of conjugated diene polymers,
Furthermore, the present invention provides a curable resin composition that also has toughness, and its significance in industry including the electronic and electrical fields is extremely large.

Claims (2)

[Claims] (1) A curable resin composition comprising the following components A, B and C. Component A: The following general formula (I)
It represents a substituted maleimide polymer block, and n is a positive number from 1 to 5. ), and the weight ratio of X and Y is 20/80
≦X/Y≦90/10, number average molecular weight is 500 to 100
,000 copolymer component B: thermosetting resin and/or
or vinyl monomer component C: liquid rubber (2) The curable resin composition according to claim (1), wherein the thermosetting resin of component B is at least one selected from the group consisting of epoxy resins, polybutadiene resins, maleimide compounds, and cyanate esters. thing.