JPS61233060A - Curable resin composition - Google Patents

Abstract

PURPOSE:To provide the titled composition having excellent workability, heat- resistance, adhesivity, electrical characteristics, etc., and suitable for a molded article for printed circuit board having low dielectric constant and low loss tangent, by compounding a cyanate resin composition with a specific copolymer of butadiene and an aromatic vinyl compound. CONSTITUTION:The objective composition can be produced by compounding (A) a resin composition composed of a polyfynctional cyanic acid ester having >=2 cyanato groups in one molecule and represented by the formula R(OCN)m(m is 2-5; R is aromatic organic group) and/or its prepolymer and/or a prepolymer of the cyanic acid ester and an amine, and if necessary, other thermosetting resin with (B) a copolymer having a melting point of >=10 deg.C and obtained by (1) copolymerizing butadiene and an aromatic vinyl compound to obtain a copolymer wherein >=50% of the butadiene unit constituting the polymer chain is 1,2-bond butadine and (2) introducing >=0.5 one or more kinds of functional groups such as hydroxyl group, carboxyl group, etc., per one molecule on an average. The ratio of A/B is 95/5-40/60.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a novel curable resin composition that provides a cured product with excellent workability and excellent heat resistance, adhesiveness, electrical properties, etc. In particular, by taking advantage of its excellent dielectric properties, it is suitably used in the production of printed wiring molded bodies and structural laminates with low dielectric constants, #, and dielectric loss tangents.

[Conventional methods and their problems]

Conventionally, the [A] component of the present invention, polyfunctional cyanate esters alone (al or this and other thermosetting resins (b)
) has excellent workability, heat resistance, and adhesion, but has a low dielectric constant,
It was still insufficient when used for low dielectric loss tangent applications. On the other hand, 1,2-polybutadiene resin provides a cured product with excellent low dielectric constant and low dielectric loss tangent, but is insufficient in adhesion and workability.

As an improvement method, polyfunctional cyanate esters and 1,
Compositions with 2-polybutadiene resins are known (
JP-A-54-142300, JP-A-55-98244
If a liquid with a normal molecular weight i, ooo to 5,000 is used as 1,2-polybutadiene, the composition will be sticky, so non-stick properties should be maintained. There was a problem in that it could not be used for the required applications such as prepregs, pellets for molding, and powder coatings. As an improvement to this, there is a method of using a compound with a molecular weight of about 100,000, and although this method eliminates the stickiness, it has poor compatibility with cyanate esters and poor solubility in general-purpose solvents. In addition to poor workability, these methods also have the disadvantage of poor adhesiveness. Furthermore, 1
．． A method in which an acid anhydride group is introduced by adding maleic anhydride to 2-polybutadiene at its double bond (
JP-A No. 57-143350), and this method shows good physical properties in terms of adhesiveness, heat resistance, etc.
Similar to the above, it exhibited tackiness.

[Means for solving problems]

The present inventors have conducted intensive studies on methods for obtaining resin compositions that can be used to produce non-tacky prepregs, powders, and molding pellets that have greatly improved the workability of the conventional methods as described above. As, by using a specific copolymer of butadiene and vinyl aromatic compound,
We have discovered a new curable resin composition that provides a cured product with excellent workability and excellent heat resistance, adhesiveness, electrical properties, etc., and completed the present invention.

That is, the present invention comprises a polyfunctional cyanate ester having two or more cyanato groups in the molecule, the cyanate ester prepolymer, or a prepolymer of the cyanate ester and an amine (a) as an essential component, and optionally 50% or more of the butadiene units constituting the polymer chain formed by the polymerization of cyanate ester resin composition [A] and other thermosetting resins (011) and butadiene and a vinyl aromatic compound .2-In the copolymer that is a bond, a hydroxyl group,
Obtained by introducing at least 0.5 functional groups per molecule on average from the group consisting of carboxyl groups, acid anhydride groups, epoxy groups, mercapto groups, and amino groups, and having a melting point of 10 It is a curable resin composition consisting of a copolymer (B) having a temperature of at least .degree.

The present invention will be explained below.

The cyanate ester resin composition [A] of the present invention is composed of a polyfunctional cyanate ester represented by the following general formula (1), its prepolymer, etc. as essential components, and contains cyanato resin (Japanese Patent Publication No. No. 1928, No. 45-11712, No. 44-1222, German Patent No. 1190184, etc.), cyanate ester-maleimide resin, cyanate ester-maleimide-epoxy resin (Japanese Patent Publication No. 54-30
No. 440, etc., Special Publication No. 52-31279, USP-41
10364, etc.) and cyanate ester-epoxy resin (Japanese Patent Publication No. 46-41112).

Here, a suitable polyfunctional cyanate ester has the following general formula (1): % formula % (1) (m in the formula is an integer of 2 or more and usually 5 or less, and R is an aromatic The cyanato group is an organic group, and the cyanato group is bonded to an aromatic ring of the organic group. To give a concrete example, 1゜3-
or 1.4-dicyanatobenzene, 1.3.5-1-licyanatobenzene, L3-. 1.4-. 1.6-. 1.
8-. 2.6- or 2゜7-dicyanatonaphthalene, 1
, 3.6-dicyanatonaphthalene, 4.4°-dicyanatobiphenyl, bis(4-cyanatophenyl)methane, 2.2-bis(4-cyanatophenyl)propane, 2
．． 2-bis(3,5-dichloro-4-cyanatophenyl)propane, 2,2-bis(3t5-cyanatophenyl)propane, bis(4-cyanatophenyl)ether, bis( 4-cyanatophenyl) thioether, bis(4-cyanatophenyl) sulfone,
Tris(4-cyanatophenyl) phosphite, tris(4-cyanatophenyl) phosphate, and terminal O
Cyanic acid ester (USP-
4026913), cyanic acid ester obtained by the reaction of novolak and cyanogen halide (5P-40
22755, USP-344807). In addition to these, Tokuko Sho 41-1928, Sho 43-1846
8, 44-4791, 45-11712, 46
-41112, 41-26853, JP-A-51-63
149, USP-3553244, USP-37554
02, USP-3740348, ELSP-35959
00, USP-3694410 and USP-41169
Cyanic acid esters described in 46 etc. can also be used.

In addition, a prepolymer obtained by polymerizing the above-mentioned polyfunctional cyanate ester in the presence or absence of a mineral acid, a Lewis acid, a salt such as sodium carbonate or lithium chloride, a phosphate ester such as tributylphosphine, etc. used as. These prepolymers generally have a 5yll-triazine ring in the molecule, which is formed by trimerization of the cyanide groups in the cyanate ester.

Furthermore, the polyfunctional cyanate esters described above can also be used in the form of prepolymers with amines. Examples of amines that can be suitably used include meta- or para-phenylenediamine;
meta- or para-xylylene diamine, 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, bis(
4-amino-3-chlorophenyl)methane, 2.2-bis(4-amino-3,5-dibromophenyl)propane, bis(4-aminophenyl)phenylmethane, 3.4
-diaminophenyl-4-aminophenylmethane, 1.
1-bis(4-aminophenyl)-1-phenylethane and the like.

The above-mentioned polyfunctional cyanate esters, their prepolymers, and prepolymers with amines can be used alone or in the form of mixtures, and the number average molecular weight of the individual and mixtures is usually 300 to 6,000, preferably 1,500. Below, the range of 300 to 1,000 is particularly preferable.

Cyanate ester-maleimide resin (Special Publication No. 54-30
440, etc.), cyanate ester-maleimide-epoxy resin (Japanese Patent Publication No. 52-31279, etc.) and cyanate ester-epoxy resin (Japanese Patent Publication No. 46-41112)
Maleimide, which is a component of the cyanate ester resin composition represented by the following, is a compound represented by the following general formula (2), or a prepolymer thereof.

(In the formula, Rt is an aromatic or alicyclic organic group with a valence of 2 or more and usually 5 or less, X I, X z are hydrogen, halogen,
or an alkyl group, and n is usually an integer of 2 to 5. ) Maleimides represented by the above formula are produced by a method known per se in which maleic anhydride and polyamines containing 2 to 5 amino groups are reacted to prepare maleamic acid, and then maleamic acid is cyclized by dehydration. can do. The polyamines used are preferably aromatic polyamines in terms of the heat resistance of the final resin, but if flexibility and flexibility of the resin are desired, alicyclic amines may be used alone or in combination. good. Further, it is desirable that the polyamines be primary amines from the viewpoint of reactivity, but secondary amines can also be used. Suitable amines include those exemplified as those used as prepolymers with cyanate esters, and melamines having an s-) lyazine ring;
These are polyamines made by reacting aniline with formalin and linking benzene rings with methylene bonds.

In addition, any epoxy resin that has been conventionally used for laminates can be used.
Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, Talesol novolac type epoxy resin, halogenated bisphenol A type epoxy resin, halogenated phenol novolac type epoxy resin, polyglycol type epoxy resin. These include resins, alicyclic epoxy resins, etc., and these can be used alone or as a mixture of two or more.

Next, the copolymer (B) of the present invention is obtained by polymerizing butadiene and a vinyl aromatic compound and introducing a functional group, and usually the butadiene and vinyl aromatic compound are mixed in a weight of 80: 20-10:90, preferably 70:30
~20: Polymerize as 80 to obtain a block or random copolymer in which 50% or more, preferably 85% or more of the butadiene units constituting the polymer chain are 1,2-bonds, and then the copolymer is The reaction solution is treated with a functional group-introducing reagent either as it is or after the reaction has been stopped,
Introducing on average 0.5 or more functional groups per molecule, preferably 1 to 4 functional groups selected from the group consisting of hydroxyl group, carboxyl group, acid anhydride group, epoxy group, mercapto group, and amino group. The melting point is 10°C or higher, preferably 20°C or higher.

Here, as the aromatic vinyl compound, styrene, α-
Methylstyrene, vinyltoluene, chlorostyrene, P
-Ethylstyrene, P-methoxystyrene, divinylbenzene, etc. are exemplified.

The copolymer can be polymerized by anionic polymerization using a hydrocarbon nonpolar solvent at a temperature of θ to 70°C using an alkali metal as a catalyst. % or more,
This method may be used, but in the use of the present invention, a Lewis base such as tetrahydrofuran is used in the presence or absence of a polycyclic or polynuclear aromatic hydrocarbon activator such as naphthalene, anthracene, biphenyl, or 1,2-diphenylbenzene. According to a method in which butadiene and a vinyl aromatic compound are simultaneously or sequentially added to a system obtained by dispersing a type compound and an alkali metal such as sodium or lithium at a temperature of -20°C or lower to carry out anionic living polymerization. , the amount of 1,2-bonds in the butadiene unit is 80
% or more, and 85 to 95% depending on conditions is easy and preferable, and furthermore, this method is preferable because it makes it easy to adjust the molecular weight.

Functional groups can be introduced at both ends of the polymer chain by treating the polymerization reaction solution obtained by this method with reagents such as carbon dioxide ffi, ethylene oxide, ethylene sulfide, and ethyleneimine, followed by treatment with water and methanol. A butadiene-vinyl aromatic compound copolymer having functional groups such as carboxyl, hydroxyl, mercapto, and amino groups can be obtained, and if the polymerization reaction solution is immediately treated with epichlorohydrin, epoxy groups are added to both ends of the polymer chain. A butadiene-vinyl aromatic compound copolymer having the following formula is obtained.

In addition, if the polymerization reaction solution obtained by the above method is immediately treated with water and methanol, a butadiene-vinyl aromatic compound copolymer having no functional groups can be obtained. Maleic anhydride, methyl maleic anhydride, etc.
By heating and mixing with an α/β-dicarboxy compound at 140 to 230°C, a butadiene-vinyl aromatic compound copolymer with an acid anhydride group introduced into a part of the polymer chain can be obtained. If a butadiene-vinyl aromatic compound copolymer with or without a functional group at the end of the chain is treated with air or oxygen at 100-150°C in the presence of a catalyst and a solvent, carboxyl groups will be formed in some of the polymer chains. A butadiene-vinyl aromatic compound copolymer into which a group or a hydroxyl group has been introduced is obtained, and a butadiene-vinyl aromatic compound copolymer having no functional group is treated with peracetic acid and perpropion in the presence of a solvent at 40 to 100°C. By treating with an organic peracid such as an acid, a butadiene-vinyl aromatic compound copolymer in which epoxy groups are introduced into some of the double bonds of butadiene in the polymer chain can be obtained.

If the amount of butadiene component in the copolymer (B) of the present invention prepared by the above method exceeds 80% by weight, the compatibility with the cyanate ester resin composition of component [A] will deteriorate, so it is preferable. On the other hand, if it is less than 10% by weight, the heat resistance of the cured product will deteriorate, which is undesirable, and if the 1,2-bond unit in the butadiene unit is less than 50%, the heat resistance of the cured product will deteriorate, which is undesirable. . Furthermore, the number average molecular weight of the copolymer (Bl) is preferably 500 to 10,000, and the melting point is 10°C or higher, preferably 20°C or higher. If the melting point is lower than 10°C, the composition becomes sticky. In addition, the functional groups are particularly preferably hydroxyl groups, carboxyl groups, and epoxy groups, and depending on the number average molecular weight, usually 0.5 or more per molecule, preferably [A
] The number is preferably in the range of 1 to 4 in consideration of the compatibility of the component with the component (B), electrical properties, etc.

The curable resin composition of the present invention is prepared by mixing or preliminarily reacting the above cyanate ester resin composition [A] with a specific butadiene-vinyl aromatic compound copolymer (B).

Preparation methods include mixing under heating without a solvent; heating preliminary reaction without a solvent; mixing as a solution of a solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, etc.; Either a method of pre-reacting by mixing as a solution of the solvent or a method of mixing a pre-reacted solution of the solvent is possible.

The composition ratio of components [A] and (B) is not particularly limited, but is usually 9515 to 40/60, especially 90/10.
A range of 50,150 to 50,150 is preferable.

The novel curable resin composition of the present invention consists of the above two components as essential components, but in addition to these components [A
] Known resins, additives, and reinforcing materials for modification can be added.

These include the viscous behavior of the composition, adhesion, curability,
Resins for the purpose of improving flexibility, such as thermosetting resins such as polyester resins, phenol resins, acrylic resins, and urethane resins; polybutadiene and butadiene.
Liquid to elastic rubbers such as acrylonitrile copolymer, polychloroprene, butadiene-styrene copolymer, polyisoprene, butyl rubber, natural rubber, etc., and their low molecular weight products with a molecular weight of several thousand or less; thermoplastic polyurethane resin, vinyl acetate Resins and other thermoplastic resins with reactive groups and their low molecular weight products with a molecular weight of several thousand or less; Engineering plastics with a molecular weight of several thousand or less such as polycarbonate, thermoplastic polyester, polyester carbonate, polyarylate, polyphenylene ether, etc. Molecular weight oligomer; polyethylene,
Low molecular weight oligomers of polyolefins such as polypropylene and 4-methylpentene-1 with a molecular weight of several thousand or less;
Resins such as low molecular weight oligomers with a molecular weight of several thousand or less of fluororesins such as polytetrafluoroethylene, polytetrafluoroethylene-propylene copolymer, perfluoroethylene propylene copolymer; Inorganic fillers - e.g. low dielectric For applications with low dielectric loss tangent, silica powder such as fused silica and crystalline silica, boron nitride powder, boron silicate powder, etc. For applications with high thermal conductivity, in addition to the above, alumina, oxidized Inorganic fillers such as magnesium (magnesia), wollastonite, mica, calcium carbonate, and talc are suitable for other purposes. These inorganic fillers may be used as they are or may be surface-treated with a silane cuff pulling agent, a titanate coupling agent, etc., and are used as particles or fibrous fillers.

In addition, cloth-like reinforcing base materials in various shapes such as roving, chopped strand mat, continuous mat, cloth, roving cloth, surfacing mat, and chopped strand mat are also suitable for use in laminated products, etc. , glass fibers, carbon fibers, wholly aromatic polyamide fibers, and mixed fabrics thereof.

Furthermore, it is a preferable embodiment to improve the processability, flexibility, etc. of the molded article by replacing some of the above-mentioned inorganic fillers with organic fillers. are polycarbonate, thermoplastic polyester, polyester carbonate, polyarylate,
High molecular weight powder of engineering plastics such as polyphenylene ether; High molecular weight powder of polyolefin such as polyethylene, polypropylene, poly-4-methyl-1-pentene; polytetrafluoroethylene, polytetrafluoroethylene-propylene copolymer Union,
Examples include powder of fluororesin such as perfluoroethylene propylene copolymer.

Although the curable resin composition of the present invention is curable as it is, the cyanate ester resin composition described above is used for the purpose of accelerating the curing reaction such as the crosslinking reaction between the [A] component and the [B] component. A known curing agent or curing catalyst is used.

Examples of these include amines, imidazoles, organic metal salts, inorganic metal salts, and organic peroxides.

Among these catalysts, organic metal salts alone and combination systems of organic metal salts and organic peroxides are suitable. Examples of organic metal salts include zinc naphthenate, lead stearate, lead naphthenate, zinc octylate, and oleic acid. These include tin acid, tin octylate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetone, manganese acetylacetone, etc., and organic peroxides include benzoyl peroxide, 2
．． Diacyl peroxides such as 4-dichlorobenzoyl peroxide, octanoyl peroxide, and lauroyl peroxide; di-t-butyl peroxide; 2.
Dialkyl peroxides such as 5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 and dicumyl peroxide; tart-butyl perbenzoate, t-butyl peracetate, di-t-butyl perphthalate , 2,5-dimethyl-2,5-di(benzoylperoxy)hexane and other peroxyesters; methyl ethyl ketone peroxide, cyclohexanone peroxide and other ketone peroxides; di-t-
Hydroperoxides such as butyl hydroperoxide, cumene hydroperoxide, α-phenylethyl hydroperoxide, cyclohexenyl hydroperoxide; 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis( Examples include peroxyketals such as 1-butylperoxy)-3,3,5-)limethylcyclohexane and sane, and the amount of these curing catalysts to be used is sufficient within the general catalyst amount range. For example, 10% by weight or less based on the total resin composition,
In particular, it is used in amounts of up to 5% by weight.

The curing conditions for the curable resin composition of the present invention by the above method are usually a molding pressure of 3 to 100 kg/cIA and a temperature of 1.
By heating and pressurizing at 60 to 240°C to form.

Here, the molding time is selected in the range of 30 seconds to 30 hours, and in the case of a relatively short time in the range of 30 seconds to 100 minutes or when low temperature is used, the molding time is selected in the oven after taking out from the molding machine. It is preferable to obtain a sufficiently cured molded product by post-curing the molded product.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Reference Examples, Examples, and Comparative Examples. Note that parts and percentages in the examples are based on weight unless otherwise specified. Reference Example-1 50 parts of butadiene was added to a system in which a sodium dispersion was added to tetrahydrofuran in which 1,2-diphenylbenzene was dissolved at -60°C. was added, and then 50 parts of α-methylstyrene was added, and the resulting polymerization reaction solution was treated with epichlorohydrin to obtain a number average molecular weight of 2,100, 49.8% of butadiene units, and 50.2 α-methylstyrene units.
%, 1.2-bond in butadiene unit 9065%, 1,
4-bond 9.5%, epoxy equivalent 1250, melting point 6
A butadiene-α/methylstyrene block copolymer at 2° C. was obtained.

Reference Example 2 Butadiene 4 was added to a system in which a sodium dispersion was added to tetrahydrofuran in which naphthalene was dissolved at -60°C.
A polymerization reaction solution produced by adding a mixture of 0 parts and 60 parts of styrene was treated with ethylene oxide, and then hydrolyzed.
Number average molecular weight 2,520, butadiene unit 39.8%,
60.2% styrene units, 1.2- in butadiene units
Bond 91.3%, 1,4-bond 8.7%, hydroxyl value 4
0.1, a butadiene-styrene random copolymer having a melting point of 66°C was obtained.

Reference Example 3 Butadiene 4 was added to a system in which a sodium dispersion was added to tetrahydrofuran in which biphenyl was dissolved at -60°C.
After adding 0 part of α-methylstyrene and then adding 60 parts of α-methylstyrene, the resulting polymerization reaction solution was treated with propylene oxide and then hydrolyzed to obtain a polymer with a number average molecular weight of 3.480, a butadiene unit of 39.1%, and α-methylstyrene. - 60.9% methylstyrene units,
1,2-bond in butadiene unit 89.4%, 1,4-
A butadiene-α/methylstyrene block copolymer having a bond of 10.6%, a hydroxyl value of 28.9, and a melting point of 75°C was obtained.

Reference Example-4 A mixture of 30 parts of butadiene and 70 parts of styrene was added to a system in which 1,2-diphenylbenzene was dissolved in tetrahydrofuran and a sodium dispersion was added at -60°C. After treatment with carbon,
Hydrolyzed, number average molecular weight 2,880, butadiene unit 29.7%, styrene unit 70.3%, 1.2-bond in butadiene unit 91°5%, ■, 4-bond 8.5
%, an acid value of 35.1, and a melting point of 78° C., a butadiene-styrene random copolymer was obtained.

Reference Example-5 Polymerization produced by adding 50 parts of butadiene and then 50 parts of α-methylstyrene at -60°C to a system in which a sodium dispersion was added to tetrahydrofuran in which 1,2-diphenylbenzene was dissolved. The reaction solution was hydrolyzed to give a number average molecular weight of 1.980 and butadiene units of 49.
4%, α-methylstyrene units 50.6%, 1,2-bonds in butadiene units 90°0%, 1,4-bonds 10.
0%, butadiene-α, which has no functional groups and has a melting point of 61°C.
A methylstyrene block copolymer was obtained.

Next, 5 parts of maleic anhydride, 0.1 part of di-t-amylhydroquinone, and 1 part of xylene were added to 100 parts of this copolymer, and heat-treated at 190°C for 8 hours in a nitrogen atmosphere to remove all the acid. A maleated butadiene-α/methylstyrene block copolymer having a acid value of 53.7 and a half acid value of 28.5 was obtained.

Reference Example 6 At 40"C, 50 parts of butadiene was added to a system in which n-butyllithium was dissolved in a mixed solvent consisting of 99.5% methylcyclohexane and 0.5% tetrahydrofuran, and then 50 parts of styrene was added. The polymerization reaction solution produced was treated with epichlorohydrin to give a number average molecular weight of 2,
280, butadiene unit 48.8%, styrene unit 51
．． 2%, 1.2-bond in the butadiene unit 31.3%,
A butadiene-styrene block copolymer having a 1.4-bond of 68.7%, an epoxy equivalent of 2,850, and a melting point of 56°C was obtained.

Example-1 2,2-Hifu! , 20 parts of the butadiene-α/methylstyrene block copolymer prepared in Reference Example-1 was added to 80 parts of the prepolymer pre-reacted at 160°C for 240 minutes, and methyl ethyl ketone (hereinafter referred to as , MEK) at a concentration of 50
% solution.

To this solution, 0.05 part of zinc octylate and 1 part of zinc octylate were added as a catalyst.
．． One part of 1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane was mixed, impregnated into a 0.2-thick glass woven fabric, and dried by heating to obtain a B-stage prepreg.

8 sheets of this prepreg were stacked and electrolytic copper foil with a thickness of 35 tna was layered on both sides.
Lamination molding was carried out for 20 minutes to obtain a copper-clad laminate.

The properties of this copper-clad laminate are shown in Table 1.

Comparative Example-1 Butadiene prepared in Reference Example-1 in Example-1
A copper-clad laminate was obtained in the same manner except that the α-methylstyrene block copolymer was not used.

The properties of this copper-clad laminate are shown in Table 1.

Comparative Example-2 100 parts of the butadiene-α/methylstyrene block copolymer prepared in Reference Example-1 was dissolved in MEK to a concentration of 50
% solution.

1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane was added to this solution as a catalyst.
The mixture was mixed and impregnated into a glass woven fabric having a thickness of 0.2 mm, and then heated and dried to obtain a B-stage prepreg.

This prepreg was used in the same manner as in Example 1 to obtain a copper-clad laminate.

The properties of this copper-clad laminate are shown in Table 1.

Comparative Example-3 Contains the epoxy group prepared in Reference Example-6 instead of the butadiene-α/methylstyrene block copolymer prepared in Reference Example-1, and the 1,2-bond in the butadiene unit is 3
The same procedure as Example 1 was carried out except that 1.3% of the copolymer was used.

The properties of the obtained laminate are shown in Table 1.

Comparative Example-4 Instead of the butadiene-α/methylstyrene block copolymer prepared in Reference Example-1, O was used as a liquid terminal functional group.
α, ω-1,2-polybutadiene glycol having FI group (Hissue Tadatatsu ■, trade name: Nl5SO-PR-G-
3000) was used, but the same method as in Example 1 was tried.

However, since the MEK solution became cloudy, it was necessary to impregnate the glass fabric while stirring the solution, and the resulting prepreg was sticky and could not be converted into a B-stage, making it suitable for lamination molding. It was unsuitable for use.

Example-2 72 parts of 2,2-his(4-cyanatophenyl)propane and 8 parts of bis(4-maleimidophenyl)methane were mixed into 1
20 parts of the butadiene-styrene random copolymer prepared in Reference Example-2 was added to 80 parts of the prepolymer pre-reacted at 50°C for 240 minutes, and dissolved in acetone to give a concentration of 50
% solution.

To this solution, 0.05 part of zinc octylate, 2
．． 5-dimethyl-2,5-di(t-butylperoxy)
31 parts of hexene was mixed, impregnated into a glass woven fabric with a thickness of 0.2 Ill, and heated and dried to obtain a B-stage prepreg.

This prepreg was used in the same manner as in Example-1 to obtain a copper-clad laminate.

The properties of this copper-clad laminate are shown in Table 1.

Comparative Example-5 A copper-clad laminate was obtained in the same manner as in Example-2 except that the butadiene-styrene random copolymer prepared in Reference Example-2 was not used.

The properties of this copper-clad laminate are shown in Table 1.

Comparative Example-6 Instead of the butadiene-styrene random copolymer prepared in Reference Example-2, the butadiene-α/methylstyrene block copolymer prepared in Reference Example-5 and having no functional group before maleation was used. An attempt was made to prepare a face in the same manner as in Example-2 except that acetone 50%
When it was made into a solution, it became cloudy. Therefore, a prepreg was prepared by impregnating a glass woven fabric with the solution while stirring, and the other procedures were the same as in Example-2.

The properties of the obtained laminate are shown in Table 1.

Comparative Example 7 A copolymer containing the epoxy group prepared in Reference Example 6 instead of the butadiene-styrene random copolymer prepared in Reference Example 2, with 31.3% of 1.2-bonds in the butadiene. The same procedure as Example 2 was carried out except that the combination was used.

The properties of the obtained laminate are shown in Table 1.

Example-3 Prepolymer 60 prepared by pre-reacting 36 parts of 2,2-bis(4-cyanatophenyl)propane and 24 parts of bis(4-maleimidophenyl)methane at 140°C for 240 minutes.
1 part, 40 parts of the butadiene-α/methylstyrene block copolymer prepared in Reference Example 3, and a novolac type epoxy resin (manufactured by Dow Chemical, trade name, DEN-43).
8) Add 2 parts and dissolve in MEK to make a 50% solution.

A copper-clad laminate was obtained in the same manner as in Example-1 except that a mixture of 0.03 parts of zinc octylate and 1 part of dicumyl peroxide was used as a catalyst in this solution.
It was cured at 0° C. for 24 hours.

Table 1 shows the properties of the obtained copper-clad laminate.

Example-4 61 parts of 2,2-bis(4-cyanatophenyl)propane, 7 parts of bis(4-maleimidophenyl)methane, 20 parts of the butadiene-styrene random copolymer prepared in Reference Example-4, and hydroquinone 1 part of 0° to 130°C
88 parts of prepolymer pre-reacted for 4 hours with
, 2.2-bis(4-
Polycarbonate homooligomer of hydroxy-3,5-dibromophenyl)propane (number average degree of polymerization 4.2
>12 parts and 5 parts of a novolac type epoxy resin (manufactured by Yuka Shell Epoxy ■, trade name: Ehicoat 152) were added, and the mixture was diluted with i8M in acetone to obtain a solution with a concentration of 50%.

This solution was added with 0.04 parts of zinc octylate and 2 parts as a catalyst.
,5-dimethyl-2,5-di(t-butylperoxy)
A copper-clad laminate was obtained in the same manner as in Example 1, except that a mixture containing 31 parts of hexene was used.

The properties of this copper-clad laminate are shown in Table 1.

Example-5 In Example-2, the maleated butadiene-α/methylstyrene block copolymer prepared in Reference Example-5 was used instead of the butadiene-styrene random copolymer prepared in Reference Example-2. was carried out in the same manner as in Example-2.

The properties of the obtained copper clad laminate are shown in Table 1.Example-
6 2,2-bis(4-cyanatophenyl) 7”o huff
4 parts and bis(4-maleimidophenyl)methane 32
Prepolymer 8 pre-reacted with
0 parts, 20 parts of the butadiene-styrene copolymer prepared in Reference Example-2, and 0 parts of iron acetylacetonate as a catalyst.
．． After mixing 1 part of G-tert-butyl peroxide and 2 parts of tert-butyl peroxide, 100 parts of wollastonite was further added, and the mixture was kneaded with an extrusion kneader at 100 to 110°C to form pellets. This pellet had good blocking resistance.

This plate L/7 was heated at a temperature of 170°C and a pressure of 300 kg/
ca! The molded product was compression molded for 3 minutes, and the molded product was further post-cured in an oven at 200° C. for 30 minutes to obtain a good molded product.

This molded product has a glass transition temperature of 185°C and a bending strength of 8.
1 dazzle/J (20℃), 4.1 kg/J (17
5℃), heating loss 0.8% (220℃, after 100 hours)
Met.

[Operation and effects of the invention]

The curable resin composition of the present invention as described above has good solubility in general-purpose low boiling point solvents, and when used as a solution, the working environment, drying, etc. are extremely easy. - It is easy to stage, has virtually no stickiness, has excellent handling and workability, and has excellent electrical properties (especially low dielectric constant and dielectric loss tangent), adhesive properties, and other properties of the cured product. It is of good quality and is suitable for use in such applications.

Claims (1)

[Scope of Claims] A polyfunctional cyanate ester having two or more cyanato groups in the molecule, a prepolymer of the cyanate ester, or a prepolymer of the cyanate ester and an amine (a) as an essential component and optionally 50% or more of the butadiene units constituting the polymer chain formed by the cyanate ester resin composition [A] mixed with other thermosetting resin (b) and the polymerization of butadiene and a vinyl aromatic compound. The copolymer, which is a 1,2-bond, has one or more functional groups selected from the group consisting of hydroxyl group, carboxyl group, acid anhydride group, epoxy group, mercapto group, and amino group, with an average of 0 per molecule. . A curable resin composition comprising a copolymer [B] obtained by introducing 5 or more copolymers and having a melting point of 10° C. or higher.