JPH0322906B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a curable resin composition with excellent heat resistance, moisture resistance, chemical resistance, abrasion resistance, adhesion, adhesiveness, etc. b. Polyfunctional cyanate esters containing two or more cyanato groups, prepolymers of the cyanate esters, or prepolymers of the cyanate esters and amines, and b. A curable resin composition obtained by mixing a curable resin composition (A) containing a functional maleimide, a prepolymer of the maleimide, or a prepolymer of the maleimide and an amine as an essential component, and a thermoplastic polyurethane resin (B). It is. Conventionally, thermoplastic polyurethane resins have high heat resistance,
It has poor chemical resistance and is not suitable for applications that involve high temperatures or contact with chemicals, solvents, etc. On the other hand, the cyanate ester-maleimide resin consisting of components a and b of the present invention had excellent heat resistance, chemical resistance, etc., but was sometimes unsatisfactory in terms of adhesion and adhesion. The inventors of the present invention have conducted extensive research in order to eliminate the above-mentioned drawbacks, and have found that by combining cyanate ester-maleimide resin and thermoplastic polyurethane resin, they have improved heat resistance, moisture resistance, chemical resistance, and resistance. The inventors succeeded in obtaining a curable resin composition with excellent abrasion properties, adhesion properties, adhesion properties, etc., leading to the present invention. The present invention will be explained below. As described above, the curable resin composition (A) of the present invention has a
and component b as essential components. First, a suitable polyfunctional cyanate ester as component a has the following general formula (1) R(-O-C≡N) _n ...(1) (m in the formula is 2 or more, usually 5 is an integer below,
R is an aromatic organic group, and the cyanato group is bonded to the aromatic ring of the organic group R. Specific examples include 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-tricyanatotratalene, 4,4'-dicyanatobiphenyl,
Bis(4-cycyanatophenyl)methane, 2,2
-bis(4-cyanatophenyl)propane, 2,
2-bis(3,5-dichloro-4-cyanatophenyl)propane, 2,2-bis(3,5-dibromo-4-cyanatophenyl)propane, bis(4-cyanatophenyl)propane
-cyanatophenyl) ether, bis(4-cyanatophenyl) thioether, bis(4-cyanatophenyl) sulfone, tris(4-cyanatophenyl) phosphite, tris, (4-cyanatophenyl) phosphate, and obtained by reaction of novolax with cyanogen halides. cyanate esters, etc. In addition to these, the special public
-1928, 43-18468, 44-4791, 45-
11712, 46-41112, 47-26853 and JP-A-Sho
Cyanic acid esters described in 51-63149 and the like can also be used. In addition, the above-mentioned polyfunctional cyanate ester,
It can be used as a prepolymer obtained by polymerization in the presence of mineral acids, Lewis acids, salts such as sodium carbonate or lithium chloride, phosphoric esters such as tributylphosphine, and the like. These prepolymers are sym-
Generally has a triazine ring in the molecule. In the present invention, it is preferable to use the prepolymer having a number average molecular weight of 300 to 6,000. 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 paraphenylene diamine, meta or para xylylene diamine, 1,4- or 1,3-cyclohexane diamine, hexahydroxylylene diamine,
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. Of course, the above-mentioned polyfunctional cyanate ester,
The prepolymers, and the prepolymers with amines, can be used in the form of mixtures. A preferred polyfunctional maleimide as component b of the present invention is represented by the following general formula (2): (In the formula, R is an aromatic or alicyclic organic group with a valence of 2 or more and usually 5 or less, X ¹ and X ² are hydrogen, halogen,
or an alkyl group, and m is usually an integer of 2 to 5. ) is a compound represented by 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. be able to. 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. Also,
It is desirable that the polyamines be primary amines in terms of reactivity, but secondary amines can also be used.
Suitable amines include the amines used in the form of a preformer with component a mentioned above, and s-
These include melamines with a triazine ring, and polyamines made by reacting aniline with formalin and linking benzene rings with methylene bonds. In the present invention, the above-mentioned polyfunctional maleimide can be used in the form of a prepolymer, or a prepolymer with the above-mentioned amine, instead of being used in the form of a so-called monomer. The thermoplastic polyurethane resin which is component B of the present invention includes dihydroxy compounds (including polyethers and polyesters) having two or more hydroxyl groups in the molecule and diisocyanates having two isocyanate groups. It is a thermoplastic polymer obtained by reaction, and it may be a polymer with trifunctional or higher functionality or a crosslinking agent within the range that maintains thermoplasticity, or it may have a functional group such as -NCO. You can leave it there. Specific examples of dihydroxy compounds include ethylene glycol, 1,2- and 1,3-propanediol, 1,3-, 1,4- and 2,3-butanediol, 1,6-hexanediol, 1 ，
Shiols such as 8-octanediol; polyether type diols such as diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycol; 2,2-bis(4- (hydroxyphenyl)propane, 1,4-phenylene-
Diols with an aromatic ring such as bis(β-hydroxyethyl ether), and dicarboxylic acids of these diols, such as succinic acid, adipic acid, superric acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, Phthalic anhydride, etc.
Examples include polyesters having a molecular weight of 10,000 or less, preferably 800 to 5,000. In addition, examples of diisocyanates include 2,2-bis(4-isocyanatophenyl)propane, bis(4-isocyanatophenyl)methane, and bis(4-isocyanatophenyl)propane.
-isocyanatophenyl)sulfone, bis(4-
isocyanatophenyl) ether, 1,1-bis(4-isocyanatophenyl)cyclohexane,
Methyl-bis(3-isocyanatophenyl)phosphine oxide, 1,5-diisocyanatonaphthalene, m-xylylene diisocyanate, p-xylylene diisocyanate, bis(4-isocyanatohexyl)methane, hexamethylene diisocyanate, etc. Illustrated. The method for preparing the curable resin composition of the present invention includes a method of dissolving component A and component B in a solvent or dissolving them uniformly and mixing them, and a method of mixing component A and component B without a solvent at room temperature or under heating, for example. By a method of uniformly mixing with a Banbury mixer, Henschel mixer, roll, extruder, etc. There is no particular limitation on the usage ratio of both components A and B in the present invention, but in heat-resistant applications, component A should be used in an amount of 50 to 99 wt%, preferably 60 to 99 wt%.
It is best to use 95wt%. Although the above-mentioned components are essential for the present invention, other resin components may also be used in combination. These include esters of (meth)acrylic acid such as esters of (meth)acrylic acid of monofunctional or polyfunctional hydroxy compounds, epoxy esters of (meth)acrylic acid, alkenyl esters of (meth)acrylic acid, and their like. Prepolymer; diallyl phthalate, divinylbenzene,
Polyallyl compounds such as diallylbenzene and trialkenyl isocyanurate and their prepolymers; dicyclopentadiene and their prepolymers; epoxy resins; phenolic resins; polyvinyl acetal resins such as polyvinyl formal, polyvinyl acetal, and polyvinyl butyral; phenoxy resins; OH groups or Acrylic resin with COOH group; Silicone resin; Alkyd resin;
Liquid to elastic rubbers such as polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, butadiene-styrene copolymer, polyisoprene, butyl rubber, and natural rubber may also be used as appropriate. The curable resin composition of the present invention itself has the property of being bonded and reticulated by heating to become a multithermal resin, but in order to promote crosslinking and reticulation, it is usually used in the form of a solvent. Such catalysts include 2-methylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole,
2-Phenylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-propyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethylimidazole , 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, and imidazoles exemplified by 1-guanaminoethyl-2-methylimidazole,
Furthermore, adducts of carboxylic acids or their anhydrides to these imidazoles; N,N-
Dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, N,N-dimethyl-p-anisidine, p-halogeno-N,N
-dimethylaniline, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine,
Quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, N,N,N',
Tertiary amines such as N'-tetramethylbutanediamine and N-methylpiperidine; phenol,
Phenols such as xylenol, cresol, resorcin, catechol, phlologlycin; lead haftate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin, malate, manganese naphthenate, cobalt naphthenate, iron acetylacetonate Organometallic salts such as;
Inorganic metal salts such as SnCl ₄ , ZnCl ₂ , AlCl ₃ ; benzoyl peroxide, lauroyl peroxide, caprylic peroxide, acetyl peroxide, parachlorobenzonyl peroxide, di-tert
- peroxides such as butyl-di-perphthalate;
Maleic anhydride, phthalic anhydride, lauric anhydride, pyromellitic anhydride, trimellitic anhydride,
Acid anhydrides such as hexahydrophthalic anhydride, hexahydro trimellitic anhydride, and hexahydropyromellitic anhydride; and furthermore, azo compounds such as azobisnitrile are included. The amount of these catalysts to be added is sufficient within a general range of catalytic amounts, and may be used, for example, in an amount of 10 wt % or less based on the gold composition. The temperature for curing the curable resin composition of the present invention varies depending on the presence or absence of a curing agent and catalyst, the types of composition components, etc., but it may be generally selected within the range of 100 to 300°C. This composition is used for various purposes, but when used for manufacturing molded products, laminates, adhesive structures, etc., it is preferable to apply pressure during heat curing, and generally speaking, the pressure is applied to a pressure of 0.1 to
It is suitably selected within the range of 500 Kg/cm ² , preferably 5 to 150 Kg/cm ² . The curable resin composition of the present invention may contain various additives as desired, as long as the original properties of the composition are not impaired. These additives include various known additives such as natural or synthetic resins; fibrous reinforcing materials; fillers; dyes and pigments; thickeners; lubricants; coupling agents; and flame retardants. They are used in appropriate combinations. Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. In addition, parts in Examples and Comparative Examples are parts by weight unless otherwise specified. Example 1 500 parts of 2,2-bis(4-cyanatophenyl)propane and 500 parts of bis(4-maleimidophenyl)methane were preliminarily reacted at 150°C for 60 minutes. This is a completely thermoplastic polyurethane resin (product name: Elastolan E-580PNAT, Nippon Elastolan Co., Ltd.)
600 parts were added and dissolved in a mixed solvent of N,N-dimethylformamide and methyl ethyl ketone at 50°C with stirring. This solution contains 0.1 iron acetylacetonate as a catalyst.
After adding and mixing evenly, impregnate the glass woven cloth.
It was dried to obtain a B-stage prepreg. Eight sheets of this prepreg were laminated and laminated and molded for 120 minutes at a temperature of 175° C. and a pressure of 40 kg/cm ² with 35 μm electrolytic copper foil arranged on both the top and bottom surfaces. The test results of the obtained copper clad laminates are shown in Table 1. Example 2 900 parts of 2,2-bis(4-cyanitophenyl)propane and 100 parts of bis(4-maleimidophenyl)ether were preliminarily reacted at 150°C for 150 minutes.
To this, 500 parts of incomplete thermoplastic polyurethane resin (trade name: Texin, Mobay Co., Ltd.) was added, and N, N-
It was dissolved in a mixed solvent of dimethylformamide and methyl ethyl ketone at 50°C with stirring. To this solution, 0.1 part of octyl dust zinc was added as a catalyst and mixed uniformly, and then a glass woven fabric was impregnated and dried to obtain a B-stage prepreg. The procedure was the same as in Example 1 except that this prepreg was used. The test results of the obtained copper clad laminates are shown in Table 1. Comparative Example 1 Table 1 shows the same results as in Example 1 except that the fully thermoplastic polyurethane resin was not used. 【table】

Claims (1)

[Scope of Claims] 1 a. A polyfunctional cyanate ester having two or more cyanato groups in the molecule, the estrel cyanate prepolymer or a prepolymer of the cyanate ester and an amine, and b. A curable resin composition (A) containing as an essential component a polyfunctional maleimide containing two or more maleimide groups, the maleimide prepolymer, or the prepolymer of the maleimide and an amine;
A curable resin composition formed by mixing a thermoplastic polyurethane resin (B). 2. Claim 1, wherein the polyfunctional cyanate ester as component a is represented by the following general formula (1), and the polyfunctional maleimide as the b component is represented by the following general formula (2). curable resin composition. General formula (1): R(-O-C≡N) _n ...(1) (m in the formula is an integer of 2 or more and usually 5 or less,
R is an aromatic organic group, and the cyanato group is bonded to the aromatic ring of the organic group R. ) General formula (2) (R in the formula is a divalent, usually pentavalent or less aromatic or alicyclic organic group, X is hydrogen, halogen, or an alkyl group, and m is usually an integer of 2 to 5. 3 The A component is 50 to 99% by weight, and the B component is 50 to 1% by weight.
The curable resin composition according to claim 1, wherein the curable resin composition is blended in a range of % by weight.