JPH0322907B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a curable resin composition having excellent heat resistance, chemical resistance, abrasion resistance, adhesion, and adhesion. This is a curable resin composition prepared by mixing a polyfunctional cyanate ester containing at least 1,000 g of a polyfunctional cyanate ester, a prepolymer of the cyanate ester, or a prepolymer of the cyanate ester and an amine, and b) a thermoplastic polyurethane resin. Conventionally, thermoplastic polyurethane resins have high heat resistance,
Applications that have poor chemical resistance and are used at high temperatures,
It was not suitable for applications that come into contact with chemicals, solvents, etc. On the other hand, although the cyanate ester resin consisting of component a of the present invention was excellent in heat resistance, chemical resistance, etc., there were cases where adhesion and adhesion were insufficient. The inventors of the present invention have conducted extensive research to resolve the above-mentioned drawbacks, and have found that by combining cyanate ester resin and thermoplastic polyurethane resin, they have improved heat resistance, chemical resistance, abrasion resistance, and adhesive properties. The inventors succeeded in obtaining a curable resin composition with excellent adhesion, leading to the present invention. The present invention will be explained below. As described above, the curable resin composition of the present invention comprises components a and b as essential components. First, a suitable polyfunctional cyanate ester as component a is expressed by the following general formula (1) R(-(O-C≡N) _n ...(1) (m in the formula is 2 or more, usually is an integer less than or equal to 5,
R is an aromatic organic group, and the cyanato group is bonded to the aromatic ring of the organic group. 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-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis((4-dicyanatophenyl)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) ether, bis(4-cyanatophenyl) thioether, bis(4-cyanatophenyl) sulfone, tris(4
-cyanatophenyl) phosphate, and cyanic acid esters obtained by the reaction of novolacs with cyanogen halides. In addition to these, Tokuko Sho 41-1928, Sho 43-18468, Sho 44-4791, Sho 44-4791,
Cyanic acid esters described in JP-A No. 45-11712, No. 46-41112, No. 47-26853, and JP-A No. 51-63149 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. The thermoplastic polyurethane resin which is component b of the present invention refers to 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 ，
Diols 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 or uniformly dispersing components a and b in a solvent, respectively, and mixing the components a and 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 to the present invention, other resin components can also be used in combination. These include esters of (meth)acrylic acid of monofunctional or polyfunctional hydroxy compounds, epoxy esters of (meth)acrylic acid,
(meth)acrylic esters such as alkenyl esters of (meth)acrylic acid and their prepolymers; polyallyl compounds and their prepolymers such as diallyl phthalate, divinylbenzene, diallylbenzene, trialkenyl isocyanurate; dicyclopentadiene and its prepolymers; Prepolymers; epoxy resins; phenolic resins; polyvinyl acetal resins such as polyvinyl formal, polyvinyl acetal, and polyvinyl butyral;
Phenoxy resin; Acrylic resin with -OH group or -COOH group; Silicone resin; Alkyd resin; Polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, butadiene-styrene copolymer, polyisoprene, butyl rubber, natural rubber, etc. Liquid to elastic rubbers may also be used as appropriate. The curable resin composition of the present invention itself has the property of becoming a heat-resistant resin by being bonded and reticulated by heating, but in order to promote crosslinking and reticulation, it is usually used in the form of a catalyst. 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, -1cyanoethyl-2-ethyl-4-methylimidazole, imidazoles exemplified by 1-guanaminoethyl-2-methylimidazole,
Furthermore, adducts of carboxylic acid or its anhydride 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 nanathenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate,
Organometallic salts such as iron acetylacetonate; SnCl ₄ ,
Inorganic metal salts such as _ZnCl2 , _AlCl3 ; peroxides such as benzoyl peroxide, lauroyl peroxide, caprylic peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate; Acid anhydrides such as maleic anhydride, phthalic anhydride, lauric anhydride, pyromellitic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, hexahydro trimellitic anhydride, hexahydropyromellitic anhydride; and azo compounds such as azobisnitrile Examples include the following. The amount of these catalysts to be added is sufficient within a general catalytic amount range, and for example, it may be used in an amount of 10 wt % or less based on the total 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, laminate products, adhesive structures, etc., it is preferable to apply pressure during heat curing, and generally speaking, pressure is applied to the composition at a pressure of 0.1 to
It is suitably selected within the range of 500Kg/cm ² , preferably 5 to 150Kg/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; fiber chamber reinforcing materials; fillers; dyes and pigments; thickeners; lubricants; coupling agents; and flame retardants. They are used in appropriate combinations. The present invention will be explained in more detail below using Examples and Comparative Examples. In addition, parts in Examples and Comparative Examples are parts by weight unless otherwise specified. Example 1 1000 parts of 2,2-bis(4-cyanatophenyl)propane was preliminarily reacted at 150°C for 4 hours. This is a completely thermoplastic polyurethane resin (product name: Elastolan E-580PNAT, Nippon Elastolan Co., Ltd.)
500 parts were added and dissolved in a mixed solvent of N,N-dimethylformamide and methyl ethyl ketone at 70°C with stirring. After adding 0.1 part of ene octylate as a catalyst to this solution and mixing uniformly, a glass woven fabric was impregnated and dried to obtain a B-stage prepreg. Eight sheets of this prepreg were stacked and laminated and molded for 120 minutes at a temperature of 175°C and a pressure of 40 kg/cm ² with 35μ electrolytic copper foil arranged on the top and bottom screens. 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 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, and b. A thermoplastic polyurethane resin. A curable resin composition formed by mixing. 2. The curable resin composition according to claim 1, wherein the polyfunctional cyanate ester of component a is represented by the following general formula (1). 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. ) 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.