JPS6328099B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel curable resin composition that is highly flexible and elastic, and has excellent water resistance. Curable resin compositions containing polyfunctional cyanate esters and polyfunctional maleimides (Japanese Patent Publication No. 54-30440), as well as epoxy resins (Japanese Patent Publication No. 52-31279) are heat resistant, mechanically resistant, It has excellent physical strength, chemical resistance, moisture resistance, etc., but has poor flexibility,
In terms of elasticity, etc., physical properties can be improved to some extent by introducing aliphatic long-chain organic groups into the so-called monomers used, but the effects are still insufficient. Furthermore, a curable resin composition in which a polybutadiene resin containing a terminal hydroxyl group is blended with a polyfunctional cyanate ester has some satisfactory improvements in heat resistance and mechanical strength, but it has poor moisture resistance, especially at high and high temperatures. The improvement in durability under humidity was insufficient. The present invention has been completed by the discovery and completion of a curable resin composition that has excellent flexibility and elasticity, as well as excellent heat resistance and moisture resistance, as a result of repeated research on the above points. That is, the present invention comprises: (a) a polybutadiene resin having a hydroxyl group or a carboxyl group at the terminal, or a hydrogenated product of the polybutadiene resin, (b) a polyfunctional cyanate ester or the cyanate ester prepolymer, and (c) a polyfunctional maleimide or the maleimide prepolymer. It is a curable resin composition which further contains a mixture with a d-epoxy resin or a pre-reacted product as required. The composition components used in the present invention will be explained. First, polybutadiene resin having a hydroxyl group or carboxyl group at the terminal of component a is one having a molecular weight of 700 to 10,000, preferably 800 to 5,000 and having 1.0 to 3.0 hydroxyl or carboxyl groups in the molecule, and is not a hydrogenated product. is obtained by hydrogenating the above polybutadiene resin using a known hydrogenation catalyst. The polyfunctional cyanate ester which is component b of the resin composition of the present invention is an organic compound having two or more cyanato groups, and a suitable cyanate ester has the general formula R-(O-C≡N)m ...(1) [In the formula, m is an integer of 2 or more and usually 5 or less, R is an aromatic organic group, and the cyanate ester group is bonded to the aromatic ring of the organic group R. It is a compound represented by 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-cyanatophenyl)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) ether
-cyanatophenyl) phosphite, tris(4
-cyanatophenyl) phosphate, and cyanic acid esters obtained by the reaction of novolak with cyanogen halides. In addition to these, Tokuko Sho 41-1928, Tokko Sho 44-4791, Tokko Sho 45-
11712, Japanese Patent Publication No. 46-41112 and Japanese Patent Publication No. 51-63149
Cyanic acid esters described in et al. may also be used. Further, a prepolymer obtained by polymerizing the above-mentioned polyfunctional cyanate ester in the presence of a catalyst such as a mineral acid, a Lewis acid, a salt such as sodium carbonate or lithium chloride, or a phosphate ester such as tributylphosphine. It can be used as These prepolymers are symylamines formed by trimerization of the cyanide groups in the cyanate ester.
- Generally has a triazine ring in the molecule.
In the present invention, it is preferable to use the prepolymer having an average molecular weight of 400 to 6,000. The polyfunctional maleimide as component c used in the resin composition of the present invention is a compound having two or more maleimide groups, which is used to create a curable resin composition with excellent heat resistance, moisture resistance, etc. . The polyfunctional maleimide suitably used in the present invention has the following general formula: [In the formula, R is an aromatic or alicyclic organic group having a valence of 2 or more and usually 5 or less, X ¹ and X ² are hydrogen, halogen, or an alkyl group, n is 2 or more,
It is an integer less than or equal to 5. ] It is a compound represented by The maleimides represented by the above formula are mixed with maleic anhydride and 2 or more, usually 5
It can be produced by a method known per se in which maleamic acid is prepared by reacting it with an amine having up to 10 amino groups, and then the maleamic acid is cyclodehydrated. It is preferable that the polyvalent amines used are aromatic amines 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. Furthermore, it is particularly desirable that the polyvalent amines be primary amines in terms of reactivity, but secondary amines can also be used. Suitable amines include meta- or paraphenylenediamine, meta- or paraxylylenediamine, 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-3methylphenyl)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(3,5-dibromo-4-aminophenyl)propane, bis(4-aminophenyl)phenylmethane, 3,4-diaminophenyl-4' -Aminophenylmethane, 1,1-bis(4-aminophenyl)-1-phenylethane, melamine with an s-triazine ring, and polyamines made by reacting aniline with formalin and linking benzene rings with methylene bonds. shown. In the present invention, the above-mentioned polyfunctional maleimide can also be used in the form of a prepolymer instead of in the form of a so-called monomer. The polyfunctional maleimide of component c above can be used alone or in a mixture of two or more,
In addition, polyfunctional maleimides may be substituted with monomaleimide compounds such as N-allylumaleimide, N-propyl-aleimide, N-hexyl-maleimide, N-phenyl-maleimide, etc. to a maximum of about 40 wt%. Good too. In addition, the epoxy resin used as component d is used as necessary to improve adhesive strength, adjust viscosity, etc., and includes compounds having two or more epoxy groups in the molecule and This is the bre polymer. For example, polyglycidyl compounds obtained by reacting polyols, polyhydroxybenzenes, bisphenols, low molecular weight novolac type phenolic resins, hydroxyl group-containing silicone resins, aniline, 3,5-diaminophenol, etc. with epihalohydrin; These include polyepoxy compounds in which double bonds are epoxidized, such as butadiene, bentadiene, vinylcyclohexene, and dicyclobentyl ether. The resin composition of the present invention, which contains the above components a, b, and c, and optionally d, can be produced by a simple mixing method, a pre-reaction method after mixing, a pre-reaction method and a pre-mixing method, or a method of pre-reacting and mixing them. It is manufactured by a method such as pre-reaction. The 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 a catalyst is
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-
Imidazoles exemplified by cyanoethyl-2ethyl-4methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-guanaminoethyl-2-methylimidazole, and further, these imidazoles such as trimellitic acid adducts; 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, Tertiary amines such as N-methylmorpholine, triethanolamine, triethylenediamine, N,N,N',N'-tetramethylbutanediamine, N-methylpiperidine; phenol, cresol, xylenol, resorcin, phloroglucin, etc. Phenols; lead naphthenate, lead stearate, zinc naphthenate,
Organometallic compounds such as zinc octylate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, iron acetylacetone; inorganic metal compounds such as SnCl ₄ , ZnCl ₂ , AlCl ₂ ; benzoyl peroxide, lauroyl peroxide, Examples include peroxides such as caprylyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, and tertiary butyl perphthalate. In addition, those generally known as curing agents or catalysts for epoxy resins, such as acid anhydrides such as pyromellitic anhydride and phthalic anhydride, can also be used in combination. The amount of the catalyst to be added is sufficient within the general range of the catalyst amount, for example, it may be used in an amount of 5% by weight or less based on the total composition. The 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:
Natural or synthetic resins for imparting new properties to the composition of the invention; fibrous reinforcement; fillers;
Various known additives such as dyes and pigments; thickeners; lubricants; and flame retardants are included, and may be used in appropriate combinations as desired. 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 is usually in the range of 100 to 250°C, preferably 120 to 200°C. It should be selected by When used in the production of molded products, laminated bonded structures, etc., it is preferable to apply pressure during heat curing, and generally speaking, the pressure is appropriately selected within the range of 10 to 200 kg/cm ² . The resin composition of the present invention described in detail above has a desirable combination of various properties such as adhesion, heat resistance, and electrical properties, as well as excellent mechanical properties, particularly elasticity, chemical resistance, It also has excellent moisture resistance. Although the crosslinking and network formation reaction mechanism of the curable resin composition of the present invention described in detail above has not been proven, the reaction of the cyanato group of polyfunctional cyanate esters and the reaction of polyfunctional maleimide The reaction of the maleimide group in the above is estimated as follows. (1) Reaction of polyfunctional cyanate ester (2) Reaction of polyfunctional maleimide Regarding the epoxy group of the epoxy resin, which is another component of the present invention, the reaction mechanism with hydroxyl group, carboxyl group, amino group, acid anhydride group, etc. is known. From the above, in the composition of the present invention, in addition to the reactions that are presumed to occur in a composition comprising a known polyfunctional cyanate ester, a polyfunctional maleimide, and an epoxy resin, It is presumed that a reaction occurs between the hydroxyl group or carboxyl group of the polybutadiene resin having a hydroxyl group or carboxyl group newly added as a component and the above-mentioned component. Also, the reason why the composition of the present invention has particularly excellent durability under high temperature and humidity compared to a composition in which a polybutadiene resin having a hydroxyl group or a carboxyl group is blended with a polyfunctional cyanate ester. Although this is still within the realm of speculation, it is also thought to be caused by a reaction between maleimide groups (and epoxy groups) and amino groups, carboxyl groups, etc. The present invention will be explained in more detail below using Examples and Comparative Examples. Example 1 18 parts by weight of 1,4-dicyanatobenzene and 2 parts by weight of bis(4-maleimidophenyl)methane were added to 100 parts by weight of polybutadiene with terminal hydroxyl groups (molecular weight 1050, intramolecular average value of hydroxyl groups 1.9) at 150°C. A resin composition pre-reacted for 100 minutes, and 0.01 parts by weight of zinc octylate and triethylenediamine as a catalyst.
After adding 0.01 part by weight and mixing uniformly at 100℃,
Pour this into a Teflon mold and heat at 160℃ for 100 minutes.
A good cast product was obtained by heating and curing at 175°C for 40 minutes. The properties of this cast product are shown in Table 1. Example 2 2,
27 parts by weight of 2-bis(4-cyanatophenyl)propane and 3 parts by weight of bis(4-maleimidophenyl) ether pre-reacted at 145°C for 150 minutes, and epoxy resin (Epicote 1001, manufactured by Ciel Chemical Co., Ltd.) After adding 5 parts by weight and uniformly mixing at 120°C, a cast product was made in the same manner. The properties of this cast product are shown in Table 1. Comparative Example 1 Polybutadiene 100 of Example 1 as a resin component
parts by weight, 20 parts by weight of 1,4-dicyanatobenzene,
A cast product was obtained in the same manner as in Example 1, except that 0.01 part by weight of zinc octylate and 0.01 part by weight of triethylenediamine were used. The properties of this cast product are shown in Table 1.

[Table] Example 3 490 parts by weight of 2,2-bis(4-cyanatophenyl)propane and bis(4-maleimidophenyl)
A preliminary reaction with 210 parts by weight of methane at 150°C for 90 minutes was added to polybutadiene with hydroxyl-terminated groups (molecular weight
1100, average value of intramolecular hydroxyl groups 2.0) 300 parts by weight and 0.1 part by weight of zinc octylate as a catalyst were added,
This was dissolved in a mixed solvent of methyl ethyl ketone and N,N-dimethylformamide by stirring and mixing. This mixture was impregnated into a glass woven cloth and dried.
Manufacture stage prepreg, stack 8 sheets of it,
Layer electrolytic copper foil with a thickness of 35 μm on both sides, and
A good copper-clad laminate was obtained by press molding at a temperature of 40 kg/cm ² at a pressure of 40 kg/cm 2 for 150 minutes. The properties of this plate are shown in Table 2. Comparative Example 2 In Example 3, 2,2-bis( A copper-clad laminate was obtained in the same manner except that 700 parts by weight of 4-cyanatophenyl)propane was used. The properties of this plate are shown in Table 2. Example 4 400 parts by weight of 2,2-bis(4-cyanatophenyl)propane and bis(4-maleimidophenyl)
A polybutadiene containing terminal hydroxyl groups and carboxyl groups (molecular weight 3000, average value of intramolecular hydroxyl groups 1.3, average value of intramolecular carboxyl groups 1.0) is pre-reacted with 400 parts by weight of ether at 150°C for 120 minutes.
150 parts by weight, 50 parts by weight of an epoxy resin (manufactured by Yuka Ciel Epoxy Co., Ltd., trade name: Epicote 1001), and 0.1 parts by weight of zinc octylate and 1.0 parts by weight of dicumyl peroxide as catalysts were added, and this was mixed with methyl ethyl ketone, N, The mixture was uniformly stirred and mixed to dissolve in a mixed solvent with N-dimethylformamide. Impregnate a glass woven cloth with this solution and dry it.
Manufacture stage prepreg, stack 8 sheets of it,
Layer electrolytic copper foil with a thickness of 35 μm on both sides, and
℃ pressure 30Kg/cm ² for 90 minutes, then temperature 230℃ and pressure
A good copper-clad laminate was obtained by press molding at 40 kg/cm ² for 120 minutes. The properties of this board are shown in Table 2. Comparative Example 3 Example 4 except that polybutadiene containing terminal hydroxyl groups and carboxyl groups (molecular weight 3000, average value of intramolecular hydroxyl groups 1.3, average value of intramolecular carboxyl groups 1.0) was used alone, and dicumyl peroxide was used as a catalyst. A copper-clad laminate was obtained according to the method. The properties of this plate are shown in Table 2.

[Table] Observe nothingness.

Claims (1)

[Claims] 1 a polybutadiene resin having a hydroxyl group or carboxyl group at the terminal or a hydrogenated product of the polybutadiene resin, b a polyfunctional cyanate ester or the cyanate ester prepolymer, c a polyfunctional maleimide or the maleimide prepolymer,
A curable resin composition further containing a mixture with an epoxy resin or a pre-reacted product, if necessary.