JPH0125343B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition containing a polyfunctional cyanate ester, a polyfunctional maleimide, and an epoxy compound, each having an adjusted curing rate. The following general formula (1) is added to the resin composition containing compounds, polyfunctional maleimides, and epoxy compounds. (In the formula, R is an alkyl group having 1 to 3 carbon atoms, m is 0 or an integer of 1 to 3, and n is 0 or an integer of 1 to 4.) Alkyl-substituted or unsubstituted benzenesulfonic acid represented by This is a curable resin composition with an adjusted curing speed by adding 0.0001 to 5 wt% of Resin compositions containing polyfunctional cyanic acid esters, polyfunctional maleimides, and epoxy compounds can be gelled and hardened simply by heating, and can also be cured by heating, and can also be cured by organic metal salts and tertiary amines. The gelation and curing speed can also be accelerated by adding a catalyst such as imidazole or the like. Conventionally, the gelation and curing speed of the above-mentioned resin compositions can be adjusted by adjusting the amount and type of catalysts that accelerate the gelation and curing speed, as described above, to create a gel that suits the purpose of use, such as the application and process. This depended on the method of adjusting the curing and curing speed. However, with this method, there are differences in the amount of catalysts added, their dispersion state, and differences in the production date and time of polyfunctional cyanate esters, polyfunctional maleimides, epoxy compounds, etc. used as raw materials, and differences in storage periods. It has been difficult to sufficiently control variations in gelation and curing rates, which are presumed to be based on subtle differences due to factors such as the following. As a result of various studies to improve the above-mentioned drawbacks, the present invention has revealed that alkyl-substituted or unsubstituted benzenesulfonic acids such as toluenesulfonic acid and benzenesulfonic acid can be used in combination with polyfunctional cyanate esters, polyfunctional maleimides, and epoxy compounds. The resin composition containing benzenesulfonic acids has the effect of retarding the gelation and curing speed of the resin composition, and the resin composition containing benzenesulfonic acids has excellent storage stability, and the gelation and curing speed can be easily adjusted by adding a catalyst. It was completed after discovering what could be done. The configuration of the present invention will be explained below. The resin composition of the present invention contains polyfunctional cyanate esters, polyfunctional maleimides, and epoxy compounds. Here, the polyfunctional cyanate esters are polyfunctional cyanate esters containing two or more cyanate groups in the molecule, prepolymers of the cyanate esters, or prepolymers of the cyanate esters and amines. , polyfunctional maleimides are polyfunctional maleimides containing two or more N-maleimide groups in the molecule, prepolymers of the maleimides, or prepolymers of the maleimides and amines, and epoxy compounds are the molecule Compounds that usually contain two or more epoxy groups and their prepolymers are known. These resin components will be further explained. First, polyfunctional cyanate ester has the following general formula (2) R(-O-C≡N)m...(2) (m in the formula is an integer of 2 or more and usually 5 or less, and R is It is an aromatic organic group, and the cyanate ester 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
-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis(4-dyanatophenyl)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) phosphite, tris(4-cyanatophenyl)
These include phosphates and cyanate esters obtained by the reaction of novolacs with cyanogen halides. In addition to these, Tokuko Sho 41-1928, Tokko Sho
43-18468, Special Publication 44-4791, Special Publication 45-11712,
Tokuko Sho 46-41112, Tokko Sho 47-26853 and Tokko Sho
Cyanic acid esters described in 51-63149 and the like can 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. 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-cyclohexanediamine, 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(3,
5-dibromo-4-aminophenyl)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. In addition, polyfunctional maleimide is represented by the following general formula (3) (In the formula, R is a divalent, usually 5 or less, aromatic or alicyclic organic group, X ¹ and X ² are hydrogen, halogen, or an alkyl group, and m is 2 or more and usually 5 or less. ) is a compound represented by The maleimide represented by the above formula has maleic anhydride and an amino group of 2 to 2.
It can be produced by a method known per se, in which maleamic acid is prepared by reacting with a polyamine having five polyamines, and then the maleamic acid is cyclized by dehydration. It is preferable that the polyamines 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. good. 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 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, bis(4-amino-
3-chlorophenyl)methane, 2,2-bis(3,5-dibromo-4-aminophenyl)propane, bis(4-aminophenyl)phenylmethane, 3,4-diaminophenyl-4'-aminophenylmethane, 1, These include 1-bis(4-aminophenyl)-1-phenylethane, melamines having an s-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 also be used in the form of a prepolymer instead of in the form of a so-called monomer. Furthermore, epoxy compounds are compounds having two or more epoxy groups in the molecule as described above, and prepolymers thereof. Examples include polyol, polyhydroxybenzene, bisphenol,
Polyglycidyl compounds obtained by reacting low molecular weight novolak type phenolic resins, hydroxyl group-containing silicone resins, aniline, 3,5-diaminophenol, etc. with epihalohydrin, butadiene, bentadiene, vinylcyclohexane, dicyclobentyl ether, etc. These include polyepoxy compounds in which double bonds are epoxidized. Examples of the alkyl-substituted or unsubstituted benzenesulfonic acids represented by the general formula (1) of the present invention include benzenesulfonic acid and para-toluenesulfonic acid. It may also contain water. The amount used is 0.0001 to 5% by weight, preferably 0.001 to 1% by weight in the resin component.
If it is less than 0.0001% by weight, the effect of retarding the gelation/curing rate will be small and the adjustment of variations will be insufficient, and if it is used more than 5% by weight, there will be no significant change in the effect, and if anything, it may have adverse effects such as impairing the balance of physical properties. I don't like it because it comes out. When the alkyl-substituted or unsubstituted benzenesulfonic acid of the present invention is added to the resin composition as described above, when it is used as a varnish, it may be added by dissolving it in a solvent such as acetone, methyl ethyl ketone, toluene, xylene, etc., or by adding it in solid form. It may be added and dissolved. When used as a solvent-free resin, it is usually preferable to add and mix the resin composition into a heated and melted resin composition. 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, catechol, phloroglucin Phenols such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate,
Organic metal salts such as dibutyltin maleate, manganese naphthenate, cobalt naphthenate, iron acetylacetone; inorganic metal salts such as SnCl ₄ , ZnCl ₂ , AlCl ₃ ; benzoyl peroxide, lauroyl peroxide, caprylyl peroxide, acetyl peroxide , parachlorobenzoyl peroxide, di-tertiary butyl deep perphthalate; maleic anhydride, phthalic anhydride, lauric anhydride, pyromellitic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, hexahydro trimellitic anhydride, hexahydro Examples include acid anhydrides such as pyromellitic anhydride. The amount of catalyst added is sufficient within the range of catalyst amount in a general sense, for example 10% by weight based on the total composition.
It may be used in the following amounts. Various additives can be added to the composition of the present invention 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 addition amounts such as dyes and pigments, thickeners, lubricants, and flame retardants are included, and these may be used in appropriate combinations as desired. The curable resin composition of the present invention as described above has excellent storage stability, the adjustment range of gelation and curing speed is widened, and the variation between product numbers is also greatly reduced. Yes, the practical significance is extremely large. The present invention will be explained below with reference to Examples. Example 1 720 g of 2,2-bis(4-cyanatophenyl)propane, 80 g of bis(4-maleimidophenyl)methane, and 200 g of bisphenol A type epoxy resin (Epicote 828: manufactured by Yuka Ciel Co., Ltd.) were heated at 135°C.
After reacting for a period of time to form a prepolymer, 1 g of p-toluenesulfonic acid monohydrate and methyl ethyl ketone
667 g was added and dissolved to obtain a resin solution. After adding and mixing 0.1 g of zinc octylate (zinc content 18%) to the obtained resin solution 167, the time required for gelation on a hot plate at 160° C. (abbreviated as gel time) was measured. The gel time was 3 minutes 31 seconds. Comparative Example 1 The same procedure as in Example 1 was carried out except that p-toluenesulfonic acid monohydrate was not added. Gel time was 1 minute 12 seconds. Example 2 260 g of 2,2-bis(4-cyanatophenyl)propane, 100 g of novolak-type cyanate ester derived from phenol novolak resin (MP-1210: manufactured by Gunei Kagaku Co., Ltd.) with a number average molecular weight of 330, and bis( After reacting with 240 g of 4-maleimidophenyl) methane at 150°C for 3 hours to obtain a prepolymer, 400 g of novolak type epoxy resin (DEN438: manufactured by Dow), 2 g of benzenesulfonic acid, and 428 g of methyl ethyl ketone were added and dissolved. A resin solution was obtained. After adding and mixing 0.1 g of zinc octylate (zinc content: 18%) to 143 g of the obtained resin solution, the gel time was measured. Gel time was 4 minutes 52 seconds. Comparative Example 2 The same procedure as in Example 2 was carried out except that benzenesulfonic acid was not added. Gel time was 1 minute 19 seconds. Example 3 560 g of 2,2-bis(4-cyanatophenyl)propane, 240 g of bis(4-maleimidophenyl)methane, 200 g of bisphenol F type epoxy resin (Epicote 807: manufactured by Yuka Ciel), and p-toluenesulfonic acid Heat and melt mix 10g at 120℃,
It was immediately cooled to obtain a resin composition. The resulting resin composition was melted by heating and stirred for 8 hours at 100°C, and the viscosity was 48 cps/100°C. Comparative Example 3 The same procedure as Example 3 was carried out except that p-toluenesulfonic acid monohydrate was not added. The viscosity after stirring at 100°C for 8 hours was 410 cps/100°C. Example 4 Same as Example 1. However, the amount of p-toluenesulfonic acid monohydrate added was 0.1 g. Gel time was 1 minute 34 seconds. Example 5 720 g of 2,2-bis(4-cyanatophenyl)propane, 80 g of bis(4-maleimidophenyl)methane, and 200 g of bisphenol A type epoxy resin (Epicote 828, manufactured by Yuka Ciel Co., Ltd.) were reacted at 135°C. The end point was when the refractive index (η ⁹⁰ _D ) at 90° C. reached 1.575, and 667 g of methyl ethyl ketone was added and dissolved to obtain a resin solution. In the same manner, two more types of resin solutions with different raw material lots and production dates and times, a total of three types, were obtained. A predetermined amount of p-toluenesulfonic acid monohydrate and zinc octylate (zinc content) of 167 g of the obtained resin solution
After adding 0.1 g of 18%) and stirring well, gel time was measured on a hot plate at 160°C. The gel times were as shown in Table 1. Comparative Example 4 Three different resin solutions obtained in Example 5
After adding 0.1 g of zinc octylate (zinc content 18%) to 167 g and stirring well, the gel time was measured on a hot plate at 160°C. The gel times were as shown in Table 1. 【table】

Claims (1)

[Scope of Claims] 1. A resin composition containing a polyfunctional cyanate ester, a polyfunctional maleimide, and an epoxy compound has the following general formula (1). (In the formula, R is an alkyl group having 1 to 3 carbon atoms, m is 0 or an integer of 1 to 3, and n is 0 or an integer of 1 to 4.) Alkyl-substituted or unsubstituted benzenesulfonic acid represented by A curable resin composition with an adjusted curing speed by adding 0.0001 to 5wt% of