JPS647091B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a curable resin composition that is solvent-free liquid at room temperature (25°C). A method for producing a curable resin composition that is liquid at room temperature, which comprises mixing or pre-reacting at 70 to 200°C, then adding and mixing 5 to 60 wt% of divinylbenzene at 30 to 100°C, and cooling. This is a method for producing a curable resin composition that is liquid at room temperature and has excellent workability and heat resistance. Conventionally, resin compositions containing polyfunctional maleimides have been subjected to various research and development in the fields of insulating materials, structural materials, adhesives, etc. because of their high curability and heat resistance. However, the resin composition is usually solid at room temperature, and is used by heating and melting it for applications that do not require a solvent, such as casting or potting. However, heating and melting requires equipment and a heat source, and furthermore, since the resin composition undergoes polymerization simply by applying heat, it has the disadvantage that its usable time is limited. In addition, reactive diluents such as aliphatic glycidyl ethers and aliphatic glycidyl esters commonly used in the field of epoxy resins, and reactive diluents such as diallylphthalate monomers and styrene monomers used in other fields are toxic and volatile. , deterioration of the properties of the cured product, etc., so it is not very preferable as a reactive diluent for liquefying a resin composition containing a polyfunctional maleimide. As a result of studies to eliminate the above-mentioned drawbacks, the present invention has revealed that when divinylbenzene is liquefied using a reactive diluent, the toxicity is low, the volatility is not so high, and there is almost no deterioration of the properties of the cured product. After mixing or preliminarily reacting 2 to 90 wt% of thermosetting resin and 4 to 90 wt% of thermosetting resin at 80 to 180°C, 5 to 60 wt% of divinylbenzene is added and mixed at 30 to 100°C. discovered that a liquid curable resin composition could be obtained by
It was completed based on that. The present invention will be explained below. The divinylbenzene of the present invention has the following formula: Of course, purified and highly pure products,
Commercially available products with a purity of 55 to 60% and containing ethylvinylbenzene and saturated compounds as impurities can also be used. Alternatively, a stabilizer containing a stabilizer such as tertiary butylcatechol can be used as is. The polyfunctional maleimide of the present invention is any organic compound having two or more maleimide groups derived from maleic anhydride and a polyamine. (In the formula, R is a divalent or trivalent aromatic or alicyclic organic group, X ¹ and X ² are hydrogen, halogen, or an alkyl group, and n is 2 or more and usually 5 or less. ). The maleimide represented by the above formula can be produced by a method known per se, in which maleic anhydride and polyamine are reacted to prepare maleamic acid, and then the maleamic acid is cyclodehydrated. It is preferable that the polyamines used are aromatic amines in terms of 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. Further, it is particularly desirable that the polyamines be primary amines in terms of reactivity, but secondary amines can also be used. These maleimides can be used alone or in combination of two or more. Moreover, those obtained by heating without a catalyst or in the presence of a catalyst to form a prepolymer can also be suitably used. Examples of amines used as raw materials for polyfunctional maleimide include metaphenylenediamine, meta- or para-xylylenediamine, 1,
4-Cyclohexanediamine, hexahydroxylylenediamine, bis(4-aminophenyl)methane, bis(4-aminophenyl)sulfone, bis(4-amino-3-methylphenyl)methane (MDT), bis(4-amino-3, 5-dimethylphenyl)methane (MDX), 1,3-bis(4
-aminophenyl)cyclohexane, bis(4-
aminophenyl) ether, 2,2-bis(4-
aminophenyl)propane, 2,2-bis(4-
Amino-3-methylphenyl)methane, α, α-
Bis(4-aminophenyl)phenylmethane, bis(4-amino-3-chlorophenyl)methane,
Bis(4-amino-3,5-dichlorophenyl)
The benzene ring of aniline obtained from methane, bis(4-amino-3,5-dibromophenyl)methane, melamine, aniline and formalin is -CH ₂
Examples include compounds formed by bonding with -. In the present invention, thermosetting resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol volak type epoxy resin,
Epoxy resins such as cresol novolac type epoxy resin, alicyclic epoxy resin, hydantoin epoxy resin, bisphenol A type cyanate resin,
Cyanate resins having one (-O-C≡N) group in the molecule, such as phenol novolac type cyanate resins and alicyclic cyanate resins, preferably two or more groups;
Acrylate or methacrylate esters of polyhydric alcohols, novolac type phenolic resins,
Phenol resins such as resol type phenolic resins,
Unsaturated polyester resins, isocyanate compounds, diene compounds, polyamide resins, polyurethane resins, amines, diallyl phthalate resins, 1,2-polybutadiene, epoxidized 1,
Examples include 1,2 polybutadiene resin liquid rubbers such as 2-polybutadiene, maleated 1,2-polybutadiene, and isocyanate-modified 1,2 polybutadiene, and mixtures of two or more thereof. Among the thermosetting resins exemplified above, cyanate resins and epoxy resins are preferred, and cyanate resins are particularly preferred. A cyanate resin is a compound having at least two or more cyanate groups in its molecule. Preferred are organic cyanate esters represented by the following general formula. Formula R(-O-C≡N)m (wherein, R is a residue having an aromatic nucleus derived from an aromatic hydrocarbon selected from the group consisting of benzene, biphenyl, and naphthalene; two or more benzene rings but

[Formula] (R ₁ and R ₂ may be the same or different, hydrogen or an alkyl group having 1 to 4 carbon atoms),
-O-, -CH ₂ OCH ₂ -, -S-,

【formula】

【formula】 【formula】

[Formula] and

A residue having an aromatic nucleus derived from a compound bonded by one or more bridges selected from the group consisting of [Formula]; Residues with an aromatic nucleus obtained by These aromatic nuclei may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group, chloro, or bromine substituent. m is a number from 2 to 10,
And the cyanate group is always bonded directly to the aromatic nucleus. ) Specific examples of such compounds 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) phosphite, tris(4-cyanatophenyl) phosphate, and the like. In addition to these, Special Publication No. 46-41112, Special Publication No. 4791-1979, Special Publication No. 4791-1973,
Cyanic acid esters described in No. 42076 and the like are used. Prepolymers having a molecular weight of 400 to 6,000 and having a triazine ring formed by trimerizing the cyanate groups of these cyanate esters are also used.
This prepolymer contains the above cyanate ester,
For example, it can be obtained by polymerization using an acid such as a mineral acid or a Lewis acid; a base such as sodium hydroxide, sodium alcoholate, or tertiary amines; or a salt such as sodium carbonate or lithium chloride as a catalyst. Polyfunctional cyanate esters can also be used in the form of mixtures of monomers and prepolymers. In the present invention, the amount of divinylbenzene used is 5 to 60 wt%, preferably 10 to 50 wt%. If the amount of divinylbenzene used is less than 5 wt%, the viscosity of the resulting resin composition will be too high, which is undesirable.
Moreover, if it is more than 60 wt %, disadvantages such as large curing shrinkage of the resulting resin composition occur, which is not preferable. The amount of polyfunctional maleimides used is 2 to 90wt.
%, preferably 5 to 80 wt%. In addition, the amount of thermosetting resin used is 4 to 90 wt%, preferably 10 to 90 wt%.
It is 80wt%. Mixing or preliminary reaction of polyfunctional maleimide and thermosetting resin is carried out at 70 to 200°C, preferably 90 to 170°C.
Repeat for a period of time that does not result in gelation. This preliminary reaction is necessary to prevent or suppress the precipitation of monomer crystals of polyfunctional maleimides and thermosetting resins, but if the reaction proceeds too much, it will increase the viscosity of the resulting resin composition.
Undesirable. When carrying out a preliminary reaction, it is carried out in the presence or absence of a catalyst, but the reaction time depends on the type and amount of polyfunctional maleimide used, the type and amount of curable resin used, and if a catalyst is used. Varies depending on the type of catalyst and amount used. Divinylbenzene is added and mixed after the polyfunctional maleimide and thermosetting resin are mixed or the temperature of the preliminary reactant is brought to 30 to 100°C, preferably 40 to 80°C. If the temperature is lower than 30°C, the viscosity of the mixed or pre-reacted product will be too high, making stirring difficult and making it virtually impossible to mix divinylbenzene, which is not preferable. On the other hand, if the temperature is too high than 100°C, the stability of divinylbenzene is poor and the reaction progresses, possibly leading to gelation, which is not preferable. As described above, the liquid curable resin composition obtained according to the present invention contains known storage stabilizers such as divinylbenzene, maleimide, and thermosetting resin storage stabilizers to improve the stability during storage. It is also a preferred embodiment to use The liquid curable resin composition produced according to the present invention as described above can be cured simply by heating. Catalysts can also be added to cure faster. Such catalysts include 2-methylimidazole, 2-undecylimidazole,
2-heptadecylimidazole, 2-phenylimidazole, 2-ethyl 4-methylimidazole, 1-benzyl-2-methylimidazole, 1
-Propyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2ethyl-4methylimidazole, 1-
Cyanoethyl-2-undecylimidazole, 1
-cyanoethyl-2-phenylimidazole, 1
-Imidazoles exemplified by guanaminoethyl 2-methylimidazole, as well as trimellitic acid adducts of 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,
Tertiary amines such as N',N'-tetramethylbutanediamine and N-methylpiperidine; Phenols such as phenol, cresol, xylenol, resorcin, and phloroglucin; Lead naphthenate,
Organometallic salts such as lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, iron acetylacetonate; SnCl ₄ ,
Inorganic metal compounds such as ZnCl ₂ and AlCl ₃ ; peroxides such as benzoyl peroxide, lauroyl peroxide, caprylyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl di-perphthalate, etc. . The liquid curable resin composition produced by the production method of the present invention is
Taking advantage of its liquid properties, it is suitable for use in applications such as casting, potting, adhesives, and impregnation, and can also be used to provide flexibility, crack resistance, and fast curing properties depending on the application. , various modifiers and inorganic fillers may be added for viscosity adjustment and the like. The liquid curable resin composition produced by carrying out the present invention as described above has a polyfunctional maleimide-containing resin composition that has conventionally been solid at room temperature, but has almost no deterioration in its heat resistance. Since it is a liquid resin composition at room temperature, there is no need to make it into a varnish using a solvent, dry it in a subsequent process, or melt it by heating, as in the past, and it has high industrial value. be. The present invention will be explained in more detail below using Examples and Comparative Examples. Example 1 421 g of bis(4-maleimidophenyl)methane,
2,2-bis(4-cyanatophenyl)propane
281g and 98g of bisphenol F type epoxy resin (Epicote 807; manufactured by Yuka Ciel Co., Ltd.) at 135℃
After reacting for 90 minutes, cool to 65℃ and add 200g of divinylbenzene (purity 57%, manufactured by Sankyo Kasei Co., Ltd.)
was added and stirred for 30 minutes while cooling to obtain a liquid resin composition with a viscosity (B-type viscometer) of 210 cps/25°C. Add 0.15 g of zinc octylate (zinc content 18%) to 300 g of the obtained liquid resin composition, stir well, and then heat at 170°C for 2 hours under pressure and then at 240°C for 3 hours to harden to a thickness of 4 mm. I got something. 10 of the cured product
A sample of mm x 80 mm x 4 mm was placed in a constant temperature bath at 280℃ for 500 minutes.
The bending strength retention rate and weight loss rate before and after being left for a period of time were measured (abbreviated as 280°C heat resistance test). The results are shown in Table-1. Example 2 420g of bis(4-maleimidophenyl)methane
and bisphenol A type epoxy resin (Epicote)
828; manufactured by Yuka Ciel Co., Ltd.) was reacted at 135°C for 90 minutes, and then cooled to 70°C, and 400 g of divinylbenzene (purity 57%; manufactured by Sankyo Kasei Co., Ltd.) was added and stirred for 2 hours while cooling. . A liquid resin composition with a viscosity of 85 cps/25°C was obtained. Add 2-ethyl to 300 g of the obtained liquid resin composition.
After adding 1.5 g of 4-methylimidazole and 1.5 g of dicumyl peroxide and stirring well, a cured product was obtained in the same manner as in Example 1, and further a heat resistance test at 280°C was conducted. The results are shown in Table-1. Example 3 400g of bis(4-maleimidophenyl)methane
100g of novolac-type cyanate ester derived from phenol novolak resin (XPS-4225B; manufactured by Gunei Kagaku Co., Ltd.) with a softening point (ring and ball method) of 45°C was heated at 80°C.
After mixing for 5 minutes, the mixture was cooled to 50° C., 500 g of divinylbenzene (purity 57%) was added, and the mixture was stirred for 1 hour while cooling. The viscosity of the resulting resin composition was 105 cps/25°C. After adding 1.5 g of benzoyl peroxide to 300 g of the obtained resin composition and stirring well, a cured product was obtained in the same manner as in Example 1, and a heat resistance test at 280° C. was conducted. The results are shown in Table-1. Example 4 90 g of bis(4-maleimidophenyl)methane and 2,2-bis(4-cyanatophenyl)propane
After reacting 810g at 140°C for 2 hours, the mixture was cooled to 40°C, 100g of divinylbenzene was added, and the mixture was stirred for 10 minutes. A liquid resin composition with a viscosity of 15,000 cps/25°C was obtained. After adding 0.15 g of zinc octylate to 300 g of the obtained resin and stirring well, a cured product was obtained in the same manner as in Example 1, and a heat resistance test at 280° C. was conducted. The results are shown in Table-1. Example 5 441 g of bis(4-maleimidophenyl)methane,
2,2-bis(4-cyanatophenyl)propane
132 g, 57 g of novolak type cyanate ester derived from phenol novolak resin (MP-1200, manufactured by Gunei Kagaku Co., Ltd.) with a number average molecular weight of 330, and 20 g of novolak type epoxy resin (Epicote 152; manufactured by Yuka Shell Co., Ltd.) to 140 g. After reacting for 90 min at 60 °C
Cool to ℃ and add 200 g of divinylbenzene (purity 80%; manufactured by Sankyo Kasei Co., Ltd.) and trimethylolpropane trimethacrylate (TMPT; manufactured by Shin Nakamura Chemical Co., Ltd.).
150 g was added and stirred for 30 minutes while cooling to obtain a liquid resin composition. The viscosity was 950 cps/25°C. 270g of the obtained liquid resin composition was maleated 1,
2 Polybutadiene (BN1015; manufactured by Nippon Soda Co., Ltd.) 15
g and urethane-modified polybutadiene (Poly bd
After adding 15 g of HPT-9PA (manufactured by Idemitsu Petrochemical Co., Ltd.) and further adding 0.15 g of zinc octylate and stirring well, a cured product was obtained in the same manner as in Example 1.
A 280℃ heat resistance test was conducted. The results are shown in Table-1. Comparative Example 1 A resin composition was obtained in the same manner as in Example 1 except that divinylbenzene was not added. The viscosity of the obtained resin composition was so high that it could not be measured with a B-type viscometer (capable of measuring up to 10,000 cps) at 25°C. Furthermore, a cured product was obtained in the same manner as in Example 1, and heated at 280°C.
A heat resistance test was conducted. The results are shown in Table-1. Comparative Example 2 A resin composition was obtained in the same manner as in Example 2 except that divinylbenzene was not added. The viscosity of the obtained resin composition was so high that it could not be measured with the B-type viscometer at 25°C. Furthermore, a cured product was obtained in the same manner as in Example 2, and heated at 280°C.
A heat resistance test was conducted. The results are shown in Table-1. Comparative example 3 Bis(4-maleimidophenyl)methane at 170
Although the mixture was heated and stirred at 25°C, no liquid resin was obtained at 25°C, and the resin was solid at all reaction times. Furthermore, bis(4-maleimidophenyl)methane
1.5 g of benzoyl peroxide was mixed in powder form with 300 g, and a cured product was obtained in the same manner as in Example 1.
A heat resistance test was conducted. The results are shown in Table-1. Comparative Example 4 A resin composition was obtained in the same manner as in Example 4 except that divinylbenzene was not added. The resulting resin composition had a viscosity so high that it could not be measured with the B-type viscometer at 25°C. Furthermore, a cured product was obtained in the same manner as in Example 4, and heated at 280°C.
A heat resistance test was conducted. The results are shown in Table-1. Comparative Example 5 A resin composition was obtained in the same manner as in Example 5 except that divinylbenzene was not added. The resulting resin composition had a viscosity so high that it could not be measured with the B-type viscometer at 25°C. Furthermore, a cured product was obtained in the same manner as in Example 5, and heated at 280°C.
A heat resistance test was conducted. The results are shown in Table-1. Comparative Example 6 A resin composition was obtained in the same manner as in Example 1, except that diallyl phthalate (Daiso tap monomer; manufactured by Osaka Soda Co., Ltd.) was used instead of divinylbenzene. The viscosity of the obtained resin composition was 4500 cps/at 25°C.
It was 25℃. Furthermore, a cured product was obtained in the same manner as in Example 1, and heated at 280°C.
A heat resistance test was conducted. The results are shown in Table-1. Comparative Example 7 Glycidyl ester of tertiary synthetic saturated carboxylic acid (Cardilla E10; instead of divinylbenzene)
A resin composition was obtained in the same manner as in Example 1 except that a resin composition (manufactured by Yuka Ciel Co., Ltd.) was used. The resulting resin composition had a viscosity of 1020 cps/25°C. Furthermore, a cured product was obtained in the same manner as in Example 1, and heated at 280°C.
A heat resistance test was conducted. The results are shown in Table-1. Comparative Example 8 A resin composition was obtained in the same manner as in Example 1 except that styrene monomer was used instead of divinylbenzene. The viscosity of the obtained resin composition is 200 cps/25
It was warm at ℃. Furthermore, an attempt was made to obtain a cured product in the same manner as in Example 1, but the process was discontinued due to severe volatilization during pressure/heat molding.

【table】

[Table] Example 6 480g of bis(4-maleimidophenyl)methane,
Bisphenol A type epoxy resin (Epicote
After reacting 288 g of 828 (manufactured by Yuka Ciel Co., Ltd.) and 32 g of dichloroaminodiphenylmethane (Kyuamine MT; manufactured by Ihara Chemical Co., Ltd.) at 140°C for 3 hours,
200 g of divinylbenzene was added to obtain a liquid resin composition. The viscosity was 2200 cps. Comparative Example 9 The same procedure as Example 1 was carried out except that the temperature when divinylbenzene was added was 120°C. After adding divinylbenzene, gelation occurred and became agar-like, and no liquid resin composition was obtained. Comparative Example 10 Same as Example 2 except that the temperature when adding divinylbenzene was 20°C. The reacted resin was almost solid and could not be stirred, so divinylbenzene could not be mixed.

Claims (1)

[Claims] 1. Mix or pre-react 2 to 90 wt% of polyfunctional maleimides and 4 to 90 wt% of thermosetting resin at 70 to 200°C, then add and mix 5 to 60 wt% of divinylbenzene at 30 to 100°C. 1. A method for producing a curable resin composition that is liquid at room temperature and is characterized by cooling the composition.