JPS629250B2 - - Google Patents

Description

[Detailed description of the invention]

In recent years, epoxy resin has been increasingly used as an insulating material, coating material, sealing material, laminated material, and prepreg material in fields such as electrical equipment and electronic components, and its importance has also increased. There is. Along with this, the requirements for the performance of epoxy resins have become stricter, and improvements in the thermal stability, mechanical strength, electrical properties, and curing properties of cured epoxy resins are particularly important for molding materials, laminated materials, impregnated varnishes, and prepregs. It is desired in almost every field. However, regarding the thermal stability of existing cured epoxy resins, the heat deformation temperature of ordinary bisphenol type epoxy resins combined with conventionally known curing agents is lower than that when room temperature curing polyamides are used. 40 to 50°C, 50 to 60°C when polyamines are used, and 70 to 80°C when aromatic polyamines are used. Furthermore, when a heat-curable aromatic polyamine is used, the temperature is relatively high at 100 to 120°C, but it has the disadvantage of low mechanical strength at high temperatures, especially low bending strength and impact strength. In addition, the thermal stability is limited to 100 to 150℃ when room temperature curing polyamine is used, and 150 to 200℃ when heat curing polyamine is used, and if exposed to such temperatures for a long time, Thermalization causes a decrease in strength, which is undesirable. As described above, it is difficult to achieve both heat resistance and mechanical strength, especially flexibility. Furthermore, in terms of curing properties, stability at room temperature and 150%
It is difficult to achieve both fast curing properties at temperatures up to 200°C, and it has been difficult to provide stable molding processability using conventional amine curing agents. On the other hand, when a carboxylic acid anhydride is used as a curing agent, it is possible to improve the thermal stability and mechanical strength of the cured product to some extent, but it is difficult to achieve both heat resistance and flexibility. In addition, as with amine-based products, it is difficult to achieve both stability at room temperature and fast curing at high temperatures, and the high hygroscopicity of carboxylic acid anhydrides leads to the problem of poor moisture resistance. be. Under these circumstances, development of epoxy resin compositions with excellent heat resistance is progressing. For example, there are those that use polyamino bismaleimide or polyhydroxylstyrene as an epoxy curing agent. However, although these cases also have excellent heat resistance, there is a problem that flexibility is impaired and cracks occur in the cured product when the metal insert is actually molded. The present invention was made in view of this situation, and its characteristics are based on the general formula [] [In the formula, R ₁ to _{R 4} represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and may be the same or different from each other. R ₅ and R ₆ are hydrogen, a methyl group, an ethyl group, a trifluoromethyl group, or a trichloromethyl group, and may be the same or different. D is a divalent organic group having 2 to 24 carbon atoms] and an epoxy resin composition containing an etherimide compound and a polyfunctional epoxy compound. The present invention is based on the general formula [] The etherimide compound represented by [wherein R ₁ to R ₄ , R ₅ , R ₆ , and D are the same as above],
General formula [] (In the formula, R ₁ to _{R 4} represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and may be the same or different from each other. R ₅ and R ₆ are hydrogen, a methyl group, ethyl group, trifluoromethyl group, or trichloromethyl group, which may be the same or different from each other), and a diamine compound having an ether bond represented by the general formula [] [In the formula, D is a divalent organic group having 2 to 24 carbon atoms. ] It can be obtained by reacting an ethylenically unsaturated dicarboxylic acid anhydride represented by: Also, general formula [] [In the formula, D is a divalent organic group having 2 to 24 carbon atoms. Examples of the ethylenically unsaturated dicarboxylic anhydride represented by
At least one type of Diels/Alder adduct is used. The reaction method for obtaining the general formula [] of the present invention from the general formula [] and [] is not particularly limited, but as an example, the general formula []
In order to produce etherimide compounds,
In the first step, the following formula [] [In the formula, R ₁ to _{R 4} represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and may be the same or different from each other. R ₅ and R ₆ are hydrogen, a methyl group, an ethyl group, a trifluoromethyl group, or a trichloromethyl group, and may be the same or different. D is 2 to 24
It is a divalent organic group with 5 carbon atoms. ] There is a method for producing ether maleamic acid. Known methods are used for this purpose. For example, there is a method in which a diamine compound having an ether bond of the general formula [] and an ethylenically unsaturated dicarboxylic acid anhydride of the general formula [] are brought into contact with each other in an organic liquid that is a solvent for both. here,
Commonly used solvents include dimethylformamide, dimethylacetamide, dimethysulfoxide, N-methylpyrrolidone, N-
Examples include methylcaprolactam, tetrahydrofuran, dioxane, acetone, and diethyl ketone. Next, in the second step, the ether maleamic acid is cyclized and dehydrated to generate an imide ring. The method is USP3018290, US
Known methods described in P3018292 and USP3127414 may be used. That is, acetic anhydride is used as an anhydride at a concentration of 1.05 to 1.05 to 1.05 per mole of amic acid group
Use 1.5 mol of tertiary amine, such as triethylamine, in an amount of 0.15 to 1 mol per mol of amic acid group.
This method is carried out in acetone by adding 0.5 mol of nickel acetate and further adding 0.5 to 0.05 mol of nickel acetate per 1 mol of amic acid group as a catalyst. In the present invention, aromatic diamines having an ether bond represented by the general formula [ ] include, for example, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[3-methyl -4-(4-aminophenoxy)phenyl]
Propane, 2,2'-bis[3-chloro-4-(4
-aminophenoxy)phenyl]propane, 2.
2'-bis[3-bromo-4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[3-
Ethyl-4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[3-propyl-4
-(4-aminophenoxy)phenyl]propane, 2,2'-bis[3-isopropyl-4-(4
-aminophenoxy)phenyl]propane, 2.
2'-bis[3-butyl-4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[3-
sec-butyl-4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[3-methoxy-
4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[3-ethoxy-4-(4-aminophenoxy)phenyl]propane, 1,1-
Bis[4-(4-aminophenoxy)phenyl]
Ethane, 1,1-bis[3-methyl-4-(4-
Aminophenoxy)phenyl]ethane, 1,1-
Bis[3-chloro-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-bromo-4-(4-aminophenoxy)phenyl]ethane, bis[4-(4-aminophenoxy)phenyl]methane , bis[3-methyl-4-(4-aminophenoxy)phenyl]methane, bis[3-
Chloro-4-(4-aminophenoxy)phenyl]methane, bis[3-bromo-4-(4-aminophenoxy)phenyl]methane, 1.1.1.
3,3,3-hexafluoro-2,2-bis[4
-(4-aminophenoxy)phenyl]propane, 1, 1, 1, 3, 3, 3-hexachloro-
2,2-bis[4-(4-aminophenoxy)phenyl]propane, 3,3-bis[4-(4-aminophenoxy)phenyl]pentane, 1,1-
Bis[4-(4-aminophenoxy)phenyl]
Propane, 1,1,1,3,3,3-hexafluoro-2,2bis[3,5-dimethyl-4-(4
-aminophenoxy)phenyl]propane, 1.
1,1,3,3,3-hexafluoro-2,2-
Bis[3,5-dibromo-4(4-aminophenoxy)phenyl]propane, 1, 1, 1, 3,
3,3-hexafluoro-2,2-bis[3-methyl-4-(4-aminophenoxy)phenyl]
There is propane, etc. The lower alkyl group and lower alkoxy group represented by R ₁ to _{R 4} in the aromatic diamine represented by the general formula [] have about 10 or less carbon atoms. Next, examples of epoxy compounds include glycidyl ether of bisphenol A, butadiene diepoxide, 3,4-epoxycyclohexylmethyl-(3,4-epoxy)cyclohexanecarboxylate, vinylcyclohexane dioxide, 4,4'-diepoxide, (1,2-epoxyethyl) diphenyl ether, 2,2-bis(3,4-epoxycyclohexyl)propane, glycidyl ether of resorcinol, diglycidyl ether of phloroglucine, diglycidyl ether of methylphloroglucine, bis -(2,3-epoxycyclopentyl)ether, 2-(3,4-epoxy)
Cyclohexane-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, bis-
(3,4-epoxy-6-methylcyclohexyl)adipate, difunctional epoxy compounds such as N・N'-m-phenylenebis(4,5-epoxy-1,2-cyclohexanedicarboximide, triglycidyl of para-aminophenol) Ether, polyacrylic glycidyl ether, 1.
3,5-tri(1,2-epoxyethyl)benzene, 2,2',4,4'-tetraglycidoxybenzophenone, polyglycidyl ether of phenol formaldehyde novolak resin, triglycidyl ether of glycerin, triglycidyl ether of glycerin, Trifunctional or higher functional epoxy compounds such as triglycidyl ether of methylolpropane, halogenated epoxy compounds such as brominated epoxy, or hydantoin epoxy compounds are used. In the present invention, the blending ratio of the etherimide compound represented by the general formula [] and the polyfunctional epoxy compound is generally 100% of the former.
If the latter is used in an amount of 10 to 1000 parts by weight, it is possible to obtain a cured product having heat resistance and flexibility, which is the object of the present invention. Further, the curing method of the epoxy resin composition of the present invention is not particularly limited, but
It is sufficiently cured by heating at ~200°C for 1 to 30 minutes. The epoxy resin composition of the present invention can contain a phenol novolak resin as a component, if necessary. That is, one or more of phenols such as phenol, cresol, xylenol, resorcinol, chlorophenol, phenylphenol or bisphenol A and aldehydes such as formaldehyde, acetaldehyde and butyraldehyde are combined in the presence of an acidic catalyst. A resin obtained by addition condensation can be added. These phenol novolac resins are generally blended in a composition containing an etherimide compound of the general formula [] and a polyfunctional epoxy compound in a range of 10 to 50 parts by weight per 100 parts by weight of the polyfunctional epoxy compound. be done. By adding the phenol novolac resin, the storage stability and mold release properties of the resin composition are improved, and the surface of the molded cured product becomes even smoother, improving its appearance. If the amount of phenol novolak resin is too large, problems such as a decrease in hardness when heated and a decrease in heat resistance may occur. Curability and moldability can be improved by adding a primary amine compound such as monoamine diamine, triamine, tetramine, pentamine, etc. to the epoxy resin composition of the present invention. In addition, depending on the purpose and use, the resin composition of the present invention may include an acrylonitrile butadiene compound having at least one of a terminal carboxyl group, a terminal amino group, and a terminal hydroxyl group, a phenoxy resin, diallyl phthalate, diallyl phthalate prepolymer, It is also possible to blend known resins such as triallyl cyanurate, triallyl cyanurate prepolymer, butadiene, polystyrene, and unsaturated polyester. Next, a known curing accelerator for epoxy resins, such as a BF ₃ -amine complex salt, can be added to the epoxy resin composition of the present invention for the purpose of imparting rapid curing properties. The amount of the curing accelerator to be added is usually 0.01 to 10 parts by weight per 100 parts by weight of the mixture of the etherimide compound represented by the general formula [] and the polyfunctional epoxy compound. . Further, in order to crosslink the etherimide compound represented by the general formula [] and the polyfunctional epoxy compound, a known organic peroxide can be used as a catalyst. Furthermore, the curing accelerator and catalyst can also be used together. Furthermore, the composition of the present invention has various uses,
Depending on the purpose, one type or a combination of two or more of the following various materials can be used. That is, for example, when used as a molding material, zircon,
Silica, fused silica glass, clay, hydrated alumina, calcium carbonate, quartz glass, glass, asbestos, whiskers, gypsum, magnesite, mica, kaolin, talc, graphite, cement, carbonyl iron, barium compounds, ferrite, lead compounds , molybdenum disulfide, zinc white, titanium white,
Fillers such as carbon black, silica sand, and wollastonite, mold release agents such as fatty acids and waxes, and coupling agents such as epoxy silane, vinyl silane, borane compounds, and alkoxy titanate compounds can be used. It is also possible to use known flame retardants such as antimony and phosphorus, or known flexibilizers. In addition, when used as a varnish, various solvents such as N-methyl-2-pyrrolidone,
N/N-dimethylacetamide, N/N-dimethylformamide, N/N-diethylformamide, N-methylformamide, dimethyl sulfoxide, N/N-diethylacetamide, hexamethylphosphoramide, pyridine, dimethylsulfone, tetramethylsulfone , dimethyltetramethylene sulfone, phenol, cresol, xylenol, and the like can be used. Moreover, toluene, xylene, petroleum naphtha, etc. can also be used in combination if the amount used is a small amount. The epoxy resin composition of the present invention is converted into a cured product with excellent high-temperature strength by heating at a relatively low temperature for a short time, has excellent storage stability at temperatures around room temperature, and can be molded at low pressure. It is extremely useful in the fields of laminated materials, prepregs, impregnated varnishes, paints, adhesives, etc. Next, the present invention will be explained by examples. In addition,
Parts in each example indicate parts by weight. Examples 1 to 9 As epoxy compounds, novolac type epoxy (manufactured by Ciba Corporation; epoxy equivalent: 225), bisphenol A type epoxy (Epicoat 1001, manufactured by Ciel Corporation;
Epoxy equivalent: 475), 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane and 2,2'-bis[3-
Using methyl-4-(4-maleimidophenoxy)phenyl]propane, nine types of compositions were prepared with various blending ratios as shown in Table 1, and to these, 75 weight of silica powder was added as a filler. %, 2 parts of stearic acid as a mold release agent, 1 part of epoxy silane (KBM403 manufactured by Shin-Etsu Chemical) as a coupling agent, and 1 part of carbon black as a coloring agent. Each blend was roll-kneaded at 70-80°C for 6 minutes, cooled and pulverized to obtain the desired epoxy resin composition. Each composition was transfer molded under the conditions of 170° C., 70 kg/cm ² , and 5 minutes to prepare specimens for measuring various characteristics. Table 1 shows the bending strength, heat deterioration characteristics, and storage stability of the material. However, in Examples 4, 8, and 9, 1 part of dicumyl peroxide was added.

[Table] Examples 10 to 14 40 of 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane to Epicote 828,
After mixing 100 and 200 parts as shown in Table 2,
A heating reaction was carried out at 80 to 100°C for 15 minutes to obtain three types of prepolymers. These three prepolymers, an amine compound, an epoxy compound, and various fillers were blended in the proportions shown in Table 2, and then kneaded and heat molded and cured under the same conditions as in Examples 1 to 9 above to obtain various properties. A specimen was prepared. Table 2 shows the measurement results of various properties.

【table】

[Table] In addition, in the above examples, the volume resistivity at 80°C is 1 to 5 × 10 ¹² Ωcm for Examples 1 to 5,
Examples 6 to 14 had a resistance of about 5×10 ¹¹ Ω·cm. Furthermore, the flame retardant grade of each example according to the UL-94 standard is V-1, and red phosphorus was added to those of Examples 1 to 5.
0.1 part, and 0.5 part of red phosphorus in Examples 6 to 14.
The one added was V-0.

Claims (1)

[Claims] 1. General formula [] [In the formula, R ₁ to _{R 4} represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and may be the same or different from each other. R ₅ and R ₆ are hydrogen, a methyl group, an ethyl group, a trifluoromethyl group, or a trichloromethyl group, and may be the same or different. D is 2 or
It is a divalent organic group with 24 carbon atoms. ] An epoxy resin composition comprising an etherimide compound represented by the following and a polyfunctional epoxy compound as essential components. 2 R ₁ to _{R 4} of the general formula [] are hydrogen, R ₅ ,
The epoxy resin composition according to claim 1, wherein R ₆ is a methyl group and D is -CH=CH-.