JPS6320243B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a heat-resistant resin composition, and more specifically,
The present invention relates to a heat-resistant resin composition that has excellent storage stability at around room temperature and has fast curing properties. In recent years, the capacity of electrical or electronic equipment has increased,
Insulating materials with excellent heat resistance are required as devices become smaller and lighter, have higher reliability, and improve productivity. Conventionally, as heat-resistant resins, heterocyclic species combinations represented by polyimide, silicone resins, and the like are known. However, most of the heterocyclic polymers are condensation type, and they produce volatile components during curing, have poor moldability, take a long time to cure, and can only be used in certain polar solvents for applications such as varnishes. There are various difficulties, especially in the fields of molding materials, laminated materials, and powder materials. On the other hand, silicone resins have low mechanical strength at high temperatures, poor adhesion, and high moisture permeability, which limits their uses. To improve these drawbacks, it is known to use polyimide in combination with epoxy compounds, unsaturated polyesters, and the like. but,
In this case as well, there are problems in providing fast curing properties, solubility in various solvents, material cost, etc. The present invention has been made in view of the above-mentioned current situation, and its purpose is to
By simply heating it for a short time (1 to 30 minutes), it is converted into a cured product with excellent high-temperature strength, has excellent storage stability at temperatures around room temperature, and has excellent heat resistance and flexibility that can be molded at low pressure. It is an object of the present invention to provide a resin composition that has the following properties. In order to achieve the above object, the present invention has the following configuration. That is, the heat-resistant resin composition of the present invention has 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. _R5 and _R6
is hydrogen, methyl group, ethyl group, trifluoromethyl group, or trichloromethyl group, which may be the same or different] and triallyl cyanurate. It is a heat-resistant resin composition comprising 5 to 500 parts by weight of a type compound. The etherimide compound represented by the general formula [] is 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. _R5 and
R ₆ is hydrogen, a methyl group, an ethyl group, a trifluoromethyl group or a trichloromethyl group, and may be the same or different. ] A diamiso compound having an ether bond represented by the general formula [] It can be obtained by reacting an ethylenically unsaturated dicarboso acid anhydride represented by the following formula: [wherein D is a divalent group having two carbon atoms]. In addition, examples of the ethylenically unsaturated dicarboxylic anhydride represented by the general formula [] include maleic anhydride, citraconic anhydride, itaconic anhydride,
Pyrosinconic anhydride, dichloromaleic anhydride,
Or these compounds and cyclodiene
At least one of Dielo and Alder adducts is used. The reaction method for obtaining the general formula [] from the general formula [], and [] is not particularly limited, but in the first step, the 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. _R5 and _R6
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 ether maleamic acid is produced. Known methods are used for this purpose. An advantageous method consists in bringing into contact a diamine compound having an ether linkage of the general formula [] and an ethylenically unsaturated carboxylic acid anhydride of the general formula [] in an organic liquid which is a solvent for both. Commonly used solvents include dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, N-methylpyrrolidone,
-Methylcaprolactam, tetrahydrofuran,
Examples include dioxane, acetone, and diethyl ketone. Next, in the second step, a known method described in USP 3018290, USP 3018292, USP 3127414, etc. may be used to generate an imide ring by cyclizing and dehydrating the ether maleamic acid. For dehydration from the amic acid of formula [], acetic anhydride is used as the anhydride in an amount of 1.05 to 1.5 mol per 1 mol of the amic acid group, and a tertiary amine is used in an amount of 0.15 to 1.5 mol per 1 mol of the amic acid group. It is preferable to carry out the reaction in acetone by adding 0.5 mol (for example, triethylamine) and further in the presence of 0.5 to 0.05 mol of nickel acetate per 1 mol of amic acid group as a catalyst. Examples of the etherimide compound represented by the general formula [ ] of the present invention include 2,2-bis[4
-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[3-methyl-4-(4-maleimidophenoxy)phenyl]propane, 2,
2-bis[3-chloro-4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[3-bromo-4-(4-maleimidophenoxy)
Phenyl] propane, 2,2-bis[3-ethyl-4-(4-maleimidophenoxy) phenyl]
Propane, 2,2-bis[3-propyl-4-
(4-maleimidophenoxy)phenyl]propane, 2,2-bis[3-isopropyl-4-(4
―Maleimidophenoxy)phenyl]propane,
2,2-bis[3-butyl-4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[3-sec-butyl-4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[3-methoxy-4-(4-maleimidophenoxy)phenyl]propane, 1,1-bis[4-
(4-maleimidophenoxy)phenyl]ethane,
1,1-bis[3-methyl-4-(4-maleimidophenoxy)phenyl]ethane, 1,1-bis[3-chloro-4-(4-maleimidophenoxy)
phenyl]ethane, 1,1-bis[3-bromo-
4-(4-maleimidophenoxy)phenyl]ethane, bis[4-(4-maleimidophenoxy)
phenyl]methane, bis[3-methyl-4-(4
-maleimidophenoxy)phenyl]methane, bis[3-chloro-4-(4-maleimidophenoxy)phenyl]methane, bis[3-bromo-4-
(4-maleimidophenoxy)phenyl]methane,
1,1,1,3,3,3-hexafluoro-2,
2-bis[4-(4-maleimidophenoxy)phenyl]propane, 1,1,1,3,3,3-hexachloro-2,2-bis[4-(4-maleimidophenoxy)phenyl] Propane, 3,3-bis[4-(4-maleimidophenoxy)phenyl]pentane, 1,1-bis[4-(4-maleimidophenoxy)phenyl]propane, 1,1,
1,3,3,3-hexafluoro-2,2-bis[3,5-dibromo-4(4-maleimidophenoxy)phenyl]propane, 1,1,1,3,3,
Examples include 3-hexafluoro-2,2-bis[3-methyl-4(4-maleimidophenoxy)phenyl]propane, and one or more of these can be used. The triallyl cyanurate compounds that can be used in this invention are preferably allyl esters of polyhydric carboxylic acids or cyanuric acid, such as triallyl trimellitate, diallyl phthalate, diallyl isophthalate, P.P-diallyloxycarbonyl Diphenyl ether, m,p'-diallyloxycarbonyl diphenyl ether, o,p'-diallyloxycarbonyl diphenyl ether, triallyl cyanurate, triallyl cyanurate prepolymer, and the like. These polyhydric carboxylic acid allyl esters can also be used in combination. In the present invention, the ratio of polyhydric carboxylic acid allyl ester to the etherimide compound represented by the general formula [] is determined depending on the purpose of use, but in general, the etherimide compound The polycarboxylic acid allyl ester is used in an amount of 5 to 500 parts by weight, preferably 50 to 350 parts by weight, based on 100 parts by weight in terms of moldability and properties of the cured resin. Moreover, an unsaturated polyester resin can also be added to the resin composition of the present invention. The unsaturated polyester resin as used in the present invention refers to unsaturated dibasic acids, saturated dibasic acids and their anhydrides, or lower alkyl ester derivatives thereof, diols, alkylene monooxides, derivatives thereof, etc., and the presence or absence of a catalyst. A polyester resin base containing unsaturated groups synthesized by condensation or addition polymerization using reactions such as esterification and transesterification in the presence of ethylene-based (e.g. vinyl groups, allyl groups, etc.) It consists of a mixture of a polymerizable compound and a peroxide catalyst. In addition, vinyl ester resins obtained by reacting epoxy compounds such as bisphenol A type and novolac type with methacrylic acid or acrylic acid are also useful. Here, typical unsaturated dibasic acids and saturated dibasic acids include maleic acid, maleic anhydride, fumaric acid, chloromaleic acid, dichloromaleic acid, citraconic acid, citraconic anhydride, mesaconic acid, and itaconic acid. acid, succinic acid, adipic acid,
Sebacic acid, azelaic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, methylglutaric anhydride, pimelic acid, hexahydrophthalic acid and its anhydride, tetrahydrophthalic acid, carpicic anhydride, hectonic acid and its anhydride tetrachlorophthalic acid and its anhydride, tetrabromophthalic acid and its anhydride,
These lower alkyl esters are used, and diol components include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, and 2,2-diethyl. Propanediol, 1,3-neopentyl glycol, dibromeneopentyl glycol, bisphenol dioxyethyl ether, hydrogenated bisphenol A,
2,2-di(4-hydroxypropoxyphenyl)propane, ethylene oxide, propylene oxide, 3,3,3-trichloropropylene oxide, phenyl glycidyl ether, allyl glycidyl ether, etc. are used. In addition, if necessary, 3
A functional or higher polybasic acid and/or a polyhydric alcohol may be used in combination. Examples of crosslinking agents include styrene, vinyltoluene, α-methylstyrene, divinylbenzene, diallyl phthalate, diallyl phthalate prepolymer, chlorostyrene, dichlorostyrene, diallylbenzenephosphonate, diallylaryl phosphinate, acrylic ester, and methacrylic acid. Acid ester, triallyl cyanurate, triallyl cyanurate prepolymer, tribromophenol allyl ether, etc. are used. In the present invention, the acid component, alcohol component, and crosslinking agent are not limited to one type, and two or more types can be used in combination. Furthermore, various modifications and addition of modifiers are also possible. Further, the unsaturated polyester resin is not limited to one type, but a mixture of two or more types is also possible. It is desirable to add a polymerization initiator to the resin composition of the present invention in order to complete its curing by short-term heating. Such polymerization initiators include benzoyl peroxide, p-chloro-
Benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, caprylyl peroxide,
lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, bis(1-hydroxy microhexyl peroxide), hydroxyheptyl peroxide, t-butyl hydroperoxide, p-menthane hydroperoxide, t-butyl peroxide Organic peroxides such as benzoate, t-butyl peracetate, t-butyl peroctoate, t-butyl peroxyisobutyrate, and di-t-butyl diperphthalate are useful, and one or more thereof can be used. In the present invention, it is also possible to use, in combination with the above-mentioned polymerization catalyst, known promoters such as mercaptans, sulfites, β-diketones, metal chelates, and metal mineral acids. In addition, in order to improve the storage stability of the resin composition at room temperature, for example, quinones such as p-benzoquinone, naphthoquinone, and phenanthraquinone, hydroquinone, p-
Known polymerization inhibitors such as phenols such as t-butylcatechol and 2,5-di-t-butylhydroquinone, nitro compounds, and metal salts can be used depending on the purpose. Furthermore, various materials may be blended into the resin composition of the present invention depending on its use. That is, for example, for use as a molding material,
Zircon, silica, alumina, aluminum hydroxide, natania, zinc white, calcium carbonate, magneite, clay, kaolin, talc, silica sand, crow, fused silica glass, asbestos, mica, various whiskers, carphone flak, graphite, molybdenum disulfide, etc. Inorganic fillers such as, mold release agents such as higher fatty acids and waxes, and coupling agents such as epoxy silane, vinyl silane, borane and alkoxy titanate compounds are blended. Further, flame retardant imparting agents such as halogen-containing compounds, antimony oxide, and phosphorus compounds can be used as necessary. It can also be used as a solution, such as a varnish. The solvent used in this case is
N-metal-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide,
N,N-dimethylformamide, N-methylformamide, dimethylsulfoxide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, hexamethylphosphoramide,
Examples of solvents include pyricine, dimethylsulfone, tetramethylsulfone, dimethyltetramethylenesulfone, and phenolic solvents include phenol, cresol, xylenol, and the like. The above materials may be used alone or in combination of two or more. Next, the present invention will be specifically explained with reference to Examples. Examples 1 to 20 Ten types of blended compositions shown in Table 1 were prepared. Each blended composition was kneaded at 50 to 70°C for 10 minutes, and then cooled to obtain the desired heat-resistant resin composition. Each composition was transfer molded at 170° C., 70 kg/cm ² for 5 minutes to prepare specimens for measuring various characteristics. Tables 1 and 2 show the glass transition point,
Bending strength at 180℃, flexural modulus, 200℃, 30
The heating deterioration characteristics after being left in the sun and the storage stability of the material were shown. All cured products have a glass transition point of 180℃ or higher.
Bending strength at 180℃, 400Kg/ ^cm2 or more, strength retention after 30 days at 200℃, 80% or more, flexural modulus 1.30×
It has excellent heat resistance of less than 10 ³ Kg/mm ² and flexibility.

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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. _R5 and _R6
is hydrogen, methyl group, ethyl group, trifluoromethyl group, or trichloromethyl group, which may be the same or different] and triallyl cyanurate. A heat-resistant resin composition comprising 5 to 500 parts by weight of a type compound.