JPS6318604B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a thermosetting resin composition, and particularly to a thermosetting resin composition that undergoes a crosslinking reaction when heated to produce a cured product with excellent heat resistance. In recent years, as electric and electronic devices have become larger in capacity, smaller and lighter, more reliable, and more dense, organic materials with excellent heat resistance and flexibility are required as materials used in these devices. ing. Conventionally, resins with excellent heat resistance include polyimide, polybenzimidazole, and silicone, but all of these have the problem that their characteristic heat resistance decreases when they are imparted with flexibility. However, there were some points that needed to be improved in terms of moldability, moisture permeability and mechanical strength of the cured product. On the other hand, unsaturated polyester and epoxy resins have excellent flexibility but are inferior to the above-mentioned materials in terms of heat resistance. There is a strong demand for the development of materials that are compatible with flexibility. The present invention has been made in view of the current situation, and its purpose is to provide a thermosetting resin composition capable of producing a cured product with excellent heat resistance and flexibility. To summarize the present invention, the thermosetting resin composition of the present invention has the general formula (In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a chlorine atom or a bromine atom, and they are the same or different,
R ₅ and R ₆ are hydrogen atoms, methyl group, ethyl group, and trifluoromethyl group are trichloromethyl groups, which are the same or different, and D has an ethylenically unsaturated bond and has 2 to 24 It is characterized by containing an etherimide compound represented by (indicating an organic group having a carbon atom) and an unsaturated polyester resin. In the present invention, the etherimide compound represented by the general formula () is the following general formula: (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ represent the same atoms or groups as in the general formula ()) and a diamine compound having an ether bond represented by the following general formula (In the formula, D represents the same organic group as in the general formula ()). As the diamine compound having an ether bond represented by the above general formula (), 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)phenylpropane, 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, 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- Screw [4-
(4-aminophenoxy)phenyl]propane,
1,1,1,3,3,3-hexafluoro-2,
2-bis[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 and 1,1,1,3,
3,3-hexafluoro-2,2-bis[3-methyl-4-(4-aminophenoxy)phenyl]
Examples include propane. Examples of the ethylenically unsaturated dicarboxylic acid anhydride represented by the general formula () include maleic anhydride, citraconic anhydride, itaconic anhydride, pyrosinconic anhydride, and dichloromaleic anhydride. , at least one compound such as a Diels-Ander adduct of these compounds and a cyclodiene or the like can be applied. A reaction method for producing an etherimide compound represented by the general formula () from a diamine compound having an ether bond represented by the general formula () and an ethylenically unsaturated dicarboxylic acid anhydride represented by the general formula (). is not particularly limited; for example, in the first step, the general formula (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and D represent the same atoms, groups or organic groups as in the general formula ()) Manufacture. This reaction is advantageously carried out using a solvent in which both raw materials are brought into contact. Generally, commonly used solvents include dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, N-methylcaprolactam, tetrahydrofuran, dioxane, acetone, and diethylketone. Next, in the second step, the ether maleamic acid obtained above is cyclized and dehydrated to produce an imide ring.
Known methods described in 3018292 and 3127414 can be used. For dehydration from the ether maleamic acid represented by the general formula (), acetic anhydride is used in an amount of 1.05 to 1.5 mol per 1 mol of the amic acid group,
A tertiary amine (for example, triethylamine) is added in an amount of 0.15 to 0.5 mole per mole of amic acid group, and as a catalyst, an amount of 0.15 to 0.5 mole per mole of amic acid group is added.
It is suitable to carry out the reaction in the presence of 0.05 to 0.5 mol of nickel acetate using acetone as a solvent. In addition, the unsaturated polyester resin in the present invention is composed of unsaturated dibasic acids, saturated dibasic acids and their anhydrides, lower alkyl ester derivatives thereof, diols, alkylene monooxides, derivatives thereof, etc., and the presence or absence of a catalyst. Polyester resin matrix containing unsaturated groups synthesized by condensation or addition polymerization using reactions such as esterification and transesterification and the polymerizability of ethylene-based (e.g. vinyl groups, allyl groups, etc.) Compound,
and a mixture with a peroxide catalyst. In addition, vinyl ester resins obtained by reacting bisphenol A type and novolac type epoxy compounds 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, itaconic 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 anhydrides,
Tetrahydrophthalic acid, carpicic anhydride, Hett's acid and its anhydride, tetrachlorophthalic acid and its anhydride, tetrapromphthalic acid and its anhydride, lower alkyl esters thereof, etc. are used. Diol components include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, 2,2-diethylpropanediol-1,3, and neopentyl glycol. , dibrome neopentyl glycol, bisphenol dioxyethyl ether, hydrogenated bisphenol A, 2,2-di(4-hydroxypropoxyphenyl)propane, ethylene oxide, propylene oxide, 3,3,3-trichloropropylene oxide , 2-methyl-3,3,3-trichloropropylene oxide, phenyl glycidyl ether, and allyl glycidyl ether. Further, if necessary, a trifunctional or higher functional polybasic acid and/or a polyhydric alcohol may be used in combination within a range that does not impair the object of the present invention. Examples of crosslinking agents for unsaturated polyester resins include styrene, vinyltoluene, α-methylstyrene, divinylbenzene, diallyl phthalate, diallyl phthalate prepolymer, chlorstyrene, dichlorostyrene, bromstyrene, dibromstyrene, diallylbenzenephosphonate, diallyl. Aryl phosphinates, acrylic esters, methacrylic esters, triallyl cyanurate, triallyl cyanurate prepolymers, tripromophenol allyl ether, and the like are used. In addition, the acid component, alcohol component, and crosslinking agent are not limited to one type, but two or more types can be used in combination, and various modifications and modifiers can be added. Furthermore, unsaturated polyester resins can also be used. It is not limited to one type, but a mixture of two or more types is also possible. In the present invention, the blending ratio of the etherimide compound represented by the general formula () and the unsaturated polyester resin is not particularly limited, but in order to impart heat resistance, the latter should be in the range of 10 to 100 parts by weight per 100 parts by weight of the former. It is appropriate to It is desirable to add a polymerization initiator to the resin composition of the present invention in order to complete its curing by heating for a short time. Examples of such polymerization initiators include benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, caprylyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, Bis(1-hydroxycyclohexyl peroxide), hydroxyhebutyl peroxide, tertiary butyl hydroperoxide,
p-menthane hydroperoxide, tertiary butyl perbenzoate, tertiary butyl peracetate, tertiary butyl peroctoate, tertiary butyl peroxyisobutyrate, di-tertiary butyl diperphthalate, etc. Organic peroxides are useful, and one or more of them can be used. In the present invention, it is also possible to use known promoters such as mercaptans, sulfites, β-diketones, metal chelates, and metal soaps in combination with the above-mentioned polymerization catalyst. 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-
Tertiary-butylcatechol and 2,5-di-tertiary
Known polymerization inhibitors such as phenols such as butylhydroquinone and nitro compounds and metal salts can be used if desired. Furthermore, various materials may be blended into the resin composition of the present invention depending on its use. For example, for use as a molding material, zircon oxide, silica, alumina, aluminum hydroxide, titania,
Subsalt flower, calcium carbonate, magnesite, clay, kaolin, talc, silica sand, glass, fused silica glass, asbestos, mica, various whiskers,
Inorganic fillers such as carbon black, graphite and molybdenum disulfide, 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. Ru. Further, flame retardant agents such as halogen-containing compounds, antimony oxide, and phosphorus compounds can be used as necessary. Various polymers, such as polystyrene, polyethylene, polybutadiene, polymethyl methacrylate, polyacrylic acid ester, acrylic acid ester-methacrylic acid ester copolymer, phenolic resin, epoxy resin, melamine resin, or urea resin, are also known modified resins. A quality agent can be used. It can also be used as a solution, such as a varnish. The solvent used at that time is N
-Methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide,
N,N-diethylformamide, N-methylformamide, dimethylsulfoxide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, hexamethylphosphoramide,
Examples include pyridine, dimethylsulfone, tetramethylsulfone, and dimethyltetramethylenesulfone, and examples of the phenolic solvent group include phenol, cresol, and xylenol. The above materials may be used alone or in combination of two or more. Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these in any way. Examples 1 to 8 Each component was blended in the proportions shown in Table 1 below,
Eight types of resin compositions were obtained by kneading using a kneader. These compositions were transfer molded at 160° C., 200 kg/cm ² for 1.5 minutes, and their properties were measured. In addition, the unsaturated polyester resin (A) is
(B) was manufactured using 50 parts by weight of isophthalic acid, 50 parts by weight of maleic anhydride, and 100 parts by weight of propylene glycol (manufactured by Hitachi Chemical, PS518, viscosity 6 poise, containing 40% styrene). , a vinyl ester type obtained by reacting a bisphenol A type epoxy compound with methacrylic acid (manufactured by Hitachi Chemical Co., Ltd., PS6100, viscosity 6 poise, styrene
40% content). These resin compositions and cured products were examined for curability, bending strength, bending strength retention, and thermal shock resistance (crack resistance). In addition, a C-shaped washer (30φ, thickness 5mm) test piece was used for the impact impact resistance test. The obtained results are also shown in Table 1 below.

【table】

[Table] As is clear from Table 1, the resin composition of the present invention has good curability, and the cured product thereof has excellent flexibility and heat resistance. Examples 9 to 14 Each component was blended in the proportions shown in Table 2 below,
Six types of resin compositions were obtained by kneading using a kneader. These compositions were transfer molded at 170° C., 70 kg/cm ² for 5 minutes, and their properties were measured. In addition, the unsaturated polyester resin (C) is
Terephthalic acid, 1,2-propylene glycol,
Fumaric acid and adipic acid in a molar ratio of 1:2:2:1
(Contains 40% styrene, acid value 27.1). (contains 40% styrene, acid value 23.5). Characteristic test results of cured products of these resin compositions are also shown in Table 2 below. In addition, for the crack resistance test, a C-shaped washer (40φ, thickness 6mm) was used.
A test piece was used.

[Table] As is clear from Table 2, by using the resin composition of the present invention, a cured product with good flexibility and heat resistance can be obtained. In addition, Example 12~
As shown in No. 14, it has been found that when the blending ratio of the etherimide compound represented by the general formula () (relative to the unsaturated polyester resin) is small, the properties of the cured product deteriorate. As explained above, according to the present invention, it is possible to provide a thermosetting resin that can produce a cured product with excellent heat resistance and flexibility.

Claims (1)

[Claims] 1. General formula (In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a chlorine atom or a bromine atom, and they are the same or different,
R ₅ and R ₆ represent a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group, or a trichloromethyl group, which are the same or different, and D has an ethylenically unsaturated bond and has 2 to 24 1. A thermosetting resin composition comprising an etherimide compound represented by (representing an organic group having a carbon atom) and an unsaturated polyester resin. 2 An etherimide compound represented by the general formula () in which R ₁ , R ₂ , R ₃ and R ₄ are hydrogen, R ₅
and R ₆ is a methyl group, and D is -CH=CH-, which is an etherimide compound, Claim 1
The thermosetting resin composition described in .