JPH0316373B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field of the Invention] The present invention relates to a heat-resistant resin composition suitable as a molding material that has good heat resistance, excellent mechanical strength, and excellent workability. [Technical background of the invention and its problems] Polyimide resin is used as a heat-resistant molding material. Among these, wholly aromatic polyimide consisting of oxydiamine and pyromellitic anhydride must be molded at extremely high temperatures and is difficult in practice. There is a reaction product of bismaleimide and aromatic primary diamine, but this also has the disadvantage that it must be molded at a high temperature of 220 to 260°C. On the other hand, it is composed of an adduct of bismaleimide and aminophenol and an epoxy resin, and although it has a well-balanced composition in terms of processability and heat resistance, it has the disadvantage that its applications are limited due to poor mechanical strength. Ta. [Object of the Invention] The present invention was made in view of the above-mentioned difficulties, and an object of the present invention is to provide a heat-resistant resin composition that has good heat resistance, excellent mechanical strength, and excellent processability. [Summary of the Invention] The present invention was completed as a result of intensive research to achieve the above object, and is a combination of an N,N'-bis-imide compound of an unsaturated dicarboxylic acid and a hydroxyamino-diphenylalkane derivative. This is a heat-resistant resin composition characterized by consisting of a heat-resistant resin containing a reaction adduct and an epoxy resin as essential components and an inorganic filler, and is suitable as a molding material. (a) N,N'-bis-imide compound of unsaturated dicarboxylic acid, which is an essential component of the heat-resistant resin used in the present invention, has the general formula (However, R ¹ represents a divalent group having at least two carbon atoms, and R ² represents a divalent group containing a carbon-carbon double bond.) , maleic acid N,N'-4,4'-diphenylmethane-bis-imide, maleic acid N,
N'-4,4'-diphenyl ether-bis-imide, maleic acid N,N'-paraphenylene-bis-imide, maleic acid N,N'-benzidine-bis-imide, maleic acid N,N'-meta Xylene-bis-imide, maleic acid N,N'-1,5-
naphthalene-bis-imide, maleic acid N,
N'-4,4'-diphenylsulfone-bis-imide, maleic acid N,N'-2,2'-4,4'--dimethylene-cyclohexane-bis-imide, maleic acid N,N'-4 , 4'-dicyclohexyl-methane-bis-imide, N,N'-4,4'-diphenylcyclohexane-bis-imide maleate, N,N'-4,4'-diphenyl-phenylamine-bis-maleate Imide, maleic acid N,N'-4,4'-
diphenyl-diphenylsilane-bis-imide,
Maleic acid N,N'-4,4'-diphenyl sulfur-bis-imide, maleic acid N,N'-2,2'-(4,
4'-diphenyl)-propane-bis-imide, maleic acid N,N'-metaphenylene-bis-imide, maleic acid N,N'-3,3'-(N,N'-metaphenylene-bis-benzamide) - bis-imide, etc. The other essential component (b)hydroxyamino-diphenylalkane derivative has the following general formula: ⁽ _{wherein ,} ^_ _{_ _} represents an atom), and specific examples include 4-hydroxy-
4'-aminodiphenyl, 4-hydroxy-4'-aminodiphenyl ether, 4-hydroxy-4'-
Aminodiphenylmethane, more preferably
2,2'-(4-hydroxy-4'-aminodiphenyl)-propane, 2,2-(4-hydroxy-4'-
aminodiphenyl)-butane, 2,2-(4-hydroxy-4'-amino-3'-methyldiphenyl)-
Propane and 2,2-(4-hydroxy-4'-
Examples include amino-3',5'-dimethyldiphenyl)-propane. The epoxy compound (c), which is another essential component, is a low molecular weight compound or a high molecular weight compound having at least two epoxy groups in the molecule. For example, Epicoat 828 (an epoxy resin trade name manufactured by Ciel Chemical Co., Ltd.), which is an epibis type compound based on bisphenol A, etc., Epiklon 800 in an alkyl-modified form, Epiclon 4050 (an epoxy resin trade name manufactured by Dainippon Ink Chemical Industries, Ltd.), Cyodyne (epoxy resin product name manufactured by Showa Denko), Araldite
Glycidyl ester compounds such as CY-183 (epoxy resin brand name manufactured by Ciba Chemical Co., Ltd.), novolac type Epicote 154 (epoxy resin brand name manufactured by Ciel Chemical Co., Ltd.), DEN431, DEN438 (epoxy resin brand name manufactured by Dow Chemical Company), cresol novolak shape
ECN1280, ECN1235 (epoxy resin product name manufactured by Ciba Chemical Co., Ltd.), urethane modified EPU-6, EPU-10
(epoxy resin product name manufactured by Asahi Denka Kogyo Co., Ltd.). Furthermore, epoxy resins represented by the following formulas (1) to (3) can also be used. In addition to the epoxy resins mentioned above, various epoxy resins can be used, and in short, all kinds of epoxy resins can be used if conditions are appropriately selected. The blending ratio of (a) N,N'-bis-imide compound of unsaturated dicarboxylic acid and (b) hydroxyamino-diphenylalkane derivative may be in the range of 0.2 to 2 moles of the latter per 1 mole of the former. desirable. That is, if the amount of the hydroxyamino-diphenylalkane derivative used is more than 2 moles, it is not preferable because it lowers the heat resistance of the final resin composition.
Moreover, if it is less than 0.2 mol, the mechanical strength will be poor, which is not preferable. Therefore, in order to have both heat resistance and mechanical strength, it is preferable to keep it within the above range. Although the proportion of the N,N'-bis-imide compound/hydroxyamino-diphenylalkane derivative and the epoxy compound can be varied over a wide range, it is usually desirable that the latter be 10 to 40% by weight. If the epoxy compound content is less than 10% by weight, the mechanical strength will be poor, and if it is more than 40% by weight, the heat resistance will be insufficient, which is not preferable. To produce a heat-resistant resin, first, N,N'-bis-imide compound and hydroxyamino-diphenylalkane derivative are placed in a suitable reaction vessel at a predetermined ratio, and the mixture is heated and stirred at 120 to 160°C. It is an adduct with a softening temperature of 80 to 140℃. After the reaction, the hot adduct is added to the epoxy compound and cooled while mixing, so that the two react and a prepolymer is obtained. Examples of the inorganic filler (B) used in the present invention include calcium carbonate, silica, asbestos fibers, and single glass fibers. Inorganic fillers are used for improving roll processability, improving hardness at high temperatures, reinforcing mechanical strength, etc. The blending ratio of the heat-resistant resin (A) and the inorganic filler (B) is preferably 30 to 70% by weight.
This is because, outside this range, the mechanical strength of the molded article decreases, making it difficult to obtain the desired properties. [Effects of the Invention] The heat-resistant resin composition of the present invention itself exhibits appropriate flexibility in a cured state, and when formed into a molded product, it exhibits less cracking and excellent mechanical strength. Moreover, when it is finally cured, it shows no deterioration even at temperatures of around 200°C and exhibits excellent heat resistance. [Embodiments of the Invention] Examples of the present invention will be described, but the present invention is not limited to these embodiments. Example 1 360 g of maleic acid N,N'-diphenyl ether-bis-imide and 2,2-(4-hydroxy-
Put 114 g of 4'-aminodiphenyl)-propane into a kneader equipped with a steam heating device and heat to 145-150 g.
The adduct was obtained by heating and kneading at a temperature of °C for 30 minutes. Next, 150g of Epicote 1001 (trade name manufactured by Ciel Petrochemical Co., Ltd.) was added to this adduct and mixed thoroughly.
It was cooled and ground to obtain a prepolymer powder. 100g of this prepolymer and calcium carbonate powder (average particle size
A molding material was prepared by mixing 100g of 10μ) with a mixer. The obtained molding material was placed in a mold heated to 180°C and press-molded under the conditions of a pressure of 150 kg/cm ² and a heating time of 1 minute/mm thickness, and then the molded body was heat-treated at 200°C for 5 hours. Post-curing was performed. When the bending properties of this molded body were measured, the bending strength was 10.5 at room temperature.
Kg/mm ² , 9.0 Kg/mm ² at 150°C, and 7.7 Kg/mm ² at 220°C, indicating that it has high mechanical properties at high temperatures. Examples 2 to 6 Prepolymers were obtained in the same manner as in Example 1 using the compositions shown in Table 1. Next, a filler was added to prepare a molding material. After that, Example 1
Molded bodies were obtained in the same manner as above, and the initial bending strength and value after thermal deterioration of each were measured. The results are also shown in Table 1. Comparative Example 1 360 g of maleic acid N,N'-4,4'-diphenyl ether-bis-imide and 55 g of meta-aminophenol were placed in a kneader 1 equipped with a steam heating device in the same manner as in Example 1 and heated at 135 ~ The adduct was obtained by heating and kneading at a temperature of 140°C for 15 minutes. Next, 150% of Epicote 1001 (trade name manufactured by Ciel Petrochemicals) was added to this adduct.
After adding g and thoroughly mixing, the mixture was cooled and pulverized to obtain a prepolymer powder. 100 g of this prepolymer and 100 g of calcium carbonate powder (average particle size: 10 μm) were mixed in a mixer to prepare a molding material. After molding and curing in the same manner as in Example 1, the bending properties were measured. Bending strength is 8.5Kg/mm ² at room temperature, 8.0Kg/mm ² at 150℃, 220℃
It was 7.2Kg/ ^mm2 .

[Table] *1: Epoxy resin product name manufactured by Shell Petrochemical Co., Ltd. *2: Epoxy resin product name manufactured by Dow Chemical Company

Claims (1)

[Claims] 1 (A) (B) General formula (In the formula, R ¹ represents a divalent group having at least 2 carbon atoms, and R ² represents a divalent group containing a carbon-carbon double bond.) N′-bis-imide compound and (b) General formula (In the formula, X is a single bond, _C1 to _C5 alkylene or isoalkylene group, oxygen atom or sulfur atom, ^R3 and ^R4 are hydrogen atoms, _C1 to _C3
(3) an epoxy compound, and (B) an inorganic filler. A heat-resistant resin composition characterized by: 2. The heat-resistant resin composition according to claim 1, comprising 70 to 30% by weight of the heat-resistant resin (A) and 30 to 70% by weight of the inorganic filler (B). 3. Claim 1, characterized in that 0.2 to 2 moles of the hydroxyamino-diphenyl alkane derivative (b) is reacted with 1 mole of the N,N'-bis-imide compound (a). Or the heat-resistant resin composition according to item 2. 4 90 to 60% by weight of the N,N'-bis-imide compound of (a) added with the hydroxyamino-diphenylalkane derivative of (b) and the epoxy compound of (c)
4. The heat-resistant resin composition according to claim 1, wherein the heat-resistant resin composition contains 10 to 40% by weight.