JPS632285B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a curable resin composition having particularly excellent impact resistance and heat resistance. Conventionally, diallyl phthalate resins, which are mainly composed of prepolymers derived from diallyl orthophthalate and diallyl isophthalate, are required to have high reliability because they have excellent retention of electrical properties, especially at high temperatures and high humidity. It is used extensively in electrical and electronic applications and has a proven track record over many years. Although the diallyl phthalate resin has excellent dimensional stability, heat resistance, water/moisture resistance, and other properties, it has been pointed out that it lacks adhesion. Since diallyl phthalate resin is usually mixed with various reinforcing materials, fillers, etc., if mutual adhesion or wetting is insufficient,
It is difficult to obtain a reinforcing effect, and the performance of the resin cannot be demonstrated. Furthermore, some molded products have metal parts inserted, enclosed, or adhered to each other, and even in such cases, mutual adhesion is strongly required. Many efforts have been made in the past, including modification of resins, blending, and selection of coupling agents, but it can be said that there are still no products that are fully satisfactory and have been put to practical use. On the other hand, epoxy resins have various favorable properties, so they are used as engineering plastics and insulating materials in the electrical and electronic fields.
It is well known that it is widely used. As is well known, epoxy resins can be cured using organic acids or their acid anhydrides, amines, amides, or the like as a curing agent to form a cured product with an insoluble and infusible three-dimensional structure. Although it is possible to select from a variety of curing agents depending on the performance required of the cured product, if the selection is incorrect or the amount used is inappropriate, the performance of the epoxy resin may deteriorate. I often end up. Further, the curing rate of commonly used curing agents is slow, and as mentioned above, the amount used is sometimes subject to restrictions, and it is difficult to control the curing rate by changing the amount of the curing agent. Furthermore, epoxy resins have drawbacks in water resistance and moisture resistance. Although it has been gradually improved by modifying the resin itself and considering its usage,
No fundamental solution has been reached. However, epoxy resin has excellent adhesion. Therefore, when a diallylphthalate resin and an epoxy resin are used in combination, it is thought that an excellent material can be provided by taking advantage of their respective strengths and complementing each other's weaknesses. Several such examples are known. These materials have excellent mechanical properties such as dimensional stability and thermal rigidity, heat resistance, and electrical properties, and are evaluated in fields that require high reliability. However, this item is fragile;
It has the disadvantage of insufficient toughness, and as molded products have become smaller in recent years, the problem of cracking and chipping in the thin inner parts and small protrusions of the molded products has become more serious. The inventors of the present invention have conducted extensive research in order to develop a new, tough resin that has various properties that exceed those of conventional resins, and also has improved high impact value and high heat resistance. . As a result, a compound containing both the terephthalic acid diallyl ester copolymer and the epoxy resin described below exceeds the properties of the conventional resin described above, and has further improved bending strength, heat resistance, and They discovered that it has improved impact resistance and completed the present invention. That is, the present invention is made by blending a diallyl phthalate resin and an epoxy resin, the diallyl phthalate resin contains 1% by weight or more of the following terephthalic acid diallyl ester copolymer, and the epoxy resin contains a diallyl phthalate resin and an epoxy resin. It is a curable resin composition with high impact resistance and high heat resistance, characterized in that the amount of the epoxy resin is 1 to 80% by weight based on the total amount of epoxy resin. The above terephthalic acid diallyl ester copolymer refers to a copolymer obtained by polymerizing terephthalic acid diallyl ester and an aromatic hydrocarbon represented by the following formula () in the presence of an organic peroxide and an azo compound. . In the present invention, a terephthalic acid diallyl ester copolymer as described below is particularly preferred as a modifier that imparts a high impact value to the composition.
That is, the following formula () However, in the above formula (), R ¹ and R ² each represent a group selected from the group consisting of a hydrogen atom and a lower alkyl group, and n = an integer of 1 to 3. An aromatic hydrocarbon having at least one hydrogen atom at the benzylic position represented by the following formula () A copolymer with terephthalic acid diallyl ester represented by (a) one monomer unit of formula () at the end of the monomer unit of formula (), and an allyl group of the monomer unit of formula () at the benzyl position and its C and/
Or it has a structure in which C and carbon-carbon bonds are formed. Furthermore, (b) the number of monomer units of the formula () in the carbon-carbon bond molecular chain portion formed by the allyl group of the monomer unit of the formula () of the copolymer is 3 to 11, preferably 3 to 10. It is a copolymer with certain structural characteristics. The structure of the copolymer, for example, when toluene (R ¹ =R ² =H, n=1) is used as the compound of formula (), is represented by the following formula (). In the above formula (), R is an unreacted allyl group and/or a chain derived from an allyl group constituting another molecular chain portion of the copolymer. represents. As an example of such an aspect, for example, the following formula () The structural part represented by can be mentioned.
In addition, in the structural part of the above formula (), the number of monomer units of the formula () in the carbon-carbon bond molecular chain part formed by the allyl group of the formula () monomer unit is 3 to 11 as shown in the formula (). However, this carbon-carbon bond molecular chain portion is the head-to-tail bond shown in formula (), that is, the following formula () In addition to , it can have a head-head bonding part as shown in the following formula (). The formula () monomer unit in the above structural subformula () constitutes a branching point that connects the two structural parts of formula () and () via two ester bonds. Further, when R is an unreacted allyl group, it can be represented by the following formula (). The structural portion of the above formula () is a portion that becomes a crosslinking point during curing of the terephthalic acid diallyl ester copolymer. The terephthalic acid diallyl ester copolymer used in the present invention is preferably a copolymer having the following properties. (C) Iodine value measured by Wijs method: 40~
85. (d) True specific gravity at 25°C is 1.20 to 1.25 (e) Softening range is about 50 to about 120°C. (f) 50% methyl ethyl ketone solution viscosity 80-300 centipoise (30°C). (g) The polystyrene equivalent number average molecular weight ( Mn ) measured by GPC (gel permeation chromatography) method is 4000 to 10000, the weight average molecular weight ( Mw ) is 70000 to 200000, and Mn The molecular weight distribution expressed as the ratio Mw / Mn to Mw is
10-40. (h) Brabender melt viscosity measured with a Brabender plastograph is 250 to 2600 m/g, and processing time is 5 to 65 minutes. In producing the terephthalic acid diallyl ester copolymer of the present invention, the aromatic hydrocarbon of the formula () and the terephthalic acid diallyl ester of the formula (), which are raw material monomers, are combined with an organic peroxide or an azo compound catalyst. By conducting a copolymerization reaction in the presence of a copolymer, preferably by setting reaction conditions to obtain a copolymer having the structures (a) and (b) and the properties (c) to (h). manufactured by R ¹ and R ² of the aromatic hydrocarbon in the above formula () are:
Each is selected from the group consisting of a hydrogen atom and a lower alkyl group, and the lower alkyl group is
Examples include _C1 to _C5 alkyl groups. Examples of such compounds of formula () include, for example, toluene, ethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene, sec-butylbenzene, n-amylbenzene, sec-amylbenzene, isoamylbenzene. Benzene, (2-methylbutyl)-benzene, o
-xylene, m-xylene, p-xylene, xylene isomer mixture, pseudocumene, 1,2-diethylbenzene, 1,3-diethylbenzene,
1,4-diethylbenzene, 1,2-dipropylbenzene, 1,3-dipropylbenzene, 1,4
-dipropylbenzene, diisopropylbenzenes, p-cymene, 1,2-dibutylbenzene,
1,3 dibutylbenzene, 1,4-dibutylbenzene, 1,2-diisoamylbenzene, 1,3-
Examples include diisoamylbenzene, 1,4-diisoamylbenzene, and 1,2,3-trimethylbenzene. Further, as examples of organic peroxide catalysts and azo compound catalysts, the following compounds can be exemplified. Dialkyl peroxides and diaryl peroxides such as di-tert-butyl peroxide, di-sec-butyl peroxide, tert-butyl-sec-butyl peroxide, and dicumyl peroxide. Diaroyl peroxides and diacyl peroxides such as benzoyl peroxide. Di-tert-butyl peroxalate, tert-perbenzoate
- alkyl esters of percarboxylic acids such as butyl; 2,2'-azobisisobutyronitrile;
2,2'-azobis-(2-methylbutyronitrile), 2,2'-azobis-(2-methylheptanitrile), 1,1'-azobis-(1-cyclohexylcarbonitrile), 2,2' -Azo compounds such as methyl azobisisobutyrate, 4,4'-azobis-(4-cyanopentanoic acid), azidobenzene, etc.; tert
-butyl hydroperoxide, sec-butyl hydroperoxide, tetralyl hydroperoxide, cumyl hydroperoxide, benzyl hydroperoxide, benzhydryl hydroperoxide, decalyl hydroperoxide, acetyl peroxide, cyclohexyl hydroperoxide,
Hydroperoxides such as n-decyl hydroperoxide; Furthermore, compounds that are easily oxidized by molecular oxygen, in the present invention, terephthalic acid diallyl ester, at least one hydrogen at the benzyl position represented by the formula () This corresponds to an aromatic hydrocarbon having atoms or the copolymer of the present invention, but if these are oxidized with air or oxygen in advance or during the copolymerization reaction to produce a peroxide, the copolymerization reaction of the present invention can be performed. Can be used satisfactorily as a catalyst. Regarding the above-mentioned terephthalic acid diallyl ester copolymer, Japanese Patent Application No. 189981, filed earlier by the present applicant,
Details are given in the issue. The ratio of the blend of diallyl terephthalate copolymer is the diallyl phthalate resin (diallyl phthalate prepolymer and diallyl terephthalate copolymer) in the total amount of diallyl phthalate resin used in the present invention. The amount of coalescence is 1% by weight or more, preferably 5% by weight or more, more preferably 20% by weight.
The above is preferable in order to improve the impact resistance of the composition. There is no particular restriction on the upper limit of the amount added,
In particular, when heat resistance is required, the blending ratio of the copolymer may be increased. In particular, in order to obtain excellent bending strength when diallyl orthophthalate resin is used, it is preferable to blend the above-mentioned copolymer in a range of 2 to 90% by weight. The diallyl phthalate resin used in the present invention contains the above-mentioned terephthalic acid diallyl ester copolymer as an essential component, and is obtained by polymerizing the ortho, iso, and tele monomers of the diallyl phthalate resin as other components. , usually has a number average molecular weight of 2000 to 20000, is soluble in solvents and fusible by heating,
A general term for a post-polymerizable diallyl phthalate prepolymer having an allyl group in the molecule, or a mixture of the prepolymer and a reactive monomer or oligomer, and/or an unsaturated polyester and/or an epoxy acrylate resin. The reactive monomers or oligomers include diallyl orthophthalate, diallyl isophthalate, diallyl terephthalate, diallyltetrachloro or bromoortho, iso, and terephthalate, diallylchlorendate, triallyl isocyanurate, triallyl cyanurate, triallyl trimeryl. tate, triallyl phosphate, styrene, α-chlorostyrene, methyl (meth)acrylate, butyl (meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate , glycidyl (meth)acrylate, allyl (meth)acrylate, methyl acrylate acrylamide, diacetone acrylamide,
N-vinylcarbazone, N-methylolacrylamide, methylenebisacrylamide, methacrylamide, N-tert-butylacrylamide,
Examples include 2,4- or 2,6-tolylene diisocyanate, maleic acid semiester, phthalic acid monoallyl ester, allyl glycidyl ether, etc., or low molecular weight polymers thereof. Can be used in combination. The amount of reactive monomer or oligomer is
The amount is preferably 200 parts by weight or less per 100 parts by weight of the diallyl phthalate resin. If the composition exceeds 200 parts by weight,
This is undesirable because the curing rate is unduly delayed and the internal distortion of the molded product increases due to an increase in the curing shrinkage rate. Unsaturated polyesters include unsaturated dibasic acids such as maleic acid, maleic anhydride,
One or more types of fumaric acid, itaconic acid, citraconic acid, glutaconic acid, mesaconic acid, etc.
Saturated dibasic acids include, for example, aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, phthalic acid,
Phthalic anhydride, isophthalic acid, terephthalic acid and their halides, tetrahydrophthalic acid,
One or more types of hexahydrophthalic acid, ethylene glycol, propylene glycol,
Refers to those synthesized from polyhydric alcohols such as neopentyl glycol. The selection of each component and the combination thereof may be determined depending on the use of the prepreg. For example, if a high degree of dimensional stability, heat resistance, etc. are required, it is preferable to use terephthalic acid-based unsaturated polyester. Epoxy acrylate resin refers to a reaction product of epoxy resin and methacrylic acid or acrylic acid. As the epoxy resin, those mentioned below are used. The epoxy resin used in the present invention preferably has an average of at least two epoxy groups per molecule, and examples of such epoxy compounds include polyhydric alcohols such as ethylene glycol, glycerin, and trimethylolpropane. ,
Ether-type epoxy compounds obtained by the reaction of epihalohydrin, glycidyl ether-type epoxy compounds obtained by the reaction of epihalohydrin with polyhydric phenols such as resorcinol, hydroquinone, catechol, bisphenol A, and halogenated bisphenol A, and phenol novo Novolac-type epoxy compounds obtained by the reaction of lacquer resin or cresol novolac resin with epihalohydrin; epoxy compounds obtained by epoxidizing aliphatic or alicyclic olefins; bis(N,N-diglycidylaminomethyl);
Benzene, cyclohexane, epoxidized polybutadiene, etc. are used. These may be selected depending on the intended use of the composition, but if, for example, a high degree of dimensional stability, heat resistance, etc. are required, a bisphenol type obtained by the reaction of bisphenol A and epichlorohydrin may be used. Preferred are epoxy resins or novolak-type epoxy resins obtained by reaction of novolak resins with epichlorohydrin. The amount of this epoxy resin used is 1 to 80% by weight, preferably 3 to 60% by weight, more preferably 5 to 50% by weight when the total resin content of the curable resin composition of the present invention is 100% by weight. is suitable, and mechanical properties such as bending properties and impact resistance, as well as adhesion to fillers and metals, are significantly improved. If the amount of the epoxy resin used is less than the above range, disadvantages such as reduced adhesion between the resin composition of the present invention and fillers, metals, or already cured molded objects may occur, and the composition may The range of effective use of objects becomes narrower. In addition, if the amount used exceeds the above range, the characteristics of the diallylphthalate resin of the present invention, which is an essential component, may be impaired, such as the dimensional stability, moisture resistance, heat resistance, and electrical properties are reduced, and reliability is reduced. This makes it difficult to achieve the objective of the present invention. Curing agents for curing materials other than epoxy resins include dialkyl peroxides and diaryl peroxides such as di-tert-butyl peroxide and dicumyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; 1,1- Bis(tert-butylperoxy)-
peroxyketals such as 3,3,5-trimethylcyclohexane; hydroperoxides such as cumene hydroperoxide; diaroyl peroxides and diacyl peroxides such as lauroyl peroxide, benzoyl peroxide, and 2,4-dichlorobenzoyl peroxide;
Peroxycarbonates such as diisopropyl peroxydicarbonate; tert-butyl peroxyacetate, tert-butyl peroxy pivalate, tert-butyl peroxyoctoate, tert-butyl peroxy acetate, tert-butyl peroxy pivalate, tert-butyl peroxyoctoate
Examples include peroxy esters such as -butylperoxybenzoate, and azo compounds such as azobisisobutyronitrile other than the above-mentioned organic peroxides can also be used. These curing agents can be used alone or in combination of two or more, and the amount used is usually 0.1 to 6 parts by weight per 100 parts by weight of the resin of the present invention. In addition, as a polymerization accelerator, for example, cobalt salts, vanadium salts of naphthenic acid or octoic acid,
Metal soaps such as manganese salts, aromatic tertiary amines such as dimethylaniline and diethylaniline, etc. may be added in an amount of, for example, 0.005 to 6 parts by weight per 100 parts by weight of the resin of the present invention. As a curing agent for curing the epoxy resin, aliphatic polyamides such as dicyandiamide, aromatic amines, and organic acid anhydrides can be used, but a curing agent that does not undergo reaction at room temperature is desirable. Examples of aromatic amines include metaphenylene diamine, xylylene diamine, diaminodiphenylmethane, diaminodiphenyl sulfone, and benzyldimethylamine. Examples of organic acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, maleic anhydride, chlorendic anhydride, pyromellitic anhydride, and 3,3',4,4'-benzophenonetetracarboxylic anhydride. , methylnadic anhydride, dodecylsuccinic anhydride, dichlorosuccinic anhydride, and hexahydrophthalic anhydride. A mixture or a eutectic modified product of an aromatic amine and an organic acid anhydride may also be used, and a trace amount of aliphatic amine may be added if necessary.
The amount of these curing agents used may be 0.5 to 1.5 gram equivalent per gram equivalent of the epoxy resin. The resin composition of the present invention may contain fillers, flame retardants, coupling agents, polymerization inhibitors, internal mold release agents, pigments, colorants, and other additives, as necessary, so as not to impair the properties of the composition. It is possible to improve the molding processability or the physical properties of the molded article by mixing it within a range where it is not necessary. As the filler, commonly used inorganic and/or organic fillers can be used, and these can be used alone or in combination. Alternatively, when producing grinding wheels or sandpaper using the composition as a binder, various commercially available abrasive grains,
It can be mixed with grinding aids, pore agents, etc. and molded. The resin composition of the present invention cures quickly, is adjustable, can be adjusted to apply various molding methods, exhibits excellent moldability, and has good dimensional stability. The molded product is heat resistant, impact resistant, water resistant,
Excellent moisture resistance, chemical resistance, and adhesion, high surface hardness, and little change over time. Therefore, the mechanical strength and electrical properties are excellent, especially at high temperatures and high humidity, and the reliability is extremely high. Hereinafter, a more detailed explanation will be given based on examples. Production example of terephthalic acid diallyl ester copolymer 1-2 A turbine blade type variable stirrer, a double pipe type supply nozzle for monomer and catalyst supply, a nitrogen purge port, a leak valve, a sampling port, a thermometer and a pressure gauge. Comes with a jacket with an inner diameter of 600 mm and an inner volume of 120 mm.
A polymerization tank made of SUS304 was used. The double-tube supply nozzle for monomer and catalyst supply is installed below the liquid level in the body of the polymerization layer, and the inner diameter of the outer tube is set to 1.5 mm before entering the polymerization tank to minimize the residence time in the supply piping. I made it shorter. Three such nozzles were installed in preparation for nozzle blockage. A sampling port was also installed in the body of the polymerization tank, making it possible to take samples of the liquid phase using the internal pressure during the polymerization reaction. An oil rotary vacuum pump and a nitrogen cylinder were connected to the nitrogen purge port so that they could be switched as needed. The above polymerization tank was charged with 60 kg of aromatic hydrocarbon (HC) of the formula () shown in Table 1 below, and the process of reducing the pressure using a vacuum pump and returning to normal pressure using nitrogen gas at room temperature was repeated three times. After replacing the air inside with nitrogen, the pressure was reduced again and the polymerization tank was sealed. The stirrer was started and while stirring at 240 RPM, steam was passed through the jacket to raise the temperature to 140°C. The stirring speed was increased to 720 RPM, and terephthalic acid diallyl ester was added from the outer pipe of the double pipe nozzle at the specified speed, and at the same time, di-tert-butyl peroxide (DTBPO) and aromatic hydrocarbon (HC) of the formula () were added. were mixed in advance at a molar ratio of 0.5:1 and supplied to the polymerization tank at a predetermined rate using a pump with a discharge pressure of 70 kg/cm ² . During this time, the temperature of the polymerization tank was 140
The steam was adjusted to maintain the temperature. The formula () diallyl terephthalate (DAT) to be supplied was cooled to 15°C, and the mixture of di-tert-butyl peroxide and aromatic hydrocarbon was cooled to 5°C.
Each pipe leading to the polymerization tank was kept cool. The polymerization tank pressure was 0.3 to 2 Kg/cm ² G. When the supply of a predetermined amount of terephthalic acid diallyl ester, aromatic hydrocarbon, and di-tert-butyl peroxide is completed, the stem is stopped and the stirring speed is lowered.
It was set to 240 RPM and cooled by passing cooling water through the jacket. After cooling to around room temperature, the leak valve was opened to return to normal pressure, and the polymerization reaction was completed. During the polymerization reaction, samples were appropriately taken from the sampling port, and the reaction was monitored using refractive index and GPC. The feed rates and amounts of diallyl terephthalate, aromatic hydrocarbon, and di-tert-butyl peroxide are shown in Table 1 below. The volatile components of the polymerization reaction solution obtained above were distilled off using a thin film evaporator, and the total of unreacted aromatic hydrocarbons, copolymer and unreacted terephthalic acid diallyl ester in the evaporation residue was removed. the ratio by weight to
0.3:1, and then the evaporation residue was stirred while being dropped into a stirring tank containing methanol in an amount 5 times the weight of the supplied diallyl terephthalate.
A copolymer was precipitated. The precipitated copolymer was thoroughly washed with the same amount of methanol, filtered, dried, and pulverized to obtain a powdery copolymer. Table 1 shows the yield and physical properties of the copolymer. [Table] In Table 1 above, (1) is a polystyrene equivalent value measured by gel permeation chromatography using a Waters "150CGPC" device. For (2), a light transmission type automatic melting point measuring device "PF61" manufactured by Hattler was used. (3) is the value measured using the Brabender Plastograph manufactured by Brabender (Germany). Kneading chamber capacity 50c.c., rotor model W50H, sample 50g
+ Zinc stearate 0.5g, kneading chamber temperature 130℃, rotor rotation speed 22RPM until kneading resistance reaches 5000m・g. From the torque curve on the recording paper, the lowest torque value is taken as the Brabender melt viscosity, and at the end of sample addition. The processing time was defined as the time from Examples 1 to 9, Comparative Examples 1 to 5 After thoroughly mixing each composition shown in Table 2, roll kneading (front roll 75 to 100°C, rear roll 30 to 80°C,
The mixture was kneaded for 6 minutes) to form a sheet, which was pulverized using a Henschel mixer to form a compound. Take 20 to 30 g of the above compound and manually press it using a mold to make a roughly disc-shaped tablet with a diameter of 50 mm and a thickness of 10 mm. After preheating it to about 80 degrees Celsius with a high-frequency preheater, immediately adjust it to the specified temperature. Place it in the center of the cavity of the compression mold that you have prepared,
20 at a mold temperature of 160℃ and a pressure of 100Kg/ ^cm2 using an automatic press.
The mixture was molded for minutes to obtain a disc-shaped molded product with a diameter of about 100 mm and a thickness of 2 mm. The molded product was subjected to a general test method according to JISK-6911, a falling weight impact test method according to JISK-7211, and a heat resistance test, and the results are shown in Table 2. In addition, among the physical properties of the molded products in Table 2, the falling weight impact value and heat resistance were measured by the following methods. Falling Weight Impact Test Thirty-six test pieces were cut out from two molded products using a diamond cutter and subjected to measurement. A Dupont-type falling ball tester (load 500g, flat support, 1/2 inch R) was used as the testing machine, and the 50% fracture height was determined by the Dickson mode method (Reference: JISK-7211). Heat Resistance Test Three molded products were left in a constant temperature bath at 150°C for 2 hours and then allowed to cool in a desiccator. The initial weight of each molded product test piece was actually measured, and then these test pieces were left in a constant temperature bath adjusted to 200±2°C for an appropriate period of time, and then allowed to cool in a desiccator, and the weight of each piece was actually measured. At this time,
The average value of the weight loss of the three test pieces is 10 of the initial weight.
%, then test these specimens again.
Leave it in a constant temperature bath at 200 + 2℃ for an appropriate time, measure the weight loss again, and repeat until the average weight loss of the three test pieces reaches 10% of the initial weight. The gender was evaluated. [Table] [Table] Example 10, Comparative Example 6 When obtaining a disk-shaped molded product using the compound of Example 2, the outer diameter was 14 mm, the inner diameter was 6 mm, and the thickness was
A flat iron washer of 0.5 mm was placed in the mold cavity together with the compound, and molded in the same manner as in Example 2 to obtain a disc-shaped molded product with the washer embedded. The molded product was heated at +80°C for 2 hours and then at -25°C.
When subjected to a temperature cycle test in which one cycle was treatment for 2 hours, no abnormality was observed even after 10 cycles. In the washer-embedded molded product obtained using the compound of Comparative Example 2 in the same manner as above, cracks appeared around the washer after two cycles. Examples 11 to 13, Comparative Examples 7 to 8 Using each resin mixture having the composition of Examples 2, 3, and 6, and Comparative Examples 2 and 3, about 1 kg of a composition consisting of the following formulation was processed in the following manner. Prepared with Compound Resin mixture 100 parts by weight Hydroquinone 0.01 〃 Methacryloxysilane 0.6 〃 Calcium stearate 2 〃 Short glass fiber * 100 〃 Calcium carbonate 40 〃 * Manufactured by Asahi Fiberglass In the above formulation, dicumyl peroxide, dicyandiamide, hydroquinone and methacrylate Roxysilane and resin were dissolved in 500 g of acetone. This was charged into a crusher with a capacity of 3, and then calcium stearate and calcium carbonate, which had been thoroughly mixed in advance, were added and mixed for about 5 minutes. Short glass fibers were then added and mixed for an additional 10 minutes. After leaving this for a day and night to volatilize the residual acetone, roll (front roll 100℃, rear roll
The mixture was kneaded at 90°C for about 10 minutes. The compound taken out in sheet form from the roll was pulverized in a feather mill equipped with a screen of 2 mm in diameter to form a granule-like compound. The obtained compounds were molded in the same manner as in Examples 1 to 9, and the physical property tests were performed. The results are shown in Table 3-
1, 3-2. [Table] [Table] Example 14, Comparative Example 10 Using each resin mixture having the composition of Example 2 and Comparative Example 2, a formulation having the following composition was thoroughly kneaded using approximately the same amount of methyl ethyl ketone. After removing the solvent, the particles are sized and heated at 170℃ using a heat press method.
A plate-shaped molded product with a thickness of 5 mm was obtained. Compound Resin mixture 20 parts by volume Abrasive grains JIS 2CWA #46 50 Cryolite 30 Table 4 shows the results of measuring the bending properties of the obtained molded product according to JISK6911. 【table】

Claims (1)

[Scope of Claims] 1. A diallyl phthalate resin and an epoxy resin are blended, the diallyl phthalate resin contains 1% by weight or more of the following terephthalic acid diallyl ester copolymer, and the epoxy resin is a diallyl phthalate resin. A curable resin composition characterized in that the amount thereof is 1 to 80% by weight based on the total amount of resin and epoxy resin. The above terephthalic acid diallyl ester copolymer is a copolymer of terephthalic acid diallyl ester and an aromatic hydrocarbon having at least one hydrogen atom at the benzyl position represented by the following formula, and is a copolymer of terephthalic acid diallyl ester unit. refers to a copolymer in which the number of aromatic hydrocarbon units is 3 to 11 per one aromatic hydrocarbon unit. However, in the above formula, R ¹ and R ² each represent a group selected from the group consisting of a hydrogen atom and a lower alkyl group, and n = an integer of 1 to 3.