JPS60208322A - Curable resin composition - Google Patents

Abstract

PURPOSE:The titled quick-curing composition, obtained by incorporating a diallyl phthalate based resin containing a diallyl terephthalate copolymer with an epoxy resin, and having improved impact and heat resistance and flexural strength. CONSTITUTION:A curable resin composition obtained by incorporating (A) a diallyl phthalate based resin prepared by copolymerizing diallyl terephthalate with an aromatic hydrocarbon, expressed by the formula (R<1> and R<2> are H or lower alkyl; n is 1-3), and having one or more hydrogen atoms in the benzyl position in an amount of 1mol based on 3-11 allyl groups with (B) 1-80wt%, based on the amount of the total resin, epoxy resin, e.g. ether, glycidyl or movolak type epoxy resin, having 2 or more epoxy groups in the molecule, and further adding an epoxy resin curing agent, e.g. dicyandiamide, and an allyl resin curing agent, e.g. dicumyl peroxide, thereto.

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, RFI water/moisture resistance, and other properties, it has also been pointed out that it lacks adhesion.

Since diallyl phthalate resin is usually used in combination with various reinforcing materials, fillers, etc., if mutual adhesion or leakage is insufficient, it is difficult to obtain a reinforcing effect and the performance of the resin cannot be exhibited. Further, some molded products have metal parts that are either in-place, enclosed, or adhered to each other, and in such cases as well, mutual adhesion is strongly required. Although many efforts have been made in the past, including modification and blending of resins and selection of coupling agents, 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, it is well known that epoxy resins have various favorable properties and are therefore widely used as engineering plastics and as insulating materials in the electrical and electronic fields. 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 put it away. Furthermore, the curing rate of commonly used curing agents is slow, and as mentioned above, the amount used is subject to restrictions, and it is also difficult to adjust the curing rate by adjusting the amount of the curing agent.

Furthermore, epoxy resins have drawbacks in water resistance and moisture resistance.

At present, although improvements have been made gradually through modification of the resin itself and consideration of usage methods, no fundamental solution has been reached.

However, the adhesion of the epoxy resin is excellent. Therefore, when a diallyl phthalate 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 material is brittle and has insufficient toughness, and as molded products have become smaller in recent years, cracks and chips in thin parts and small protrusions have become a growing problem. .

The inventors of the present invention have conducted extensive research in order to develop a new, tough resin that has properties that are superior to those of conventional resins, and that also has improved high impact value and high heat resistance. I've been piling it up.

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 a curable resin composition with high impact resistance and high heat resistance, which is characterized by blending an epoxy resin with a diallylphthalate-1 resin containing the following terephthalic acid diallyl ester copolymer. .

The above terephthalic acid diallyl ester copolymer is a copolymer obtained by polymerizing terephthalic acid diallyl ester and an aromatic hydrocarbon represented by the above formula (I) in the presence of an organic peroxide and an azo compound. say. In the present invention, a terephthalic acid diallyle 4-ester copolymer as described below is particularly preferred as a modifier for increasing the impact value of the composition. That is, the following formula, however, in the above formula (I), R
1 and R2 each represent a group selected from BY consisting of a hydrogen atom and a lower alkyl group, and are an integer of TL=1 to 3.

A copolymer of an aromatic hydrocarbon having at least one hydrogen atom at the benzyl position represented by the following formula (I) and a terephthalic acid diallyl ester represented by the following formula (I), wherein (a) 3 formula (I[) It has a structure in which one monomer unit of the formula (I) is bonded to the terminal of one monomer unit of the formula (I) at the benzyl position. Furthermore (
b) The number of the formula (I) monomer units in the carbon-carbon bond molecular chain portion formed by the allyl group of the formula (II) monomer unit of the copolymer is 3 to 11, preferably 3 to 10. It is a copolymer with the structural characteristics of

The structure of the copolymer is represented by the following formula (III), for example, when toluene (R1=R'=1-1, TL=1) is used as the compound of formula (I).

(χ-3 to 11) In the above formula (III), R is an unreacted allyl group and/
or represents a chain -012-04-0(2-) derived from an allyl group constituting another molecular chain portion of the copolymer.As an example of such an embodiment, for example, the following formula (
IV) -012-0-1- 1...2-[](- Structural moieties represented by - can be mentioned.

In addition, in the lfi-forming moiety of formula (I[) above, the number at the 11th position of the formula (I[) heptamer of the carbon-carbon bond molecular chain moiety formed by the allyl group of the formula (I) monomer unit is As shown in [I], the carbon-carbon bond molecular chain portion is a head-to-tail bond shown in formula (III), that is,
In addition to the following formula () 7-, it is possible to have a head-head bonding part as shown in the following formula (Vl).

The formula (I[) monomer unit in the structural subformula (IV) above connects two formulas () and (VI
) constitutes a branching point that connects the structural parts of

When R is an unreacted allyl group, the moiety formed by the formula (vII) is a moiety 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 a bamboo quality as listed below.

(C) Iodine value 40~ by Rice (WijS) method measurement
True specific gravity at 85° (d>30°C is 1.20 to 1.25 (e
) Softening range from about 50 to about 120°C.

(f) 50% methyl ethyl ketone solution viscosity 80-300
centipoise (30℃).

(o) Polystyrene equivalent number average molecule 1 (measured by GPC (gel permeation chromatography) method)
Rπ) is 4,000 to 10.000, and the weight average molecular weight is 1 (
i:IIW) is 70,000 to 200,000, and the molecule m distribution expressed as stationary W/mouth 1 between 8 turtles and day W is 1.
0 to 40° (h) Brabender melt viscosity measured with a Brabender plastograph is 250 to 2600 m -(]
The processing time is 5 to 65 minutes.

In producing the terephthalic acid diallyl ester copolymer of the present invention, the aromatic hydrocarbon of formula (I), which is a raw material monomer, and the terephthalic acid diallyl ester of formula (1) are mixed with an organic peroxide or an azo compound catalyst. In the presence of
Preferably the structures (a>, (b) and <C,') to (1
A copolymer having the properties of 1) is produced by conducting a copolymerization reaction by setting suitable reaction conditions.

R1 and R2 of the aromatic hydrocarbon in the above formula (1) are each selected from the group consisting of a hydrogen atom and a lower alkyl group, and examples of the lower alkyl group include C1 to C5 alkyl groups. Examples of such compounds of formula (1) include toluene, ethylbenzene, 1-propylbenzene, isopropylbenzene, 1-butylbenzene, isoethylbenzene, 5ec-butylbenzene, 1-amylbenzene, 5eC-amylbenzene. , isoamylbenzene, (2-methylbutyl)-benzene, 0
-xylene, m-xylene, p-xylene, xylene isomer mixture, pseudocumene, 1,2-diethylbenzene, 1,3-diethylbenzene, 1,4-diethylbenzene, 1,2-dipropylbenzene, 1,3-dipropyl Benzene, 1,4-dipropylbenzene,
+Bilbenzenes, p-cymene, 1.2-dibutylbenzene, 1.3-dibutylbenzene, 1.4-dibutylbenzene, 1,2-diisoamylbenzene, 1,3
Examples include -diisoamylbenzene, 1,4-diisoamylbenzene, and 1,2.3-1-limethylbenzene.

In addition, examples of organic peroxide catalysts and azo compound catalysts include:
The following compounds can be exemplified.

Dialkyl peroxides and diaryl peroxides such as di-tert-butyl peroxide, di-5ec-ethyl peroxide, tert-butyl-5ec-butyl peroxide, and dicumyl peroxide.

Sialyl peroxides and diacyl peroxides such as benzoyl peroxide.

Di-tert-butyl peroxalate, perbenzoic acid tQ
alkyl esters of percarboxylic acids such as r t-butyl, etc.: 2,2'-azobisisobutyronitrile, 2.
2”-Azobis-(2-methylbutyronitrile), 2
．． 2'-azobis-(2-methylhebutani-1-lyl),
1,1'-azobis-(1-cyclohexylcarbonitrile), 2.2'-methyl azobisisoacetate, 4.4
Azo compounds such as "-azobis-(4-cyanopentanoic acid), azidobenzene, etc.; tert-butyl hydroperoxide, 5ec-butyl hydroperoxide, tert-butyl hydroperoxide,
- Hydroperoxides such as laryl hydroperoxide, cumyl hydroperoxide, benzyl 12-droperoxide, penzhydryl hydroperoxide, decalyl hydroperoxide acetyl peroxide, cyclohexyl hydroperoxide, 1-decyl hydroperoxide; Furthermore, compounds easily oxidized by molecular oxygen, in the present invention diallyl terephthalate, aromatic hydrocarbons having at least one hydrogen atom at the benzyl position represented by formula (I>), or copolymer of the present invention. However, if these are oxidized with air or oxygen in advance or during the copolymerization reaction to produce a peroxide, they can be sufficiently used as a catalyst for the copolymerization reaction of the present invention.

Regarding the above-mentioned terephthalic acid diallyl ester copolymer, Japanese Patent Application No. 57-189 related to the applicant's earlier application
It is described in detail in No. 981.

The blend ratio of the terephthalic acid diallyl ester copolymer may be arbitrary, but in particular when higher performance such as heat resistance and impact resistance is required, it may be added to the total amount of diallyl phthalate resin used in the present invention. , 1% by weight or more, preferably 5% by weight of terephthalic acid diallyl ester copolymer
In order to improve the impact resistance of the composition, the content is more preferably 20% by weight or more. There is no particular upper limit to the amount of the copolymer to be blended, and when heat resistance is particularly 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 copolymer in an amount 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 as other components, the diallyl phthalate resin is usually obtained by polymerizing the ortho, iso, and tele monomers of the diallyl phthalate resin. A single diallyl phthalate bripolymer having a number average molecular weight of 2,000 to 20,000, solvent-soluble, heat-fusible, and having an allyl group in the molecule and capable of post-polymerization;
Alternatively, a mixture of the bripolymer and a reactive monomer or oligomer and/or an unsaturated polyester and /32 collectively refers to an epoxy acrylate-1-resin.

The above-mentioned reactive bamboo nitrates or oligomers include diallyl orthophthalate, diallyl isophthalate, diallyl terephthalate, diallytetrachloro or
” moortho, iso, and terephthalic acid 1~, diallylchlorendate, triallyl isocyanurate-1, triallyl cyanurate, l-lylyl trimerite-1,
Triallyl phosphate, styrene, α-chlorsubrene, methyl (meth)acrylate, butyl (meth)acryle-1~, ethylene glycol di(meth)acrylate
]・, polypylene glycol di(meth)acrylate,
1 ~ Limethylolpropane tri(meth)acrylate-j.
, glycidyl (meth)acrylate, allyl (meth)acrylate, mesolua 15-acrylate acrylamide, diacetone acrylamide, N-vinylcarbazone, N-methylolacrylamide, methylenebisacrylamide, methacrylamide, N-tert-butylacrylamide, 2 .4- or 2,6-tolylene diisocyanate, maleic acid semiester, phthalic acid monoallyl ester, allyl glycidyl ether, etc., or low molecular weight polymers thereof, and these may be used alone or in appropriate combinations. It can be used as

The content of the reactive monomer or oligomer is preferably 200 parts by weight or less per 100 parts by weight of the diallyl phthalate resin. If the amount exceeds 200 parts by weight, the curing speed will be unduly delayed and the internal distortion of the molded product will increase significantly due to an increase in curing shrinkage rate, which is not preferable.

As an unsaturated polyester, as an unsaturated dibasic acid,
For example, one or more of maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, daltaconic acid, mesaconic acid, etc.; Acids, aliphatic dicarboxylic acids such as sebacic acid and dodecanedicarboxylic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid and their halides, one or more of these acids, tetrahydrophthalic acid, hexahydrophthalic acid, etc., and ethylene. Refers to those synthesized from polyhydric alcohols such as glycol, propylene glycol, and 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 shrimp halohydrin, glycidyl ether type epoxy compounds obtained by the reaction of shrimp halohydrin with polyhydric phenols such as resorcinol, hydroquinone, catechol, bisphenol Δ, halogenated bisphenol A, etc., phenol novolac resins or cresol novolak resins. Novolac-type epoxy compounds obtained by the reaction of 1q with shrimp halohydrin, epoxy compounds obtained by epoxidizing aliphatic or alicyclic olefins, bis(N,N-diglycidylaminomethyl)benzene or cyclohexane, epoxidized products of polybutadiene, etc. is used.

These may be selected depending on the intended use of the composition, but if high dimensional stability, heat resistance, etc. are required, for example, bisphenol-type epoxy resin obtained by the reaction of bisphenol A and epichlorohydrin or novolac Preferred are novolak-type epoxy resins obtained by reaction of a resin and epichlorohydrin.

The amount of this epoxy resin used is 1 to 8 when the total resin content of the curable resin composition of the present invention is 100% by weight.
0% by weight, preferably 3 to 60% by weight, more preferably 5 to 50% by weight, and bending properties, impact resistance +i
Mechanical properties such 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 hardened molded objects will occur, and the composition will 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 deteriorate, such as dimensional stability, humidity resistance, heat resistance, electrical properties, and reliability. Dialkyl peroxides and diaryl peroxides such as monoethyl and dicumyl peroxide that do not cause any damage; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; 1,1-bis(tart-
peroxyketals such as (butylperoxy)-3,3,5-trimedelcyclohexane; hydroperoxides such as cumene hydroperoxide; lauroyl peroxide;
sialoyl peroxide and diacyl peroxide such as benzoyl peroxide and 2,4-dichlorobenzoyl peroxide; peroxycarbonates such as diisopropylberoxydicarbonate-1; tert-butylperoxyacetate;
Examples include peroxy esters such as tert-butylperoxyvivalate, tret-butylperoxyoctoate, and tert-butylperoxybenzoate, and also azo compounds such as azobisisobutyronitrile other than the above-mentioned organic peroxides. It can be used for.

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, metal soaps such as cobalt salts, vanadium salts, and manganese salts of naphthenic acid or off-acid, aromatic tertiary amines such as dimethylaniline and diethylaniline, etc. can be used in the present invention. Resin content 10
For example, 0.005 to 6 parts by weight may be added per 0 parts by weight.

As curing agents for curing epoxy resins, aliphatic polyamides such as dicyandiamide, aromatic amines,
Although acid anhydrides can be used, it is desirable to use a curing agent that does not undergo reaction at room temperature.

Examples of aromatic amines include metaphenylenediamine, xylylenediamine, diaminodiphenylmethane,
Examples include diaminodiphenylsulfone and benzyldimethylamine.

Examples of organic acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, maleic anhydride, phosphoric anhydride, pyromellitic anhydride, 3.3', 4.4'-
Examples include benzophenone tetracarboxylic anhydride, methylnadic anhydride, dodecylsuccinic anhydride, dichlorosuccinic anhydride, and hexahydro-D-phthalic 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 is 0.5 to 1.0% per 1 gram equivalent of epoxy resin.
The amount may be adjusted to correspond to 5 grams equivalent.

The resin composition of the present invention may contain, for example, fillers, flame retardants, coupling agents, polymerization inhibitors, internal mold release agents,
Pigments, colorants, and other additives can be blended within the range that does not impair the properties of the composition to improve molding processability or the physical properties of the molded article.

As the filler, commonly used inorganic and/or organic fillers can be used, and these can be used alone or in combination.

Alternatively, when using the composition as a binder to make a grinding wheel or sandpaper, 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, can be adjusted to suit various molding methods, exhibits excellent moldability, and has good dimensional stability. The molded product has excellent heat resistance, impact resistance, water/moisture resistance, chemical resistance, and adhesion, has high surface hardness, and has little change over time.

Therefore, the mechanical strength and electrical properties are outstanding, especially at high temperatures and high humidity, and the reliability is extremely high.

A more detailed explanation will be given below using examples.

Production examples 1 and 2 of terephthalic acid diallyl ester copolymer Equipped with a turbine blade type variable stirrer, a double pipe type supply nozzle for monomer and catalyst supply, a nitrogen persilo, a leak valve, a sampling port, a thermometer and a pressure gauge. Inner diameter 600II1
A jacketed 5US304 polymerization tank with an internal volume of 120 m and an internal volume of 120 e was used. The double pipe 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 pipe is set to 1.5 mm before entering the polymerization tank, and the residence time in the supply piping is controlled. I kept it as short as possible. In case of nozzle blockage, install 3 such nozzles.
I installed one. The sampling port is also installed in the body of the polymerization tank.
The internal pressure during the polymerization reaction was used to allow samples of the liquid phase to be collected. An oil rotary vacuum pump and a nitrogen cylinder were connected to the nitrogen versilor so that they could be switched as needed.

The above polymerization tank was charged with 60 to 1 of the formula (I) aromatic hydrocarbon (HC) shown in Table 1 below, and the pressure was reduced with a vacuum pump at room temperature, and the pressure was returned to normal pressure with nitrogen gas three times. After repeatedly replacing the air in the tank with nitrogen, the pressure was reduced again and the polymerization tank was sealed. Start the stirrer and while stirring at 240RI)M, pass steam through the jacket to a temperature of 14
The temperature was raised to 0°C.

The stirring speed was increased to 720 PPM, and terephthalic acid diallyl ester was added at a predetermined rate from the outer pipe of the double pipe nozzle, and di-tert-butyl peroxide (DTB) was added at the same time.
PO) and aromatic hydrocarbon (+-IC) of formula (I) were mixed in advance at a molar ratio of 0.5:i at a predetermined speed and at a discharge pressure of 70 h/co? was supplied to the polymerization tank using a pump. During this time, the steam was adjusted to maintain the temperature of the polymerization tank at 140°C. Furthermore, the supply equation (I)
Terephthalic acid diallyl ester (DAT) was heated to 15°C.
The mixtures of di-tert-butyl peroxide and aromatic hydrocarbon were each cooled to 5° C., and the piping leading to the polymerization tank was kept cold. m@tank pressure was 0.3-2 kcJ/cIjG.

When the supply of predetermined amounts of terephthalic acid diallyl ester, aromatic hydrocarbon, and di-butyl peroxide was completed, the steam was stopped, the stirring speed was lowered to 24 ORPM, and cooling water was passed through the jacket for cooling. 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 by refractive index and GPC.

The feed rates and amounts of diallyl terephthalate, aromatic 1M 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 unreacted aromatic hydrocarbons in the evaporation residue were removed.
The ratio of the copolymer to the unreacted diallyl terephthalate to the gold article 1 was set to 0.3:1 by weight, and then the evaporation residue was mixed with the supplied diallyl terephthalate.
The copolymer was precipitated by stirring while dropping the mixture into a stirring tank containing 5 times the amount of methanol by weight. The precipitated copolymer was thoroughly washed with methanol from the same city, filtered, dried, and pulverized to obtain a powdered copolymer.

Table 1 shows the yield and physical properties of the copolymer.

27- Table 1 28- In Table 1 above, (1) is the measured value in terms of polystyrene by the gel permeation chroma graph method.
A 150CGPCI device was used.

For (2), a light transmission type automatic melting point measuring device manufactured by Hattler Co., Ltd. rPF 61J was used.

(3) is a value measured using a Brabender Plastograph manufactured by Brabender (Germany).

Mixing chamber capacity 50cc, rotor model W501-1, sample s
og + zinc stearate o, sg, mixed Il! Total temperature 1
Crosstalk resistance is 5000 at 30℃ and rotor rotation speed 22RPM.
Continue until m-0 is reached, and from the torque curve of the recording paper,
The lowest torque value was defined as the Brabender melt viscosity, and the time from the end of sample loading to 5000 mQ was defined as the processing time.

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, kneading I
) for 6 minutes) to form a sheet, which was ground in a Henshi I Lumiki machine to form a compound.

Take 20 to 30 liters of the 10-pound pound, make a nearly disk-shaped tablet with a diameter of 50 nm and a thickness of 1 ounce using a mold and press it manually. Place it in the center of the cavity of a compression mold that has been adjusted to the desired temperature, and mold with an automatic press for 20 minutes at a mold temperature of 160°C and a pressure of 100 mm to form a circle with a diameter of about 10 On and a thickness of 2 nm. A plate-shaped molded product was obtained.

The molded product was subjected to a general test method according to JIS K-6911, a drop tlti impact test and a heat resistance test according to JIS K-7211, 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.

Drop 519Ii Impact Test Thirty-six test pieces were cut out from two molded products using a diamond cutter and subjected to measurement.

The testing machine was a DuPont falling ball tester (length: 500g, flat support, 1/2 inch R), and 50% destruction was determined using the Dixon mode method (Reference: J
] SK-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 left to cool in a desiccator, and each part was actually measured. . At this time, if the sp average value of the mold foil reduction of the three test pieces does not reach 10% of the initial weight, leave these test pieces in a constant temperature bath at 200 ± 2°C for an appropriate period of time and heat them again. In order to reduce the weight, the test was repeated until the average value of the weight loss of the three test pieces reached 10% of the initial weight, and the heat resistance ↑1 was evaluated based on the time required for this test.

Notes (1) “Epotote YD-011” manufactured by Tobu Kasei Co., Ltd. (2
) [Epotote YDCN-20HJ (3) "Daiso Sodap" manufactured by Osaka Soda Co., Ltd. (4) [Daiso Isodap] (5) Iodine value 91, number average molecular weight 7900 (6) Manufactured by Nippon Yubikane 1 [Yubika 8524J (7) Osaka Organic Co., Ltd. Kagakusha 1 [Viscoat #540J (8) Oligomer Example 10 with an iodine value of 13 and a number average molecule ω of 1350 produced in the same manner as Production Example 2. Comparative Example 6 A disc-shaped molded product was obtained using the compound of Example 2, with an outer diameter of 14 cm and an inner diameter of 6 nm.

An iron mold washer with a thickness of 0.5 nm 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 in which the washer was embedded. The molded article was subjected to a temperature cycle test in which one cycle was treatment at +80°C for 2 hours and then at -25°C for 2 hours, and 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 11-13. Comparative Examples 7 to 8 Using each resin mixture having the composition of Examples 2, 3 and 6 and Comparative Examples 2 and 3, a composition 1k (l
was prepared in the following manner.

34- Blend Resin Mixture 100 Heavy Color Part Hydroquinone 0.011! Methacryloxysilane 0,6. 1 Calcium Stearin 2 II Short Glass Fiber * ioo n Calcium Carbonate 40 * Manufactured by Asahi Fiberglass In the above formulation, dicumyl peroxide, dicyandiamide, hydroquinone and methacryloxysilane were dissolved together with the resin in 500 g of acetone. This was charged into a crusher with a capacity of 31, then calcium stearate and calcium carbonate, which had been mixed well in advance, were added and mixed for about 5 minutes.
Mixed for a minute. This was left to stand for a day and night to volatilize the residual acetone, and then kneaded for about 10 minutes with rolls (front roll: 100°C, rear roll: 90°C). The compound taken out in the form of a sheet from the roll was ground in a feather mill equipped with a 2-n diameter Sufi 35-lean to obtain a granule-like compound.

Each of the obtained dung pounds was molded in the same manner as in Examples 1 to 9, and the physical properties were tested. The results are shown in Table 3-1.3-2.

Table 3-1 Table 3-2 38 Example 14 Comparative Example 10 Using each resin mixture having the composition of Example 2 and Comparative Example 2,
A compound consisting of the following composition was thoroughly kneaded using methyl ethyl ketone manufactured by Habodo City, and after removing the solvent, the mixture was sized to form 1
A plate-shaped molded product with a thickness of 5n was made by hot pressing at 70℃ (
It was.

Compound resin mixture 20 volumes Obu Nagi grain JIS 2CWA #46 50 n Cryolite 30
, +1i7 The bending properties of the molded products were measured according to JIS K6911, and the results are shown in Table 4.

Table 4 39-

Claims (1)

[Scope of Claims] A curable resin composition characterized by blending an epoxy resin with a diallyl phthalate resin containing the following terephthalic acid diallyl ester copolymer. 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. However, in the above formula, R1 and R2 are , each represents a group selected from the group consisting of a hydrogen atom and a lower alkyl group, and TL is an integer of 1 to 3.