JPS6228979B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a resin composition having particularly excellent impact resistance. More specifically, the present invention provides diallyl phthalate resin with diallyl terephthalate and 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.) The present invention relates to a highly impact-resistant resin composition characterized in that a copolymer with an aromatic hydrocarbon having one hydrogen atom is blended in an amount of 1% by weight or more based on the total amount of the resin. Traditionally, diallyl phthalate resins have excellent mechanical properties such as dimensional stability and rigidity under heat, and electrical properties, and are widely used in fields that require high reliability. It has the disadvantage of being brittle and lacking in toughness, and in recent years, as molded products have become smaller, the problem of cracking and chipping in thin parts and small protrusions of the molded products has become more serious. In order to overcome these technical problems, many proposals have been made to improve the brittleness of diallyl phthalate resins by improving blending techniques and polymer blends. For example, methods of reinforcing with fillers such as glass fibers, and methods of modifying with flexible polyester or rubber-like polymers are known.
However, although all of these methods were intended to impart toughness to the diallyl phthalate resin without impairing its excellent properties, it is difficult to say that these methods have achieved the objective. For example, in the method using the filler described above,
It is necessary to leave the long fiber filler in the molded product, but this imposes significant restrictions on the kneading method and molding method, making it impractical. In addition, in the method of modifying with other polymers etc. mentioned above, dimensional stability,
Usually, any one of heat resistance, moisture resistance, mechanical strength, electrical properties, and moldability is unduly reduced.
As described above, the conventionally proposed methods have reached their limits of improvement, and the current situation is that the conventionally proposed methods cannot offer much in order to achieve satisfactory improvements. On the other hand, polybutylene terephthalate (PBT)
Thermoplastic resins such as PPS and polyphenylene sulfide (PPS) have made remarkable progress, and resins and compounding techniques with excellent heat resistance and electrical properties have been developed, and they are also highly productive. It has come to be adopted in a wide range of fields, including fields where thermosetting resins are used. However, since it is a thermoplastic, there are problems with deformation due to creep and heat resistance, and its reliability is not as high as that of thermosetting resins, especially when used for long periods of time under high temperature and high humidity conditions. The present inventors conducted various studies with the aim of improving the properties of such diallyl phthalate resins, and as a result, the present inventors added diallyl terephthalate and at least the benzyl position represented by the above formula () to the resin. When a copolymer consisting of an aromatic hydrocarbon having one hydrogen atom (hereinafter referred to as a terephthalic acid diallyl ester copolymer) is blended, the resin can be improved without impairing the desirable properties inherent in the diallylphthalate resin. It has been found that the brittleness, which has traditionally been considered a drawback, is significantly improved, and a resin composition having a high impact value can be obtained. In addition, by blending the copolymer, the heat resistance of diallyl orthophthalate resins, which were conventionally considered to be somewhat inferior in heat resistance, can be significantly improved. At the same time, it was also discovered that bending strength was significantly improved. The diallyl phthalate resin used in the present invention refers to ortho diallyl phthalate resin,
Obtained by polymerizing the monomers of iso and tele, usually number average molecular weight 2000 to 20000, solvent soluble,
A general term for a heat-fusible, post-polymerizable diallyl phthalate prepolymer having an allyl group in the molecule, or a mixture of the prepolymer and a pseudo-reactive monomer and/or an unsaturated polyester. The above reactive monomers include ortho,
Diaryl phthalate monomers consisting of iso and tele isomers, styrene monomers such as styrene and α-chlorostyrene, methyl (meth)acrylate, butyl (meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di( Examples include acrylic acid ester monomers such as meth)acrylate and trimethylolpropane tri(meth)acrylate. The amount of the reactive monomer blended is preferably 70% by weight or less based on the total resin content of the composition of the present invention. If the amount exceeds 70% 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. The above-mentioned unsaturated polyesters may be those commonly known, such as polybasic unsaturated acids such as maleic acid and fumaric acid, polybasic saturated acids such as phthalic anhydride, isophthalic acid, and terephthalic acid, diethylene glycol, propylene Acid value 5~ manufactured by conventional method using polyhydric alcohol such as glycol
From a viscous liquid at room temperature of about 100°C to a softening point of 150°C
There are the following solid forms. The amount of unsaturated polyester blended is preferably 80% by weight or less based on the total resin content of the composition of the present invention. If the composition exceeds 80% by weight,
This is undesirable because the properties of conventional diallyl phthalate resins are significantly reduced and the moisture resistance of the resulting molded products is also reduced. The terephthalic acid diallyl ester copolymer blended into the composition of the present invention is a polymer newly developed by the present applicant, and is a polymer in which terephthalic acid diallyl ester and an aromatic hydrocarbon represented by the following formula () are organically combined. A copolymer obtained by polymerization in the presence of a peroxide or 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. It has a structure in which C and/or 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.
It is a copolymer having a structural feature of 3 to 10 atoms, preferably 3 to 10 atoms. 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. Examples of such aspects include, 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 part is the head shown in formula ().
Tail join, i.e. () 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. (g) The polystyrene equivalent number average molecular weight (n) measured by GPC (gel permeation chromatography) method is 4000 to 10000, the weight average molecular weight (w) is 70000 to 200000, and n
The molecular weight distribution expressed as the ratio w/n of w and w is 10 to 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 by setting reaction conditions to preferably 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 of the above formula ()
are each selected from the group consisting of a hydrogen atom and a lower alkyl group, and examples of the lower alkyl group include C ₁ -C ₅ alkyl groups. Examples of such compounds of formula () include toluene, ethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene, sec-butylbenzene, n-amylbenzene, sec-amylbenzene, and isoamylbenzene. Benzene, (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-dipropylbenzene, 1,4-dipropylbenzene, diisopropylbenzenes, p-cymene, 1,2-dibutylbenzene, 1,3-dibutylbenzene, 1,4-
Examples include dibutylbenzene, 1,2-diisoamylbenzene, 1,3-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, n-decyl hydroperoxide, etc. Hydroperoxides; Furthermore, compounds easily oxidized by molecular oxygen, in the present invention, terephthalic acid diallyl ester, aromatic carbide having at least one hydrogen atom at the benzylic position represented by the formula () Hydrogen or the copolymer of the present invention corresponds to this, and 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. In addition,
Regarding the above-mentioned terephthalic acid diallyl ester copolymer, the patent application filed in 1982-
It is described in detail in No. 189981 (Japanese Unexamined Patent Publication No. 59-80409). The amount of the terephthalic acid diallyl ester copolymer blended in the composition of the present invention is 1% by weight or more, preferably 5% by weight or more, more preferably 20% by weight or more, based on the total amount of the diallylphthalate resin and the copolymer. It is preferable that the amount is at least % by weight in order to improve the impact resistance of the composition. There is no particular restriction on the upper limit of the amount to be blended, and when heat resistance is particularly required, the blending ratio of the copolymer may be increased. Also, especially
In order to obtain excellent bending strength when using a diallyl orthophthalate resin, it is preferable to blend the above-mentioned copolymer into the resin in an amount of 2 to 90% by weight. As already mentioned, it is often pointed out that conventional diallylphthalate resins lack toughness.
If the molded product is dropped while being handled, it is likely to chip.
In practical use, various complaints such as protruding parts such as ribs are easily damaged, the contact surface with the printed wiring board is easily damaged when used as an electronic circuit connector, and easily cracked when screws are tapped. It was hot. Furthermore, in recent years, with the miniaturization of electronic devices and components, for example, the spacing between connector pins has been required to be narrower, and in addition to soldering, which requires heat resistance, wiring methods using pressure bonding have become widespread. Although thermoplastic resins are allowed to be used, thermosetting resins are often used due to requirements for dimensional stability, heat resistance, creep resistance, etc. Therefore, there has been a strong demand in the industry to improve the toughness and impact resistance of diallylphthalate resins. Conventionally, impact resistance has been compared using shear py and isot impact values, but although these can be used as a measure for thick walls, the situation often changes when it comes to thin walls. Therefore, the inventors of the present invention decided to mainly adopt a drop weight test using a thin plate, taking into consideration the trend of miniaturization of products. As a result of this comparative test under the same conditions, the falling weight impact value of the resin composition of the present invention was approximately 80 mm at most for the conventional diallyl phthalate resin, while that of the terephthalic acid diallyl ester copolymer. The composition containing 5% by weight of the resin reaches about 180 mm, and the one containing 20% by weight reaches about 190 mm, which is similar to the value of the copolymer, which is unexpected and significantly improved. It was found to have impact properties. In addition, the bending strength of the diallyl phthalate resin alone and the diallyl terephthalate copolymer alone is about 8 Kg/mm ² for the former and about 7 Kg/mm ² for the latter,
Among the compositions of the present invention, those containing 2 to 90% by weight of terephthalic acid diallyl ester copolymer in the resin content show a bending strength of about 10 Kg/mm ² , which is much larger than that of each resin alone. I found out. Furthermore, the heat resistance of molded products made of diallyl orthophthalate resin as a sole resin component is, for example, 200°C.
When exposed to an air oven and measured for weight loss, it shows a 10% decrease in initial weight in 260 to 288 hours, but in the present invention, 20% by weight of terephthalic acid diallyl ester copolymer The copolymer containing the copolymer takes about 1000 hours to reduce by 10% of the initial weight, and the copolymer containing 50% by weight takes about 1600 hours, showing a remarkable heat resistance improvement effect. I understand. As described above, the composition of the present invention significantly improves the brittleness that has been considered a drawback of conventional diallylphthalate resins, and also has improved bending strength and heat resistance. Dimensional stability, which was considered to be an excellent feature of diallylphthalate resin,
It exhibits characteristic properties such as chemical resistance, moisture resistance, and electrical properties. In addition, processability during molding,
It has excellent moldability, both in terms of curing speed and on par with conventional diallyl phthalate resins. As the curing agent for the composition of the present invention, peroxides commonly used in diallyl phthalate resins, such as dicumyl peroxide, tert-butyl perpenzoate, benzoyl peroxide, etc., can be used as they are. The compounding amount is based on the resin content.
0.1 to 6% by weight is suitable. The composition of the present invention may contain fillers, polymerization accelerators, polymerization inhibitors, internal mold release agents, coupling agents, pigments, flame retardants, etc. as desired, as in the case of conventional diallylphthalate resin compositions. The molding processability or the physical properties of the molded article can be improved by adding these additives within a range that does not impair the properties of the composition. Examples of fillers that can be used include inorganic and/or organic fillers, and these can be used alone or in combination. The amount used may range from about 1 to about 300% by weight based on the weight of the resin. Specific examples of these fillers include talc, mica, asbestos, glass powder, silica,
Clay, shirasu, titanium oxide, magnesium oxide, calcium carbonate, alumina, asbestos fiber, silica fiber, glass fiber, silicate glass fiber, alumina fiber, carbon fiber, boron fiber, beryllium fiber, steel fiber, whisker, etc.; organic filler Examples include natural fibers such as cellulose, pulp, acrylic fibers, polyester fibers such as polyethylene terephthalate, cotton, rayon, and vinylon. Examples of the polymerization accelerator include metal soaps such as cobalt salts, vanadium salts, and manganese salts of naphthenic acid or octoic acid, and aromatic tertiary amines such as dimethylaniline and diethylaniline. Examples of the amount used include about 0.005 to about 6% by weight based on the weight of the resin of the present invention. Furthermore, examples of polymerization inhibitors include, for example,
Examples include quinones such as p-benzoquinone and naphthoquinone, polyhydric phenols such as hydroquinone, p-tert-butylcatechol, hydroquinone monomethyl ether, and p-cresol, and quaternary ammonium salts such as trimethylammonium chloride. The amount used is, for example, about 0.001 to about 0.1% by weight based on the weight of the resin of the present invention. Examples of internal mold release agents include metal salts of stearic acid such as calcium stearate, zinc stearate, and magnesium stearate. The amount used is
Examples of amounts used include from about 0.1% to about 5% by weight based on the weight of the resin of the present invention. Furthermore, examples of coupling agents include r-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and the like. The amount used is approximately
Examples include amounts of 0.01 to about 3% by weight. Examples of pigments include carbon black, iron black, cadmium yellow, benzidine yellow, cadmium orange, red iron, cadmium red,
Pigments such as cobalt blue and anthraquinone blue can be exemplified, and the amount used thereof can be exemplified in an amount of about 0.01 to about 10% by weight based on the weight of the resin of the present invention. Examples of flame retardants include inorganic compounds such as antimony oxide and aluminum hydroxide, tris(chloroethyl)phosphate, tris(2-bromo3-
chloropropyl) phosphate, phosphorus compounds such as ammonium polyphosphate, chlorinated paraffin,
Examples of known diallyl phthalate resins include chlorine compounds such as diallyl chlorendate, bromine compounds such as decabromodiphenyl ether, and tetrabromo phthalic anhydride. The appropriate amount is from about 1 to about 30% by weight based on the weight of the resin of the present invention. As a method for molding the composition of the present invention, known molding methods and molding conditions similar to those for conventional diallyl phthalate resins can be used as they are. That is, a casting method in which the composition of the present invention is injected into a mold and cured. heating the composition to a fluid state;
An injection molding method or a transfer molding method involves putting the composition into a mold and heating it to harden it. A compression molding method involves heating and pressurizing the composition in a mold to harden it. A fibrous molding method involves dissolving the composition in an appropriate organic solvent. A laminate forming method in which the sheet is impregnated and, after drying, the resin is cured in the fibrous sheet under pressurized conditions if necessary, a fine powder or solution of the composition is applied to the substrate, and Examples include a coating method for curing, and a decorative board molding method for impregnating printing paper or the like with the composition solution, drying, and curing by heating and pressing on a substrate. During molding, the heating temperature for curing is approximately 120~
Examples include temperatures such as about 190°C. In addition, when using pressurized conditions, the pressure is about 5 to about 1000
A pressure such as Kg/cm ² can be exemplified. The composition of the present invention can be used as a molding material in a wide range of fields as listed below. For example, connectors, motor commutators, governors, coil bobbins, relays, switches, terminal boards, ignitions, breakers, sockets, binders for sliding resistors, printed wiring boards, encapsulating materials for electronic parts and elements, coil encapsulation, and other light electrical appliances. Electrical and electronic fields such as insulating materials in the heavy electrical field; For example, plastic brake pistons and other mechanical fields; For example, tableware and other daily necessities fields; For example, medical materials field such as trays and containers that require chemical or steam sterilization. It is useful as a molding material in Furthermore, the composition is impregnated or applied onto a fibrous sheet such as paper, non-woven fabric, glass cloth, etc. in the presence or absence of a solvent, and the composition is pressed and cured onto a wood, paper, metal or other inorganic substrate, or the composition is pre-cured. The cured product is applied to the above-mentioned base material in the form of a decorative board and is useful for various building materials, furniture, interiors, cabinets, kitchen equipment, axles, ship interior materials, and other fields. In addition, if the composition is directly impregnated into wood and cured, a wood-plastic composite (so-called
WPC), which can be used in fields such as flooring materials, edge decks, floorboards, architectural structural materials, and sporting goods, and can also be used as a laminate made by impregnating and laminating glass cloth or other fibrous sheet structures at high temperatures and high humidity. Fields that require various characteristics at the same time, such as terminal plates, motor wedges, insulation collars, slot armors, coil separators, and other rotating machine-related fields, duct pieces, barriers, terminal plates, operating rods, switchboards, etc. It is useful in static equipment related fields such as panels, printed wiring boards, variable cap insulating supports, etc. Furthermore, it is useful in fields that require excellent dimensional stability and good mechanical strength even when there are severe changes in temperature and humidity. For example, fields that require chemical resistance such as laser domes, missile blades, rocket nozzles, jet aircraft air ducts, and parts of various chemical equipment, antennas, etc.
Fields that require weather resistance, chemical resistance, and mechanical strength such as skis, ski stocks, and fishing rods, other paints, materials for molds for molding other resins, hot stamping resins, UV curing inks, lenses, and other optical products. It can be used in a wide range of applications, such as a material for commercial purposes, a binder for glass fibers and carbon fibers, and a resin for resist films in phosphorography using light, electron beams, or X-rays. A more detailed explanation will be given below using examples. Production examples 1 and 2 of terephthalic acid diallyl ester copolymer 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. The mixture was mixed in advance at a molar ratio of 0.5:1 and was supplied to the polymerization tank at a predetermined speed 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 predetermined amounts of diallyl terephthalate, aromatic hydrocarbon, and di-tert-butyl peroxide was completed, the steam was turned off, the stirring speed was lowered to 240 RPM, and cooling water was passed through the jacket for cooling. After cooling to around room temperature, open the leak valve and return to normal pressure.
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 was set to 0.3:1 by weight, and then the evaporated residue was stirred while being dropped into a stirring tank containing methanol in an amount 5 times the weight of the supplied diallyl terephthalate to precipitate a copolymer. . Wash the precipitated copolymer thoroughly with the same amount of methanol,
A powdered copolymer was obtained by filtration, drying, and pulverization. Table 1 shows the yield and physical properties of the copolymer. Production Examples 3 to 6 Production Example 1 using ethylbenzene, isopropylbenzene, diethylbenzene (commercially available, mixture of 1,2-, 1,3-, and 1,4-compounds) and pseudocumene as aromatic hydrocarbons of formula () Polymerization was carried out in the same manner as in 2 to obtain a terephthalic acid diallyl ester copolymer. The yield and physical properties of the copolymer are shown in Table 1.

[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 Mettler 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 the 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 8 Comparative Examples 1 to 6 After adding 2 parts by weight of dicumyl peroxide to each composition shown in Table 2 and mixing well, roll kneading (front roll 90 to 100°C, contact roll 60 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°C with a high-frequency preheater, immediately adjust it to the specified temperature. Place it in the center of the cavity of the compression molding circular mold that you prepared.
10 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 (500g load, flat support, 1/2 inch R) was used as the tester, 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°C 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 heat resistance was evaluated.

【table】

[Table] Examples 9 to 12 20 parts by weight of the terephthalic acid diallyl ester copolymer obtained in Production Examples 3 to 6 above, 80 parts by weight of the same diallyl orthophthalate prepolymer as in Example 1, and 2 parts by weight of dicumyl peroxide. A composition consisting of the above was rolled to form a compound in the same manner as in Examples 1 to 8, and test pieces were prepared from this and physical property tests were conducted in the same manner as in Examples 1 to 8. The results are shown in Table 3.
It was shown to.

【table】

[Table] Examples 13-14 Comparative Examples 7-8 Using each resin mixture of Examples 1 and 3 and Comparative Examples 1 and 6 or the resin alone, approximately 1 kg of a full compound consisting of the following formulation was mixed into the following mixture. Prepared by method. Compound resin 100 parts by weight Dicumyl peroxide 2 Hydroquinone 0.01 Methacryloxysilane 0.6 Calcium stearate 2 Short glass fiber * 60 Calcium carbonate 40 * Manufactured by Asahi Fiberglass In the above compound, dicumyl peroxide, Hydroquinone and methacryloxysilane were dissolved together with the resin 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. 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 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 8, and the physical properties were tested. Table 4 shows the results.

【table】

【table】

Claims (1)

[Scope of Claims] 1. A highly impact-resistant resin composition comprising a diallyl phthalate resin blended with the following terephthalic acid diallyl ester copolymer in an amount of 1% by weight or more based on the total amount of the 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.