JPH0151486B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to diallylphthalate resin compositions having improved curing speed and high mechanical strength and stiffness. Conventionally, 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. However, on the other hand, the resins are brittle and It has the disadvantage of insufficient 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. The present applicant has developed and proposed a new terephthalic acid diallyl ester copolymer and a diallyl phthalate resin composition containing the copolymer with the aim of improving the properties of such diallyl phthalate resins (Japanese Patent Application No. 1983- No. 189981 (Special Application No. 10766/1989). As a result of intensive research to further improve the physical properties of the above resin composition, the present inventors discovered that the addition of fumaric acid or fumaric acid derivatives was extremely effective in improving mechanical strength, rigidity, etc., and completed the present invention. This is what I did. That is, the present invention includes blending one or more compounds selected from fumaric acid, a monoalkyl ester of fumaric acid, and a dialkyl ester of fumaric acid into a diallyl phthalate resin containing a terephthalic acid diallyl ester copolymer. This is a characteristic resin composition. The terephthalic acid diallyl ester copolymer referred to in the present invention has the formula () Terephthalic acid diallyl ester represented by the formula () (wherein R ₁ R ₂ each represents a group selected from the group consisting of a hydrogen atom and a lower alkyl group, and n represents an integer of 1 to 3) at least one hydrogen atom at the benzyl position A terephthalic acid diallyl ester copolymer derived from an aromatic hydrocarbon having the formula (a), one monomer unit of the formula () at the end of the monomer unit of the formula (), and one monomer unit of the formula () at the benzyl position It has a structure in which the allyl group of the monomer unit and its C ^* and/or C ^* are carbon-carbon bonded. 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 the structural characteristics of 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 the 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 the formula ()
3 to 11 as shown in , but this carbon-carbon bond molecular chain portion is a head-to-tail bond shown in formula (), that is, the following formula () In addition to , it can have a head-to-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 from 1.20 to 1.25 (e) Softening range from about 50 to about 120°C (f) 50% methyl ethyl ketone solution viscosity from 80 to 300 centipoise (30°C). (g) The polystyrene equivalent number average molecular weight (n) measured by GPC (gel permeation chromatography) method is 4,000 to 10,000, the weight average molecular weight (w) is 70,000 to 200,000, and the relationship between n and Mw is The molecular weight distribution expressed as the ratio w/n is
10-40. (h) The Brabender melt viscosity measured with a Brabender plastograph is 250 to 2600 m·g, and the 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 (e) 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 toluene, ethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene, sec-butylbenzene, n-amylbenzene, sec-amylbenzene, and 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, 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
-Alkyesters of percarboxylic acids such as butyl; 2,2'-azobisisobutyronitrile, 2,
2-azobis-(2-methylbutyronitrile),
2,2'-azobis-(2-methylheptanitrile), 1,1'-azobis-(1-cyclohexylcarbonitrile), methyl 2,2'-azobisisobutyrate, 4,4'-azobis-(4-cyano azo compounds such as pentanoic 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 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. The above-mentioned terephthalic acid diallyl ester copolymer is described in detail in Japanese Patent Application No. 189981/1989 filed earlier by the present applicant. 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, a diallyl phthalate prepolymer 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 may be used alone, or a mixture of the prepolymer and a reactive monomer or oligomer. and/or a reaction product of unsaturated polyester and/or epoxy resin with (meth)acrylic acid, that is, a general term for resins that may contain epoxy acrylate and the like. The reactive monomers or oligomers include diallyl orthophthalate, diallyl isophthalate, diallyl terephthalate, diallytetrachloro or bromoortho, iso and terephthalate, diallyl chlorendate, triallyl isocyanurate, triallyl cyanurate, triallyl trimellitate. , 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, Diacent acrylamide, N
-Vinylcarbazone, N-methylolacrylamide, methylenebisacrylamide, methacrylamide, N-tert-butylacrylamide, 2,4- or 2,6-tolylene diisocyanate, maleic acid semiester, phthalic acid monoallyl ester, allylglycidyl Examples include ethers and low molecular weight polymers thereof, and these can be used alone or in appropriate combinations. 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 prepolymer. 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. The unsaturated polyester includes one or more unsaturated dibasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, mesaconic acid, etc.
Examples of saturated dibasic acids include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and their halides, tetrahydrophthalic acid, hexahydrophthalic acid, etc. refers to one synthesized from one or more of these and a polyhydric alcohol such as ethylene glycol, propylene glycol, or neopentyl glycol. The selection of each component and the combination thereof may be determined depending on the intended use of the molded article. For example, if a high degree of dimensional stability, heat resistance, etc. are required, it is preferable to use terephthalic acid-based unsaturated polyester. The amount of unsaturated polyester blended is preferably 400 parts by weight or less per 100 parts by weight of diallyl phthalate prepolymer.
If it exceeds 400 parts by weight, the properties of the conventional diallyl phthalate resin will be significantly reduced and the moisture resistance of the resulting molded product will be reduced, which is not preferable. When the terephthalic acid diallyl ester copolymer is mixed with other diallyl phthalate resins such as those mentioned above, the ratio is preferably 5% by weight or more of the terephthalic acid diallyl ester copolymer in the total amount of the diallyl phthalate resin. is preferably 20% by weight or more in order to improve the impact resistance of the composition. 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. The alkyl group of the monoalkyl ester or dialkyl ester of fumaric acid blended into the composition of the present invention is a linear or branched saturated aliphatic hydrocarbon group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 1-amyl,
Isoamyl, neopentyl, n-octyl, 2-
Examples include ethylhexyl, but other fumaric acid mono- or dialkyl esters can also be used, and can be used alone or in appropriate combinations. The blending amount of fumaric acid and/or fumaric acid alkyl ester is preferably 0.01 to 5 parts by weight per 100 parts by weight of diallylphthalate resin, and if it is less than 0.01 parts by weight, mechanical properties such as bending strength, rigidity, and impact resistance will be improved. If the amount exceeds 5 parts by weight, the curing speed and mechanical properties may be improved, but water resistance and electrical properties tend to deteriorate. As a curing agent for curing the composition of the present invention,
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)-3,3,5-
peroxyketals such as trimethylcyclohexane; hydroperoxides such as cumene hydroperoxide; diaroyl and diacyl peroxides such as lauroyl peroxide, benzoyl peroxide, and 2,4-dichlorobenzoyl peroxide; peroxycarbons such as diisopropyloxycarbonate. tert-butyl peroxyacetate, tert
Examples include peroxy esters such as -butylperoxypivalate, tert-butylperoxyoctoate, and tert-butylperoxybenzoate, and azo compounds such as azobisisobutyronitrile other than the above-mentioned organic peroxides can also be used. can. Each of these curing agents alone,
Alternatively, two or more types can be used in combination,
The amount used is 0.1 to 6 parts by weight per 100 parts by weight of diallylphthalate resin. In addition, as a polymerization accelerator, for example, 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 are added to 100 parts by weight of diallylphthalate resin. It may be added in an amount of 0.005 to 6 parts by weight. Fillers, flame retardants, coupling agents, polymerization inhibitors, internal mold release agents, pigments, and other additives may be freely added to the resin composition of the present invention as needed within the range that does not impair the properties of the composition. can do. Examples of fillers include inorganic fillers such as talc, mica, asbestos, glass powder, silica, clay,
Organic fillers include natural fibers such as cellulose, whitebait, titanium oxide, magnesium oxide, calcium carbonate, alumina, glass fiber, asbestos fiber, alumina fiber, carbon fiber, boron fiber, beryllium fiber, steel fiber, whisker, etc.
Pulp, acrylic fiber, polyester fiber such as polyethylene terephthalate, cotton, rayon,
Examples include Vinylon (trade name) and the like, and the amount used is about 1 to about 300% by weight based on the weight of the resin component.
Examples of flame retardants include inorganic compounds such as antimony oxide and aluminum hydroxide, phosphorus compounds such as tris(chloroethyl) phosphate, tris(2-bromo-3-chloropropyl) phosphate, ammonium polyphosphate, and chlorinated paraffins. , chlorine compounds such as diallyl chlorendate, decabromodiphenyl ether, bromine compounds such as tetrabromo phthalic anhydride, and other known diallyl phthalate resins. Examples of coupling agents include γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, and allyltrimethoxysilane. Examples of polymerization inhibitors include quinones such as P-benzoquinone and naphthoquinone, hydroquinone, and P-benzoquinone.
Examples include polyvalent phenols such as tert-butylcatechol, hydroquinone monomethyl ether, and P-cresol, and quaternary ammonium salts such as trimethylammonium chloride. Examples of internal mold release agents include metal salts of stearic acid such as calcium stearate, zinc stearate, and magnesium stearate. Pigments include carbon black, iron black, cadmi yellow, benzidine yellow, cadmi orange,
Examples include pigments such as red iron, cadmium red, cobalt blue, and anthraquinone blue. 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. Furthermore, fumaric acid and fumaric acid derivatives may be integrally blended with a diallylphthalate resin, or may be used as a reinforcing agent for fiber sheets, etc., or as a pre-treatment agent for fillers. When used as such a pretreatment agent, the fumaric acid or fumaric acid derivative may be dissolved in a suitable solvent, mixed with the filler or reinforcing material, and then the solvent may be removed. Since the resin composition of the present invention has a faster curing speed than conventional diallyl phthalate resin compositions, it is possible to significantly shorten the molding cycle, and the resulting molded products do not have the drawbacks of conventional diallyl phthalate resins. In addition, it has improved bending strength and heat resistance, and has improved the dimensional stability, chemical resistance, moisture resistance, and electrical resistance that were considered to be the excellent characteristics of diallyl phthalate resins. Indicates the property of possessing a property. Furthermore, it exhibits much higher mechanical strength and rigidity than diallyl phthalate-based resins containing diallyl terephthalate copolymer that do not contain fumaric acid or fumaric acid derivatives. The improvement in curing speed is thought to be due to the good copolymerizability of fumaric acid and fumaric acid derivatives with the diallyl phthalate resin, and the improvement in strength and rigidity is due to the coupling effect of fumaric acid and fumaric acid derivatives with resin and molding. This is thought to be due to improved adhesion with various reinforcing agents and fillers that are sometimes used. This will be explained below using Examples and Comparative 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. 60 kg of aromatic hydrocarbon (HC) of the formula () shown in Table 1 below was charged into the above polymerization tank, and the operation of reducing the pressure with a vacuum pump at room temperature and returning to normal pressure with nitrogen gas 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 tube of the double tube nozzle at the specified rate, 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. Once the specified amount of diallyl terephthalate, aromatic hydrocarbon, and di-tert-butyl peroxide has been supplied, turn off the steam and reduce the stirring speed.
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】

[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 by Brapender Plastograph manufactured by Brapender (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 Brapender melt viscosity, and from the end of sample addition. The time up to 5000 m·g was defined as the processing time. Examples 1 to 7 Comparative Examples 1 to 4 After thoroughly mixing each composition shown in Table 2, the compositions were kneaded with rolls (front roll 90 to 100°C, rear 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, use a mold to manually press it into 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 mold that had been prepared, and mold with an automatic press at a temperature of 160℃ and a pressure of 100Kg/ ^cm2 for 5 to 20 minutes to form a disc with a diameter of 100mm and a thickness of 2mm. I got the item. The molded product obtained at each pressing time was immersed in boiling chloroform for 1 hour and then taken out, and the pressing time at which the surface of the molded product showed no change compared to before the chloroform was boiled was taken as the minimum curing time. JISK-6911 for molded products molded with the lowest curing time
A general test according to JISK-7211 and a falling weight impact test according to JISK-7211 were conducted, 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 was measured by the following method. That is, 36 test pieces were cut out with a diamond cutter from two molded products and subjected to measurement.
The testing machine is a Dupont falling ball tester (load 500g,
The 50% fracture height was determined by the Dickson mode method using a flat support base and a striking center of 1/2 inch R). (Reference: JISK-7211).

[Table] (4) Asahi Fiberglass products.
(5) 〓A−174〓 (Nippon Unicar product)
Example 8 Comparative Example 5 A 0.5% by weight aqueous solution of fumaric acid was prepared, and a glass cloth (L7628-S502, manufactured by Co., Ltd.) with a basis weight of 200 g/m ² was added to it.
A glass cloth coated with about 0.6 g/m ² of fumaric acid was obtained by impregnating it with fumaric acid (product of Arisawa Manufacturing Co., Ltd.), air-drying it, and then drying it with hot air at 110°C for 2 hours. Separately, a composition having the following formulation was dissolved in methyl ethyl ketone to a concentration of 50% by weight. Diallyl terephthalate copolymer (manufacturing example)
95 parts diallyl terephrate monomer 5 parts tert-butyl perbenzoate 2 parts The glass cloth obtained in the above treatment was impregnated with this resin solution, air-dried, and then dried with hot air at 90° C. for 20 minutes to obtain a prepreg. Eight sheets of this were laminated and pressed through a cushion plate at a hot plate temperature of 160° C. and a pressure of 30 kg/cm ² for 25 minutes to obtain a laminate with a thickness of about 1.6 mm. For comparison, we used glass cloth that was not treated with fumaric acid.
A laminate was obtained in exactly the same manner as above except that the pressing time was 40 minutes. The amount of resin was 46% by weight in each case, and the measurement results of the bending properties of the laminates according to JISK-6911 are listed in the table below. Table 3 Example 6 Comparative Example 5 Bending strength 54Kg/mm ² 41Kg/mm ² Bending modulus 1810 〃 1560 〃

Claims (1)

[Claims] 1. One or more compounds selected from fumaric acid, monoalkyl esters of fumaric acid, and dialkyl esters of fumaric acid are blended into a diallyl phthalate resin containing a terephthalic acid diallyl ester copolymer. A resin composition characterized by: However, the terephthalic acid diallyl ester copolymer refers to 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. 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,
n=an integer of 1 to 3.