JPH0885747A - Cross-linkable diallyl phthalate resin composition excellent in crack resistance - Google Patents

Abstract

PURPOSE: To obtain a cross-linkable resin compsn. suitable as a crack-resistant sealing material in the surface mounting of electronic devices by compounding a diallyl phthalate resin, a specific chlorinated polyethylene or a specific acrylic rubber, and an org. peroxide. CONSTITUTION: A diallyl phthalate resin in an amount of 70-95wt.% (A), 5-30wt.% (pref. 10-25wt.%) chlorinated polyethylene having a chlorine content of 5-50-wt.% and obtd. from polyethylene having a mol.wt. of 1×10<4> -300×10<4> (B), and an org. peroxide (C) are compounded. Component A is a post-curable prepolymer as a polymer of a diallyl phthalate monomer or a copolymer thereof with an unsatd. monomer. Component B is cross-linked with component C to become a rubber and thus reinforces component A. A cross-linkable diallyl phthalate resin excellent in crack resistance is similarly obtd. by using, instead of component B, an acrylic rubber produced by using a monomer having a chlorine group (e.g. chloroethyl vinyl ether) or an epoxy monomer (e.g. glycidyl acrylate) as a comonomer for forming cross-linking sites.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crosslinkable diallyl phthalate resin composition having excellent crack resistance, which is useful as a material for encapsulating elements, molded products to be processed later, laminates and the like.

[0002]

2. Description of the Related Art Conventionally, diallyl phthalate resins, which are mainly composed of prepolymers derived from diallyl orthophthalate, diallyl isophthalate and diallyl terephthalate, are highly reliable because they have excellent electrical characteristics at high temperature and high humidity. Molding materials for electrical and electronic parts that require high performance,
It is also used as a casting resin, and has a track record of many years. Further, the diallyl phthalate-based resin has excellent dimensional stability, heat resistance, moisture resistance and water resistance, and is partially used as a resin for laminated boards.

In recent years, with the miniaturization of electric and electronic equipment, miniaturization of each component and surface mounting technology on a substrate have been rapidly advanced, and the required characteristics such as heat resistance are inevitably severe.
In such a trend, the heat resistance of diallyl phthalate resin is re-evaluated. However, the brittleness of the thermosetting resin becomes a problem as these molded products become thinner. In order to improve this brittleness, various additions of various elastomers, thermoplastic resins, rubber materials such as NBR, etc. have been variously studied, but those which maintain the excellent characteristics of the above diallyl phthalate resin have been obtained. The current situation is not.

[0004]

The diallyl phthalate resin, like other thermosetting resins, is usually obtained by curing a monomer or low molecular weight polymer (prepolymer) by heating and pressurizing it and then cooling it to room temperature. Molded. At that time, internal stress occurs in the molded product due to curing shrinkage and cooling shrinkage. Further, since the crosslink density at the time of curing is high, the resin breaks with almost no elongation even in a pulling operation, resulting in a so-called brittle resin. Such a resin is apt to be broken due to the cracks existing in the resin growing due to contraction or expansion due to an abrupt temperature change due to an external force or thermal shock, or due to internal stress.
Toughening a resin includes elements such as elongation at break, increase in impact strength, improvement in fatigue endurance, and improvement in wear resistance. Paying attention to the growth of this crack, the toughness of the diallyl phthalate resin was examined using the fracture toughness value K _1C , which is an evaluation method (reference, Journal of Japan Adhesion Association Vol, 24 No.
5 (1988) pp. 186- "Toughening and stress reduction by transformation of epoxy resin (I)" Nakamura, Kitayama, Yamaguchi, Ika, Okubo, Matsumoto).

Therefore, an object of the present invention is to impart toughness while maintaining the excellent characteristics of the conventional diallyl phthalate resin, and to prevent package cracks due to thermal shock in a solder bath at the time of surface mounting of an element-sealed molded product, Prevents cracks from occurring in molded products such as crack prevention during pin press-fitting during secondary processing of connector molded products and prevention of cracks during punching and bending during secondary processing of other molded products and laminated plates This is to provide a diallyl phthalate resin composition having excellent crack resistance.

[0006]

As a result of various studies, the present inventors have found that a diallyl phthalate resin has a specific amount of chlorinated polyethylene, an acrylic rubber having a chlorine group at a crosslinking point or an acrylic rubber having an epoxy group at a crosslinking point. The inventors have found that the toughness of a diallyl phthalate resin is improved by blending it with maleic anhydride and crosslinking it with an organic peroxide, and completed the present invention.

That is, the first invention is (a) 70 to 95% by weight of diallyl phthalate resin, (b) 5 to 30% by weight of chlorinated polyethylene having a molecular weight of raw material polyethylene of 10,000 to 3,000,000 and a chlorine content of 5 to 50% by weight, and ( c) A diallylphthalate-based resin composition for crosslinking, which comprises an organic peroxide.

The second invention is characterized by containing (a) 65 to 95% by weight of a diallyl phthalate resin, (b) 5 to 35% by weight of an acrylic rubber having a chlorine group at a crosslinking point, and (c) an organic peroxide. And a cross-linked diallyl phthalate resin composition.

The third invention is (a) 65 to 95% by weight of diallyl phthalate resin, (b) 5 to 35% by weight of acrylic rubber having an epoxy group at a crosslinking point, and (c) the acrylic rubber.
A cross-linked diallyl phthalate resin composition containing 2 to 10 parts by weight of maleic anhydride and (d) an organic peroxide with respect to 100 parts by weight. All of these resin compositions have excellent crack resistance.

The chlorinated polyethylene used in the first invention means polyethylene having a molecular weight of 10,000 to 3,000,000 and a chlorine content of 5 to 5 by an aqueous suspension method, a solution method, a gas phase method or the like.
It is chlorinated up to 50% by weight, and the amount of remaining crystals does not matter. If the molecular weight of the raw material polyethylene is lower than the above range, the crack resistance is less effective, and if it is too high, the dispersibility with the diallyl phthalate resin deteriorates. On the other hand, if the chlorine content is less than 5% by weight, the properties of polyethylene become so strong that it becomes difficult to disperse it in diallyl phthalate resin, and the mechanical strength such as bending strength becomes low. If it exceeds 50% by weight, it is decomposed by the heat coming from the mold at the time of molding to easily generate hydrochloric acid, and it is necessary to increase the amount of the acid acceptor, resulting in deterioration of water resistance. The blending amount of chlorinated polyethylene is 5 to 30% by weight, preferably 10 to 25% by weight based on the total amount of the above (a) and (b). If the amount of chlorinated polyethylene is less than this range, the effect of improving toughness is reduced,
If the amount is more than this range, the rubber-like property becomes strong, resulting in a decrease in rigidity during heating and a decrease in bending strength.

Chlorinated polyethylene has the property of undergoing peroxide cross-linking with an organic peroxide, which can be used as a curing agent for diallyl phthalate resin, in the presence of a cross-linking aid to form a tough rubber. Usually, 0.5 to 7 parts by weight of organic peroxide is mixed with 100 parts by weight of chlorinated polyethylene. It is considered that this peroxide crosslinking causes some bonding relationship with the diallyl phthalate resin which is also cured by peroxide, and contributes to the improvement of physical properties. Examples of the cross-linking aid include polyfunctional monomers such as sulfur, triallyl isocyanurate, divinylbenzene and diallyl phthalate, and oxime compounds such as p-quinonedioxime. Usually, 1 to 15 parts by weight relative to 100 parts by weight of chlorinated polyethylene. Compound.

Further, the composition containing chlorinated polyethylene is contained in the chlorinated polyethylene particles during post-processing such as kneading, molding, and heating, or hydrochloric acid is liberated by thermal decomposition. It is preferable to add an acid acceptor in order to prevent adverse effects such as corrosion from occurring on the molding machine, molding die, and insert-molded metals. Usually, 2 to 15 parts by weight is blended with 100 parts by weight of chlorinated polyethylene. As the acid acceptor, magnesium oxide, magnesium hydroxide, calcium carbonate, hydrotalcite, epoxy resin or the like is used.

The acrylic rubber used in the second invention is an alkyl acrylate ester (CH ₂ ═CHCOO).
R ¹ ) and / or acrylic acid alkoxyalkyl ester (CH ₂ ═CHCOOR ² OR ³ ) as a main component and a typical chemical structure is

[0014]

Embedded image It is a rubber-like elastic body represented by. Alkyl group (R ¹ )
Is generally a methyl group, an ethyl group or a butyl group, and the alkoxyalkyl group (R ² OR ³ ) is generally a methoxyethyl group or an ethoxyethyl group.

Homopolymers or copolymers of these
Since it is difficult to crosslink, acrylic rubber usually has
It is a copolymer with a monomer having an active group. Starting
Acrylic rubber with chlorine groups as crosslinking points in Ming
Is chlorine in the active group of the monomer of the copolymerization component that becomes the crosslinking point.
Group containing 1 to 20% by weight of monomer
%, Preferably 2-15% by weight, at 100 ° C.
Mooney viscosity ML _{1 + 4}Is between 15 and 90
To tell. The types of such monomers include 2-chloro
Chlorine-based active groups such as ethyl vinyl ether,
Chlorovinyl acetate and cyclol chloroacetate
Some have such active chlorine groups. Inclusion of these monomers
If the amount is less than the above range, peroxide crosslinking will be difficult
If it exceeds the above range, the crosslink density becomes high and the toughness improving effect is improved.
The fruit will decrease. Mooney viscosity ML_{1 + 4}(100 ° C)
If the value is less than 15 or more than 90, the adhesion to the kneading machine or
Extending the kneading time is necessary, and the workability deteriorates, which is preferable.
Not good.

When these acrylic rubbers and diallyl phthalate resin are mixed, and an organic peroxide is added and cured, some bonding relationship is generated between the acrylic rubber and diallyl phthalate resin, and the physical properties of the diallyl phthalate resin deteriorate. It is thought that the toughness can be greatly improved with a small amount. Usually, 0.5 to 7 parts by weight of organic peroxide is blended with 100 parts by weight of acrylic rubber. Further, in this case, a crosslinking aid that facilitates the above-mentioned bonding can be used. As the cross-linking aid, polyfunctional monomers such as sulfur, triallyl cyanurate, divinylbenzene and diallyl phthalate, and oxime compounds such as p-quinoline dioxime are used, and usually 1 to 15 parts by weight per 100 parts by weight of acrylic rubber.
Add parts by weight. The amount of acrylic rubber compounded in the diallyl phthalate resin is 5 to 35% by weight, preferably 10 to 25% by weight, based on the total amount. If it is less than this range, the effect of improving toughness is reduced, and if it is more than this range, the rubber-like property becomes strong, resulting in a decrease in rigidity during heating and a decrease in bending strength.

The acrylic rubber having an epoxy group at the cross-linking point used in the third aspect of the invention is one in which the active group of the monomer of the copolymerization component at the cross-linking point contains an epoxy group, and the content of the monomer is Is 1 to 15% by weight, preferably
2-10% by weight, Mooney viscosity ML at 100 ℃
_{1 + 4} is in the range of 15 to 90. Examples of the epoxy group-containing monomer include allyl glycidyl ether, methallyl glycidyl ether, vinyl ether, glycidyl acrylate, and glycidyl methacrylate. Acrylic rubbers having an epoxy group at the cross-linking point obtained as a copolymerization component of these are generally cross-linked with an organic ammonium carboxylate or a dithiocarbamate as a cross-linking agent. It is unsuitable as an agent. That is, when organic ammonium carboxylate is used, ammonia is liberated by heat during molding, water resistance is deteriorated and the inserted metal is liable to corrode. This leads to poor tracking performance. Further, the use of dithiocarbamate inhibits the curing of the diallyl phthalate resin, and only a cured product having extremely low physical properties can be obtained. On the other hand, when only acrylic rubber having an epoxy group at the cross-linking point and diallyl phthalate resin are used and organic peroxide is added and mixed and cured, the toughness is slightly improved but the load deflection of the diallyl phthalate resin is improved. This is not preferable because it greatly lowers the temperature.

From the above points, the inventors of the present invention investigated various additives for producing a bond relationship between the diallyl phthalate resin and the acrylic rubber having an epoxy group at the crosslinking point, and maleic anhydride was effective. I found that. That is, if maleic anhydride, which is used as an acid anhydride-based curing agent for epoxy resin and has excellent copolymerizability with diallyl phthalate resin, is used, the unsaturated double bond portion of maleic anhydride is diallyl phthalate resin. Copolymerized with
We paid attention to the fact that the acid anhydride part is easily bonded to the epoxy group of acrylic rubber. A suitable amount of maleic anhydride is 2 to 10 parts by weight with respect to 100 parts by weight of an acrylic rubber having an epoxy group at a crosslinking point. When the maleic anhydride content is less than this range, a sufficient crosslinking effect does not appear and the toughness improving effect is low. On the other hand, if the amount exceeds this range, the diallyl phthalate resin remains unreacted during curing, resulting in deterioration of water resistance and electrical characteristics.

The content of the monomer having an epoxy group as an active group is as described above. If the content is less than this range, the bond between the acrylic rubber and the diallyl phthalate resin via maleic anhydride becomes weak and it is difficult to improve the toughness. The load deflection temperature of the diallyl phthalate resin is lowered. On the other hand, if the content of the monomer is more than this range, the crosslink density also becomes high, and the toughness improving effect becomes small.

The Mooney viscosity of acrylic rubber ML _{1 + 4}
If the (100 ° C.) is less than 15 or more than 90, adhesion to the kneading machine or extension of the kneading time becomes necessary, resulting in deterioration of processability, which is not preferable. Further, a polyfunctional monomer such as triallyl isocyanurate, divinylbenzene or diallyl phthalate can be added to accelerate the reaction between maleic anhydride and diallyl phthalate resin. The blending amount thereof is preferably 1/2 to 2 times the weight of maleic anhydride.
The compounding amount of such an acrylic rubber having an epoxy group with respect to the diallyl phthalate resin is 5 to 35% by weight, preferably 10 to 25% by weight based on the total amount. If it is less than this range, the effect of improving toughness is reduced, and if it is more than this range, the rubber-like property becomes strong, resulting in a decrease in rigidity during heating and a decrease in bending strength.

Other types of the copolymerization component monomer which becomes the cross-linking point of the acrylic rubber include those having a carboxyl group such as acrylic acid or those having no cross-linking point containing no active group. Such an acrylic rubber does not have a binding relationship with the diallyl phthalate resin, and therefore has a low toughness improving effect. In the case of acrylic rubber containing chlorine groups, if the chlorine content is too high, an acid acceptor is required.However, if an acid acceptor is added to an acrylic rubber that generally does not have good water resistance, the electrical properties of the diallyl phthalate resin when wet will increase. It is not preferable because it will worsen.

The diallyl phthalate resin referred to in the present invention is a homopolymer, a copolymer or a mixture of homopolymers obtained by polymerizing at least one selected from ortho, iso and tere diallyl phthalate monomers. A post-curable diallyl phthalate prepolymer, or a mixture of the diallyl phthalate prepolymer and at least one reactive monomer having an unsaturated group such as an allyl group or a vinyl group, or selected from the above isomer monomers. And at least one diallyl phthalate monomer and a post-curable copolymerizable prepolymer provided by at least one polymerization selected from the above reactive monomers, and further the above diallyl phthalate prepolymer, copolymer prepolymer and unsaturated polyesters Two or more selected from Mixture, or as a general term indicating such a mixture of at least one of the reactive monomer to the mixture.

Examples of the reactive monomer having an unsaturated group are styrene, styrene-based monomers such as α-chlorostyrene, methyl (meth) acrylate, butyl (meth).
Acrylate, n-octyl (meth) acrylate, 2
-Ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethyleneglycolyl (meth) acrylate, propylene Acrylic monomers such as glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, vinyl ester monomers such as vinyl acetate and vinyl benzoate, Acrylic acetate, allyl benzoate, allyl (meth) acrylate, diallyl oxalate, diallyl adipate,
Examples include allyl ester monomers such as diethylene glycol bis (allyl carbonate), diethylene glycol bis (allyl phthalate), polyethylene glycol bis (allyl phthalate), diallyl maleate, diallyl fumarate, diallyl citrate, diallyl phthalate and the like. The amount of the compound is about 70% by weight or less, preferably about 50% in the diallyl phthalate resin.
A compounding amount such as a weight% or less can be exemplified.
Further, the component ratio of the reactive monomer in the copolymerization prepolymer is usually appropriate to be 50% by weight or less, and the copolymerization prepolymer is further selected from the compounding range of the reactive monomer. Can also be added.

Examples of the curing agent for the diallyl phthalate resin used in the present invention include di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) -hexane and 1,3-bis. -(Tert-butylperoxy-isopropyl) -benzene, 2,5-dimethyl-2,5-di- (tert
-Butylperoxy) -hexyne-3, dialkyl peroxides such as dicumyl peroxide and diaryl peroxides; ketone peroxides such as methylethylketone peroxide and cyclohexanoneperoxide; 1,1-bis (tert-butylperoxy) -3,3 Peroxyketals such as 5,5-trimethylcyclohexane; Hydroperoxides such as cumene hydroperoxide; Diaroyl peroxides and diacyl peroxides such as lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide; Diisopropyl peroxycarbonates such as Peroxycarbonate ； te
Examples thereof include peroxyesters such as rt-butylperoxyacetate, tert-butylperoxypivalate, tert-butylperoxyoctoate, tert-butylperoxybenzoate, and tert-butylperoxyisopropylcarbonate, and azobis compounds other than the above organic peroxides. Azo compounds such as isobutyronitrile can be used as well.

Practically, the peroxides usually used for diallyl phthalate resins such as dicumyl peroxide, tert-butyl peroxybenzoate, benzoyl peroxide and the like are directly applied. A proper amount of the compound is 0.1 to 6% by weight based on the diallyl phthalate resin content.

When the chlorinated polyethylene or acrylic rubber described above is mixed and dispersed in the diallyl phthalate resin, it is possible to reduce the amount of use by mixing and dispersing the additives in advance, and the cured product is manufactured. Less likely to deteriorate the physical properties of the body. That is, when mixing and dispersing chlorinated polyethylene, chlorinated polyethylene and organic peroxide, a crosslinking aid, an acid acceptor, etc. are mixed and dispersed in advance with a mixing roll, a pressure kneader, etc., and then diallyl phthalate resin. And an organic peroxide as a curing agent are mixed and dispersed to obtain a composition.

When the acrylic rubber containing a chlorine group at the cross-linking point is mixed and dispersed, the acrylic rubber, the organic peroxide and the cross-linking aid are mixed in advance and the acrylic rubber containing the epoxy group at the cross-linking point is mixed and dispersed. In this case, the acrylic rubber and maleic anhydride, a polyfunctional monomer, an organic peroxide, etc. are mixed and dispersed by a mixing roll or a pressure kneader in advance, and then the diallyl phthalate resin and the organic peroxide of the curing agent are mixed. A composition is obtained by mixing and dispersing. In the above case, chlorinated polyethylene or acrylic rubber and an organic peroxide, a crosslinking aid, an acid acceptor, a polyfunctional monomer, maleic anhydride, and other additives are mixed and dispersed, and once taken out from the kneader. It is not necessary to store and continuously mix and disperse with the diallyl phthalate resin.

The composition of the present invention can be used in the same manner as in the case of the conventional diallyl phthalate resin composition, if desired, for example, a filler, a polymerization accelerator, a polymerization inhibitor, an internal release agent, a coupling agent, a pigment, a hardener. A molding agent or other additives may be added within a range that does not impair the characteristics of the composition of the present invention to improve molding processability or physical properties of a molded article. As the molding method of the composition of the present invention, the known molding method and molding conditions similar to those of the conventional diallyl phthalate resin can be applied as they are. That is, a casting method in which the composition of the present invention is injected into a mold and cured,
An injection molding method or a transfer molding method in which the composition is heated to be in a fluid state and is put into a mold to be heat-cured, a compression molding method in which the composition is heated and pressed to be cured in the mold, and the composition Is dissolved in an appropriate solvent, impregnated into a fibrous sheet, dried, and optionally cured under pressure, to cure the resin in the fibrous sheet, a laminated plate molding method, a fine powder or a solution of the composition. Examples of the method include a coating method in which the composition is applied to a base material and cured on the base material, and a decorative board molding method in which the composition solution is impregnated into a printing paper or the like and dried and then heated and pressed to be cured on the substrate. . In the above molding, the mold temperature is about 60 to 220.
An example is ° C. The pressure for compression molding may be about 5 to 500 kgf / cm ² .

[0029]

EXAMPLES The present invention will be described in more detail with reference to the following examples and comparative examples. First, the composition having the composition shown in the rubber composition table of Table 1 was kneaded with a mixing roll having a diameter of 9 inches at a roll temperature of the same kneading temperature as shown in Table 1. In this case, only chlorinated polyethylene or acrylic rubber was put into the roll, wrapped around the roll and blended well, and then other additives were added. After all the additives were added, the mixture was kneaded for 5 minutes, taken out, and cooled. Using these compositions, diallyl phthalate resin compositions were produced as shown in the following examples and comparative examples.

Examples 1 to 3 and 6 to 12 Comparative Examples 1 to 7 Examples 1 to 3 and 6 to 12 in Table 2 and Comparative Examples 1 to 1
The diameter of the diallyl phthalate resin composition having the composition shown in FIG.
The mixture was kneaded with a 9-inch mixing roll at a roll temperature of 80 to 100 ° C. for 15 minutes, taken out, cooled, and roughly crushed in a mortar. The composition obtained has a pressure of 100 kgf / in a mold at 160 ° C.
cm ^2, is molded into a plate of 4mm thickness using a curing time of 7 minutes. Eleven samples of 15 mm × 80 mm were cut out from this molded plate and
The flexural strength and flexural modulus of the sheets were measured by the JIS K6911 thermosetting plastic general test method. The other 7 are ASTM
According to E399, the fracture toughness value K _1C was measured by a 3-point bending test method with a test piece height of 15 mm, a test piece thickness of 4 mm, a fulcrum distance of 60 mm, and a load speed of 0.5 mm / min.

Next, in order to measure the deflection temperature under load of the above composition, a plate having a thickness of 6.4 mm was formed at a mold temperature of 160 ° C., a pressure of 100 kgf / cm ² , and a curing time of 10 minutes. From this molded plate
Three 12.7 mm x 120 mm samples were cut out and measured by JIS K6911 thermosetting plastic general test method. Furthermore, in order to measure the volume resistivity and boiling water absorption of the above composition, a mold having a diameter of 10 cm and a thickness of 3 mm to obtain a disk-shaped molded product is used, the mold temperature is 160 ° C., the pressure is 100 kgf / cm ² , and the curing time is A disc was formed by molding for 6 minutes, and the boiling water absorption was measured by the JIS K6911 thermosetting plastic general test method. The results of these measurements are shown in Table 3.

Examples 4 and 5 The compositions having the compositions shown in Examples 4 and 5 in Table 2 were kneaded and molded in the same manner as in other examples except that the mold temperature at the time of molding was 180 ° C. After that, the same measurement was performed as it was or after cutting out. The results are shown in Table 3.

[0033]

[Table 1]

[0034]

[Table 2]

In Table 1, (1) Product name "Daisolac G235" (manufactured by Daiso, chlorine content 35% by weight, PE molecular weight 50,000 to 100,000) (2) Product name "Daisolak U303" (manufactured by Daiso, chlorine content 30 % By weight, PE molecular weight 50,000 to 100,000) (3) Product name "Daisolak H135" (manufactured by Daiso Co., chlorine content 35% by weight, PE molecular weight 150,000 to 200,00)
0) (4) Product name "Daisolak MR104N" (manufactured by Daiso Co., chlorine content 40% by weight, PE molecular weight 200,000-250,0)
00) (5) Product name “Noxtite PA301” made by Nippon Mektron (6) Product name “Knoxtite PA302” made by Nippon Mektron (7) Product name “Toa Akron AR-601” made by Toa Paint (8) Product name "Noxtite A1095" manufactured by Nippon Mektron (chlorine content: about 5% by weight) (9) Product name "Noxtite PA501" manufactured by Nippon Mektron (10) Product name "Noxtite PA502L" manufactured by Nippon Mektron (11) Product name "JSR AREX 290" manufactured by Japan Synthetic Rubber Co., Ltd. (12) Diallyl orthophthalate monomer (13) Diallyl isophthalate monomer (14) Triallyl isocyanurate (15) Magnesium oxide (trade name "Kyowamag 15
(0) Made by Kyowa Chemical Industry Co., Ltd. (16) Hydrotalcite (brand name "DHT-4A" made by Kyowa Chemical Industry Co., Ltd.) (17) Dicumyl peroxide (brand name "Park Mill D" made by NOF Corporation (18) 2, 5-Dimethyl-2,5-di (tert-butylperoxy) -hexane (trade name "Kayahexa AD" manufactured by Kayaku Akzo)

[0036]

[Table 3]

[0037]

[Table 4]

In Table 2, (19) diallyl orthophthalate prepolymer (trade name "Daiso Dup" manufactured by Daiso Co., Ltd.) (20) Diallyl isophthalate prepolymer (the same) (17) (18) Same as Table 1

[0039]

[Table 5]

As shown in Table 3, the molded article made of the composition of the present invention has a fracture toughness value which is an evaluation of durability in the case of only diallyl phthalate resin containing no chlorinated polyethylene or acrylic rubber (Comparative Example 1, 2) When the acrylic rubber has a carboxyl group at the cross-linking point or does not have the cross-linking point (Comparative Examples 4 to 6), when the acrylic rubber has an epoxy group but does not contain maleic anhydride (Comparative Example 3)
It is clearly superior to the molded product according to.

[0041]

EFFECTS OF THE INVENTION The resin composition according to the present invention has improved brittleness as compared with the conventional diallyl phthalate resin composition and can prevent troubles due to cracking of molded articles. Therefore, it is particularly useful for applications such as thin-walled molded articles, which accompany miniaturization of electric and electronic parts.

Claims (5)

[Claims] 1. A molecular weight of (a) diallyl phthalate resin 70 to 95% by weight, and (b) raw material polyethylene of 10,000 to 3,00.
Chlorinated polyethylene with 0,000 and chlorine content of 5 to 50% by weight 5
-30% by weight and (c) an organic peroxide, and a cross-linked diallyl phthalate resin composition having excellent crack resistance. 2. (a) 65 to 95% by weight of diallyl phthalate resin, and (b) 5 to 5 of acrylic rubber having a chlorine group at a cross-linking point.
A cross-linked diallyl phthalate resin composition having excellent crack resistance, which comprises 35% by weight and (c) an organic peroxide. 3. Acrylic rubber is a copolymer with a monomer having a chlorine group at a cross-linking point, and the content of the monomer is 1 to 1.
20% by weight, Mooney viscosity ML at 100 ° C
_The diallyl phthalate resin composition for crosslinking according to claim 2, wherein _{1 + 4} is 15 to 90. 4. Acrylic rubber having (a) a diallyl phthalate resin of 65 to 95% by weight and (b) an epoxy group at a cross-linking point.
5 to 35% by weight, (c) 2 to 10 parts by weight of maleic anhydride per 100 parts by weight of the acrylic rubber, and (d) an organic peroxide, which is excellent in crack resistance. Composition. 5. The acrylic rubber is a copolymer with a monomer having an epoxy group at a cross-linking point, and the content of the monomer is
1-15% by weight, Mooney viscosity M at 100 ° C
L _{1 + 4} is 15 to 90, The diallyl phthalate resin composition for crosslinking according to claim 4.