JPH02191656A - Thermoplastic polymer composition - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent balance of characteristics such as impact resistance, thermal aging resistance, weather resistance and mechanical resistance by blending a specific thermoplastic resin with copolymer rubber. CONSTITUTION:(A) 20-99wt.% thermoplastic resin selected from polyacetal, polycarbonate, polyphenylene oxide, thermoplastic polyester, styrene-based resin, acrylic resin, polyarylate, polysulfone, polyether sulfone, polyallyl sulfone, polyether imide and poly(4-methylpentene) is blended with (B) 80-1wt.% copolymer rubber comprising 10-95wt.% alpha, beta unsaturated carboxylic acid ester, 0.1-10wt.% crosslinkable monomer, 0.1-20wt.% monomer containing a functional group selected from carboxyl group, amino group, epoxy group and hydroxyl group, 0-50wt.% vinyl cyanide monomer and 0-50wt.% conjugated diene monomer as copolymer components and having >=20wt.% gel content.

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to a thermoplastic polymer composition having an excellent balance of impact resistance, heat deterioration resistance, weather resistance, mechanical strength, etc.

b. Conventional technology Conventionally, thermoplastic resins include polyester, polycarbonate, polyoxymethylene, polyphenylene ether,
Styrene resins and the like are commonly used. For example, thermoplastic polyester resins, especially polybutylene ethylene υ-t (hereinafter referred to as rPBTJ), have well-balanced physical properties and excellent moldability, and are used for mechanical parts, electronic/electrical parts, and automobile parts. , widely used in other fields. However, these thermoplastic resins have a major drawback of low notch impact strength. For example, PBT is
It shows good impact strength without notches, but with notches, the impact strength decreases significantly.
This is an obstacle to expanding its use.

Various proposals have therefore been made to improve the properties of these resins, particularly their impact resistance. For example, as an additive to improve the impact resistance of these thermoplastic resins,
Conjugated diene compound-styrene copolymer (Japanese Patent Publication No. 46-5
229), a polymer obtained by grafting acrylonitrile and aromatic vinyl onto a conjugated diene rubber (Japanese Patent Publication No. 51-25
No. 261) etc. have been proposed. but,
Because these conjugated diene polymers contain unsaturated bonds, molded products obtained by adding these polymers have poor heat resistance and weather resistance, and the improvement in impact resistance is also insufficient. .

In addition, in order to improve this heat deterioration resistance and weather resistance, partially hydrogenated conjugated diene polymers (Japanese Patent Application Laid-Open No. 60-130642)
However, the impact resistance is insufficient and the drawbacks have not yet been overcome.

C1 Problems to be Solved by the Invention The present invention was made against the background of the above-mentioned problems of the prior art. The present invention provides a resin composition with excellent deterioration properties.

Means for Solving Problem d1 The present invention provides a thermoplastic polymer comprising 20 to 99% by weight of the following thermoplastic resin (X) and 80 to 1% by weight of the following copolymer rubber (Y). Coalescing composition.

(a) The thermoplastic resin (X) is polyacetal, polycarbonate, polyphenylene oxide, thermoplastic polyester, styrene resin, acrylic resin, polyarylate, polysulfone, polyether sulfone, polyallylsulfone, polyetherimide and poly(4- At least one type selected from methylpentene).

(B) Copolymer rubber (Y) is A: α, β unsaturated carboxylic acid ester 10 to 95% by weight B: Crosslinkable monomer 0.1 to 10% by weight C: Functional groups include carboxyl group and amino group , an epoxy group, and a hydroxyl group.

0.1 to 20% by weight D: 0 to 50% by weight of vinyl dianide monomer E: 0 to 50% by weight of conjugated diene monomer A rubber having a gel content of 20% by weight or more as a constituent copolymer component .

It provides:

The present invention will be explained in detail below.

- Thermoplastic resins (X) include polyacetal, polycarbonate, polyphenylene oxide, thermoplastic polyester, styrene resin, acrylic resin, polyarylate, polysulfone, polyether sulfone, polyallylsulfone, polyetherimide, and (4-methyl At least one type selected from (pentene) can be mentioned.

Among the above resins, polyphenylene oxide also includes modified polyphenylene oxide in which a styrene resin is blended with polyphenylene oxide.

Among the above resins, styrene resins are homopolymers of vinyl aromatic compounds, copolymers with other monomers copolymerizable with vinyl aromatic compounds, or polymers in the presence of rubber-like polymers. , a vinyl aromatic compound, a graft copolymer obtained by polymerizing a vinyl aromatic compound and another copolymerizable monomer, or a mixture of at least two thereof.

Examples of the vinyl aromatic compound include styrene, α-methylstyrene, methylstyrene, p-methylstyrene, vinylxylene, chlorostyrene, bromustyrene, etc., and these may be used alone or in combination of two or more.

In addition, examples of copolymerizable monomers include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, which may be used alone or in combination of two or more. Acrylonitrile is particularly preferred.

Furthermore, alkyl acrylates such as methyl acrylate, ethyl acrylate, propylene acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate, etc. Esters: Acrylic acid alkoxyalkyl esters such as methoxyethyl acrylate, ethoxyethyl acrylate, ethoxypropyl acrylate; methyl methacrylate, ethyl methacrylate, propylene methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate,
Methacrylic acid alkyl esters such as octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, and benzyl methacrylate; unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, etc. substance; acrylic acid,
Unsaturated acids such as methacrylic acid, maleimide, N-
Methylmaleimide, N-butylmaleimide, N-(Pmethylphenyl)maleimide, N-phenylmaleimide,
Examples include imide compounds of α- or β-unsaturated dicarboxylic acids such as N-cyclohexylmaleimide, which may be used singly or in two amounts within a range that does not impede the purpose of the present invention. .

Examples of the rubbery polymer include diene rubbers such as polybutadiene, polyisoprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene, ethylene-butene, ethylene-propylene-nonconjugated genter polymer, Examples include non-diene rubber such as acrylic rubber, and these may be used alone or in combination of two or more.

In the case of a mixture in which the monomer component consists of a vinyl aromatic compound and another copolymerizable monomer, the proportion of the vinyl aromatic compound in the mixture is preferably 50% by weight or more] 2. More preferably. is 70% by weight or more -F, and when it is in this range, moldability and surface appearance of the molded product are further improved, so it is preferable.

Among the above resins, acrylic resins are homopolymers of (meth)acrylic acid alkyl esters or (meth)acrylic acid alkyl esters.
Copolymers of acrylic acid alkyl esters and other copolymerizable monomers, or (meth)acrylic acid alkyl esters or other copolymers copolymerizable with (meth)acrylic acid alkyl esters in the presence of a rubbery polymer. or a mixture of at least two thereof.

Examples of the (meth)acrylic acid alkyl ester include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, etc.
Preferably it is methyl methacrylate.

The above-mentioned copolymerizable monomers include the copolymerizable monomer components shown in the styrene resins except for the (meth)acrylic acid alkyl ester. As the rubbery polymer in L, the rubbery polymers shown in styrene resins are applicable.

In the case of a mixture in which the monomer component is a (meth)acrylic acid alkyl ester and another copolymerizable monomer, the proportion of the (meth)acrylic acid alkyl ester in the mixture is preferably 55% by weight. More preferably 70
% by weight or more. If it is within this range, even better weather resistance can be obtained, so it is preferable.

Among the above resins, polybutylene terephthalate is preferably used as the thermoplastic polyester.

Preferred heat distortion temperature (ASTM) of thermoplastic resin (X)
D648, load 18.6 kg/cd, l/2' test piece) is 250°C or less. If it exceeds 250° C., the molding temperature becomes high, causing thermal deterioration of the copolymer rubber (Y), which is undesirable because it causes deterioration of the physical properties of the obtained thermoplastic polymer composition.

The preferred thermoplastic resin (X) is at least one selected from polyacetal, polycarbonate, polyphenylene oxide, thermoplastic polyester, styrene resin, acrylic resin, etc. This is preferred because a thermoplastic polymer composition can be obtained.

Next, the copolymer rubber (Y) will be explained.

The α,β unsaturated carboxylic acid ester (A) which is a copolymerization component of the copolymer rubber (Y) is represented by the general formula (R+ hydrogen or methyl group, R2 is an alkyl group having 1 to 12 carbon atoms). . Specific examples include methyl acrylate, ethyl acrylate, -propyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, and 2-ethyl-hexyl acrylate. ,
Examples include dodecyl acrylate, 2-methoxyethyl acrylate, methyl methacrylate, n-butyl methacrylate, -octyl methacrylate, 2-ethylhexyl methacrylate, and -dodecyl methacrylate. Among these, preferred are methyl acrylate,
Ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate, particularly preferred is acrylic acid. Butyl and ethyl acrylate.

The amount of the copolymer of component (A) is 10 to 95% by weight, preferably 30 to 90% by weight. If it is less than 10% by weight, the impact resistance and heat deterioration resistance will be poor, while if it exceeds 95% by weight, the dispersibility in the thermoplastic resin (X) will be poor and good impact resistance will not be obtained.

A crosslinkable monomer (
Examples of B) include divinylbenzene, 1, 3.
Aromatic compounds such as 5-trivinylbenzene, ester compounds such as diallyl phthalate and diallyl fumarate,
Acrylic acid esters such as trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, diethylene glycol dimethacrylate, and triethylene glycol methacrylate can be mentioned.

The amount of copolymer alloy of component (B) is 0.1 to 10% by weight, preferably 0.5 to 5% by weight. The copolymer rubber (Y) to which a gel has been imparted by the above-mentioned crosslinking monomer has better dispersibility in the thermoplastic resin (X) than that to which a gel has been imparted by other methods. As a result, the effect of improving impact resistance, which is the objective of the present invention, can be obtained.

If the amount of the copolymer alloy of component (B) is less than 0.1% by weight, the dispersibility will be poor, while if it exceeds 10% by weight, the copolymer rubber (Y) will become brittle and have poor impact resistance and mechanical strength.

Among the functional group-containing monomers (C) which are copolymerization components of the copolymer rubber (Y) of the present invention, monomers having a carboxyl group include, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, Examples include acids, and among these dicarboxylic acids, acid anhydrides can also be used. Examples of monomers having an amino group include tertiary amino group-containing monomers such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dibutylaminoethyl (meth)acrylate. .

Furthermore, as a monomer having a hydroxyl group, 1-
Examples include hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and hydroxyethyl (meth)acrylate.

Furthermore, examples of monomers having an epoxy group include glycidyl (meth)acrylate, allyl glycidyl ether, vinyl glycidyl ether, and the like. These functional group-containing monomers can be used alone or in combination of two or more.

The content of monomer (C) is 0.1 to 20% by weight, preferably 0.1 to 10% by weight. If it is less than 0.1% by weight, a good effect of improving impact resistance cannot be obtained, and if it is more than 20% by weight, the glass transition temperature of the copolymer rubber (Y) becomes high and the cold resistance is poor.

Examples of the vinyl cyanide single solid (D) which is a copolymerization component of the copolymer rubber (Y) of the present invention include acrylonitrile, methacrylonitrile, α-taloloacrylonitrile, and the like, with acrylonitrile being particularly preferred.

The amount of the copolymer of the vinyl cyanide monomer (D) is 0 to 50% by weight, preferably 0 to 40% by weight.

In order to obtain the copolymerization effect of the vinyl cyanide monomer, the amount is preferably 5 to 40% by weight.

If it exceeds 50% by weight, the rubbery properties will be poor and the effect of improving impact resistance and imparting flexibility will be poor.

The conjugated diene monomer (E) which is a copolymerization component of the copolymer rubber (Y) of the present invention is represented by the general formula (R, R', R' are hydrogen or an alkyl group). Specific examples include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, piperylene, 1,3-
Examples include hexadiene, but butadiene and isoprene are particularly preferred.

The amount of copolymer of component (E) in copolymer rubber (Y) is 0 to 5
It is 0% by weight, preferably 1 to 45% by weight.

If the content of component (E) exceeds 50% by weight, the heat deterioration resistance and weather resistance, which are the characteristics of the present invention, will be poor.

The gel content of the copolymer rubber (Y) is 20% by weight or more, preferably 50% by weight or more. Gel content is 20% by weight
If it is less than 1, the dispersibility in the thermoplastic resin (X) will be poor, resulting in poor impact resistance and mechanical strength.

The gel content here is a value measured by the following method. Weigh out about 1g of rubber accurately, put it in an Erlenmeyer flask, and add 1g of rubber.
Add 00ml of tetrahydrofuran and let stand at 25°C for 24 hours. Next, a filtration operation was performed using a 200 mesh wire mesh, and the portion that did not pass through the wire mesh was vacuum dried, and the amount thereof was determined. The accurately weighed amount of rubber is Wo (g), and the amount that cannot pass through the wire mesh is W (
g), the gel content is determined by W/WoxlOO (%).

The composition ratio of thermoplastic resin (X)/copolymer rubber (Y) is 2
0-99% by weight/80% by weight, preferably 40-9
5% by weight and 15-60% by weight.

If (Y) is less than 1% by weight, the effect of improving impact resistance cannot be obtained, while if it exceeds 80% by weight, moldability deteriorates, which is not preferable.

In order to exhibit the effects of the invention in the thermoplastic polymer composition of the present invention, it is necessary to adjust the temperature at the time of mixing the thermoplastic resin component (
It is preferable to set the temperature to be higher than the melting point of X). If the temperature of the thermoplastic resin component during mixing is lower than the melting point, not only will the torque required during mixing increase, but also the mixing will be insufficient and the physical properties of the resulting composition will not be fully exhibited, which is undesirable. Also, if the temperature during mixing is too high, the copolymer rubber (Y)
This is not preferable because the soft component causes thermal decomposition and deterioration, making it impossible to obtain a composition with high physical properties.

Therefore, the temperature during mixing is preferably 5°C or more, more preferably 10°C or more higher than the melting point of the thermoplastic resin, and preferably 300°C or less, more preferably 280°C.
It is as follows.

There are no particular restrictions on the method used for mixing the thermoplastic resin component (X) and copolymer rubber (Y), and known methods such as an open type mixing roll, a non-release type Banbury mixer extruder, and a kneader 1 continuous mixer can be used. method can be used.

The thermoplastic polymer composition of the present invention may contain fillers such as calcium carbonate, calcium silicate, clay kaolin, talc, silica, diatomaceous earth, mica powder, asbestos, etc., within a range that does not impair moldability and mechanical strength. Alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, carbon fiber, glass fiber, etc., or coloring agents such as carbon black, ultramarine blue, titanium oxide, zinc white, red pepper, navy blue, azo Pigments, nitroso pigments, lake pigments, phthalocyanine pigments, etc. can be blended.

In addition, mineral oil-based rubber softeners called process oils or extender oils, dioctyl phthalate,
Dibutyl phthalate, diethyl phthalate, dimethyl phthalate I, tricresyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, trimellitic acid ester, dioctyl adipate, dioctyl azelaate, dioctyl sebacate, epoxy fatty acid Plasticizers such as esters, liquid rubbers such as liquid NBR1 liquid acrylic rubber, liquid polybutadiene rubber, benzenesulfonic acid butylamide,
Fluidity can be improved by blending a nylon plasticizer such as POBO, a special product of Yoshitomi Pharmaceutical Co., Ltd., and Nylon Socizer N400, a product of Shin Nippon Chemical Co., Ltd. within a range that does not impair mechanical strength.

Furthermore, when mixing, add phenylene diamine antioxidants (Tsukrac CD, Tsukrac TD, manufactured by Iriuchi Shinko Chemical Co., Ltd.).
Tsukurak G1, Tsukurak WRITE) and imidazole-based antioxidants (Tukurak MB manufactured by Ohmukai Shinko Chemical Industry)
, Tsukrak MMB) and hindered phenolic antioxidants (BHT).

300) can be added.

Of course, the polymer composition of the present invention can also be used by mixing it with other resins or elastomers.

Applications of the thermoplastic polymer composition of the present invention include body panels, bumper parts, molesite shields, steering wheels, joint boots, strut suspension boot handles and other automotive parts, shoe soles, sandals and other footwear, and electric wires. cover, connector, cap plug,
Electrical parts such as gears, golf club grips, baseball bat grips, car and motorcycle grips, swimming fins, leisure goods such as underwater glasses, gaskets, waterproof cloth, hydraulic hoses, fuel hoses, freon hoses, power steering hoses, coils. Tube, Pa. I King, Roll,
It is possible to use it as a material for garden hoses, belts, damping materials for damping steel plates, etc.

e. Examples The present invention will now be explained in more detail with reference to Examples.
The present invention is not limited to these examples in any way unless it exceeds the gist thereof.

In addition, physical properties were measured by the following method.

[Method for producing copolymer rubbers (a) to (n)] Using the emulsion polymerization recipe shown below, the copolymer rubbers were produced by carrying out emulsion 1R polymerization under the following polymerization conditions in an autoclave with an internal volume of 20 g.

Emulsion polymerization recipe Parts by weight Butadiene 15 Acrylonitrile 25 Ethyl acrylate 52 Methacrylic acid 7 Divinylbenzene 1 Water 200 Sodium dodecylbenzenesulfonate 3.5 Tertiary dodecyl mercaptan 0.025 Potassium phosphate 0.3 Ferrous sulfate 0.005 Paramenthane hydroperoxide 0.02 After the polymerization conversion rate reached 90%, 0.2 parts of hydroxylamine sulfate per 100 parts of monomer was added to stop the polymerization. The resulting polymerized product was heated and the residual supernatant was recovered by steam distillation at about 70°C under reduced pressure. 1 part of alkylated phenol was added as an anti-aging agent, and the residual supernatant was removed by steam distillation. The reaction monomer was removed and calcium chloride was added to solidify. Next, the coagulated polymer was washed with water and dried using a vacuum dryer to obtain a copolymer rubber (A).

Table 1 summarizes the properties of copolymer rubbers (B) to (N) obtained in the same manner using the feed composition shown in Table 1.

Examples 1 to 8, Comparative Examples 1 to 4 The copolymer rubber shown in Table 1 and polybutylene terephthalate (Mitsubishi Kasei Novad Wool 5010) were mixed in the ratios shown in Tables 2 and 3, manufactured by Haake Co. After mixing for 5 minutes at 280°C using a small extrusion model of Rheometwiss 254 manufactured by Rheo, the mixture was formed into an L knot, dried, and then molded using a 0.5 oz injection molding machine into a test piece for Izotsu impact test according to JIS K7110 and as shown in JIS K7203. However, a test piece for bending strength testing was molded.

The Izot impact test was performed after making a 1/4' notch on the test piece, and the test piece was placed in a constant temperature bath preset at 120°C for 120 hours as a heat deterioration resistance test. .

The bending strength test was conducted at a test speed of 50 mra/win.

The test results are shown in Table-2 and Table-3.

Examples 1 to 8 are thermoplastic polymer compositions within the scope of the present invention and provide the objects of the present invention.

Comparative Examples 1 to 3 are all flIs using copolymer rubbers outside the scope of the present invention, and cannot obtain the object of the present invention.

Comparative Example 4 uses only polybutylene terephthalate without using copolymer rubber, and has poor impact resistance.

Examples 9 to 12, Comparative Examples 5 to 8 In Examples 9 to 12, various thermoplastic resins of the present invention shown in Table 2 were used in place of the polybutylene terephthalate in Example 1, and in the other examples The same procedure as 1 was carried out. On the other hand, Comparative Examples 5 to 8 did not use copolymer rubber, and Examples 9 to 1
This is an evaluation of the thermoplastic resin used in Example 2. The evaluation results are shown in Table-2 and Table-3.

When Examples 9 to 12 are compared with Comparative Examples 5 to 8, it can be seen that the desired effects of the present invention are obtained.

Effects of the F1 invention Conventionally, as a method for improving the impact resistance of thermoplastic resins,
Rubber or a graft copolymer obtained by graft copolymerizing a monomer onto rubber was blended.

Rubber has poor dispersibility in thermoplastic resins, making it impossible to obtain sufficient impact resistance, and also causing deterioration of other physical properties. on the other hand,
Graft copolymers have better dispersibility than rubber, so they are more effective in improving impact resistance than rubber. However, since graft copolymers contain graft polymer components other than rubber in thermoplastic resins, This causes a decline in the properties of the resin. Furthermore, if a rubber component that imparts heat deterioration resistance and weather resistance is used as the rubber component of the graft copolymer, the effect of improving impact resistance will not be sufficient.

The copolymer rubber (Y) of the present invention has excellent impact resistance, heat deterioration resistance, weather resistance, and mechanical properties because it contains α, β unsaturated carboxylic acid ester as a copolymerization component and has excellent dispersibility. In addition, since it does not contain a graft polymer component, it does not reduce the excellent attributes of thermoplastic resins. Furthermore, since it is a rubber, it has the effect of improving impact resistance with a small amount. Depending on the blending amount, a hard to soft resin composition can be obtained.

The thermoplastic polymer composition of the present invention comprising the thermoplastic resin (X) and copolymer rubber (Y) has extremely high industrial value.

Patent applicant: Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] (1) A thermoplastic polymer composition comprising 20 to 99% by weight of the following thermoplastic resin (X) and 80 to 1% by weight of the following copolymer rubber (Y). (a) The thermoplastic resin (X) is polyacetal, polycarbonate, polyphenylene oxide, thermoplastic polyester, styrene resin, acrylic resin, polyarylate, polysulfone, polyether sulfone, polyallyl sulfone, polyetherimide, and poly(4- At least one type selected from methylpentene). (B) Copolymer rubber (Y) is A: α, β unsaturated carboxylic acid ester 10 to 95% by weight B: Crosslinkable monomer 0.1 to 10% by weight C: Functional groups include carboxyl group and amino group , 0.1 to 20% by weight of a monomer having at least one selected from epoxy groups and hydroxyl groups D: 0 to 50% by weight of vinyl cyanide monomers E: 0 to 50% by weight of conjugated diene monomers A rubber having as a constituent copolymer component and having a gel content of 20% by weight or more.