JPH07113034A - Thermoplastic resin composition and production of processed resin product using the same - Google Patents

Abstract

PURPOSE:To obtain thermoplastic resin compositions, good in compatibility and excellent in impact and chemical resistances, tensile toughness and rigidity. CONSTITUTION:These thermoplastic resin compositions are obtained by blending (A) a styrenic thermoplastic resin with (B1) a modified polyolefinic rubber prepared by grafting an alpha,beta-unsaturated carboxylic acid or a derivative thereof onto an ethylene-alpha-olefinic rubber and (C) a modified vinyl polymer containing epoxy groups or blending (A) the styrenic thermoplastic resin with (B2) a modified polyolefin resin composition obtained by grafting the alpha,beta-unsaturated carboxylic acid or derivative thereof onto the ethylene-alpha-olefinic rubber and polypropylene resin and (C) the modified vinyl polymer containing the epoxy groups. Furthermore, this method for producing resin moldings is to melt mold either of the resin compositions.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention has good compatibility,
The present invention relates to a thermoplastic resin composition containing a styrene-based thermoplastic resin excellent in chemical resistance, impact resistance, rigidity and tensile toughness.

[0002]

2. Description of the Related Art Styrenic thermoplastic resins (GP-PS,
HI-PS, AS, ABS, AES, AAS, ACS,
MBS resin, etc.) are characterized by high rigidity, good dimensional accuracy, and low hygroscopicity, but their chemical resistance and heat resistance are insufficient compared to other engineering plastics, limiting their applications. .

In order to improve the drawbacks of such styrenic thermoplastic resins, attempts have been made to blend polyolefins having excellent chemical resistance. Polyolefins are generally heat resistant,
It has excellent chemical resistance and low specific gravity. When both are melt-kneaded to obtain a composition, the compatibility of both is poor and it cannot be put to practical use. As a method of improving the compatibility of a resin composition composed of a styrene resin and a polyolefin, for example, a method of using a thermoplastic resin obtained by graft-polymerizing a vinyl monomer such as styrene with a polyolefin (Japanese Patent Publication No. 4-1023). A method of adding a carboxyl group-modified polyolefin and a hydroxyl group-containing aromatic vinyl multi-component copolymer (JP-A-5-93110) is known.

[0004]

However, the methods generally proposed so far have not yielded a composition which is sufficiently satisfactory in terms of total balance of compatibility, mechanical properties and chemical resistance. . For example, the above-mentioned method using a thermoplastic resin obtained by graft-polymerizing a vinyl monomer onto a polyolefin (disclosed in Japanese Patent Publication No. 4-1023) is not practical because the compatibility is insufficient and the surface condition of the molded product is poor. Further, the above method of adding a modified polyolefin and an aromatic vinyl multi-component copolymer having a hydroxyl group (disclosed in JP-A-5-93110) has insufficient compatibility and has a problem in mechanical properties, which is satisfactory. Not a thing.

That is, the object of the present invention is to obtain a thermoplastic resin composition having excellent tensile toughness and chemical resistance without impairing the impact resistance of styrene-based thermoplastic resin such as ABS resin.

[0006]

The present invention has the following constitution in order to solve the above problems.

That is, "(A) styrene type thermoplastic resin, (B1) ethylene / α-olefin type rubber with α, β
A modified ethylene / α-olefin rubber in which an unsaturated carboxylic acid or a derivative thereof is grafted to the rubber in an amount of 0.1 to 15% by weight, and (C) a modified vinyl polymer containing an epoxy group, The weight mixing ratio (A) / (B1) of the component (A) and the component (B1) is 50/50 or more.
95/5 parts by weight, and the components (A) and (B)
A thermoplastic resin composition in which the compounding amount of the component (C) is 1 to 100 parts by weight based on 100 parts by weight of 2) in total. And “(A) Styrene-based thermoplastic resin, (B2) ethylene / α-olefin-based rubber and polypropylene resin with α, β-unsaturated carboxylic acid or a derivative thereof, and ethylene / α-olefin-based rubber and polypropylene resin A modified olefin resin composition grafted by 0.1 to 15% by weight with respect to the total amount, and (C) a modified vinyl polymer containing an epoxy group, and blended by weight of component (A) and component (B2). The ratio is (A) / (B2) is 5/95 ~
95/5 and a total of 10 of the components (A) and (B2)
A thermoplastic resin composition in which the compounding amount of the component (C) is 1 to 100 parts by weight with respect to 0 parts by weight. It is composed by ".

The present invention will be specifically described below.

The styrene-based thermoplastic resin (A) in the present invention may be any styrene-containing thermoplastic resin, and those containing 10% by weight or more of styrene units are preferably used. For example, if the styrene monomer is 10
Examples thereof include a (co) polymer obtained by (co) polymerizing a monomer or a monomer mixture containing at least wt%, and a rubber-reinforced styrene thermoplastic resin. Above all, a rubber-reinforced styrene thermoplastic resin is preferably used. As the rubber-reinforced styrene-based thermoplastic resin, a rubbery polymer 1 to
Graft (co) polymer obtained by graft polymerizing 80 to 20 parts by weight of a monomer containing 10% by weight or more of styrene or a mixture thereof with 99 to 20 parts by weight, and further the graft (co) polymer and 10% by weight or more of styrene. A graft copolymer composition comprising a polymer obtained by copolymerizing a monomer mixture containing the same is generally used.

The rubbery polymer shown above is preferably one having a glass transition temperature of 0 ° C. or lower, and specifically, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene- Diene rubbers such as butadiene block copolymers, butyl acrylate-butadiene copolymers and hydrogenated products thereof,
Examples thereof include acrylic rubber such as polybutyl acrylate, polyisoprene, polychloroprene, ethylene-propylene-diene monomer terpolymer, and chlorinated polyethylene.

Specific examples of the (A) styrene type thermoplastic resin in the present invention include polystyrene (GP-P).
S), styrene-acrylonitrile copolymer (AS),
Examples of the rubber-reinforced polystyrene-based thermoplastic resin belonging to the styrene-based thermoplastic resin include rubber-modified polystyrene (HI-PS resin), styrene-rubber polymer-acrylonitrile copolymer (ABS resin, AES resin, AAS).
Resin, ACS resin) and the like. Two or more of these may be used. Furthermore, a part of styrene is α-methyl styrene, p-methyl styrene, pt-butyl styrene, ester compounds such as methyl (ethyl), propyl and n-butyl of (meth) acrylic acid, maleimide, N.
-Methylmaleimide, N-cyclohexylmaleimide,
Those substituted with a vinyl monomer copolymerizable with styrene such as N-phenylmaleimide monomer are also included. It is also possible to replace part or all of acrylonitrile with methacrylonitrile.

Among them, HI-PS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin and the like are preferably used as the rubber-reinforced styrene thermoplastic resin. In that case, it is preferable that the content of the rubbery polymer in the thermoplastic resin composition is 40% by weight or less, preferably 30% by weight or less. When it exceeds 40% by weight, the resin composition becomes too soft, which is not preferable.

The method for producing the styrene thermoplastic resin (A) is not particularly limited, and a usual method such as a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method and a bulk-suspension polymerization method can be used. Next, (B1) "modified ethylene / α obtained by grafting 0.1 to 15% by weight of α, β-unsaturated carboxylic acid or its derivative onto ethylene / α-olefin rubber.
-Olefin-based rubber "will be described.

The ethylene / α-olefin rubber, which is one of the constituents, is a copolymer mainly containing ethylene and α-olefin, and has a repeating unit derived from ethylene and a repeating unit derived from α-olefin. Are randomly combined.

Examples of such α-olefins include:
Propylene, butene-1, pentene-1, 2-methylbutene-1,3-methylbutene-1, hexene-1,3-
Methylpentene-1,4-methylpentene-1,3,3
-Dimethylbutene-1, heptene-1, methylhexene-1, dimethylpentene-1, trimethylbutene-1,
Ethylpentene-1, Octene-1, Methylpentene-
1, dimethylhexene-1, trimethylpentene-1,
Ethylhexene-1, methylethylpentene-1, diethylbutene-1, propylpentene-1, decene-1,
Examples thereof include methylnonene-1, dimethyloctene-1, trimethyloctene-1, trimethylheptene-1, ethyloctene-1, methylethylheptene-1, diethylhexene-1, dodecene-1 and hexadecene-1. . Of these, propylene is preferably used.

The content of repeating units derived from ethylene is usually 95 mol% or less, preferably 3 mol% or more and 90 mol% or less.
The α-olefin rubber is low crystalline or amorphous.

Further, the melt index of this ethylene / α-olefin rubber measured at 220 ° C. is usually 0.01 to 100 g / 10 minutes, preferably 0.05 to
It is 50 g / 10 minutes. Further, ethylene / α-olefin rubber is a copolymer component other than the above olefins.
It is also possible to copolymerize polyene compounds. The polyene compound is a monomer containing two or more radical-reactive non-conjugated double bonds in the same molecule, and specific examples include 5-ethylidene-2-norbornene, 1,4-hexadiene, Cyclopentadiene etc. can be mentioned. The copolymerization amount of the polyene compound is preferably in the range of 0 to 30 parts by weight with respect to 100 parts by weight of the ethylene / α-olefin rubber.

Examples of the α, β-unsaturated carboxylic acid and its derivative which are the other constituents of the modified ethylene / α-olefin rubber are acrylic acid, methacrylic acid,
Maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methylfumaric acid, mesaconic acid, citraconic acid, glutaconic acid, methyl hydrogen maleate, methyl hydrogen itaconic acid, methyl acrylate, ethyl acrylate,
Butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride , Fumaric anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- [2,2,1] -5-heptene 2,3-dicarboxylic acid, endobicyclo- [2,2,1] -5-heptene-2 , 3-dicarboxylic anhydride can be mentioned. Among these, α, β-unsaturated carboxylic acid in which hydrogen of both α carbon and β carbon is substituted with carboxylic acid is preferably used from the viewpoint of stability of the obtained modified ethylene / α-olefin rubber. Of these, maleic anhydride is preferably used for economic reasons.

The method of introducing the components of these α, β-unsaturated carboxylic acids or their derivatives is not particularly limited,
Known methods of grafting onto polyolefins can be used. The amount of the α, β-unsaturated carboxylic acid or its derivative component introduced is 0.1 to 15% by weight, preferably 0.5 to 10% by weight based on the ethylene / α-olefin rubber.
A range of weight% is suitable. When the amount of the component is less than 0.1% by weight, the affinity with the styrene resin is insufficient and a composition in an intimate mixed state cannot be obtained, which is not preferable. On the other hand, when the amount of the functional group-containing component exceeds 15% by weight, Due to the influence of side reactions, the stability of the modified ethylene / α-olefin rubber is lowered and gelation is likely to occur, which is not preferable.

(B1) Modified ethylene / α in the present invention
The olefinic rubber is prepared in the usual way. Utilizing a method in which an α, β-unsaturated carboxylic acid or a derivative thereof is mixed with ethylene / α-olefin rubber and melt-kneaded at 120 to 300 ° C. by using an extruder, a Banbury mixer or the like to cause a chemical reaction. You can In this case, it is preferable to add an organic peroxide together, because the graft reaction proceeds efficiently. In addition, a pre-prepared modified ethylene / α-olefin rubber having a high grafting ratio is added to unmodified ethylene / α-olefin rubber so that the grafting ratio falls within a preferable range.
It can also be adjusted by blending an α-olefin rubber. Further, (B1) a modified ethylene / α-olefin rubber, a polyolefin other than the unmodified ethylene / α-olefin rubber, or a derivative or modified product thereof can be added.

In order to control mechanical properties such as rigidity,
Instead of part of this ethylene / α-olefin rubber,
It is possible to use polypropylene resin. That is, instead of (B1) modified ethylene / α-olefin rubber, (B2) “modified polyolefin resin obtained by grafting α, β-unsaturated carboxylic acid or its derivative on ethylene / α-olefin rubber and polypropylene resin. A composition can be used.

Examples of polypropylene resins include commercially available polypropylene homopolymers and propylene / α-olefin copolymers obtained by copolymerizing other α-olefins within a range that does not impair the properties of polypropylene. A propylene homopolymer is preferably used.
Further, the melt index of this polypropylene resin measured at 220 ° C. is usually 0.01 to 100 g / 1.
Those having 0 minutes, preferably 0.05 to 50 g / 10 minutes are preferably used.

The mixing ratio by weight of ethylene / α-olefin rubber and polypropylene resin is preferably 100/0.
Those having a ratio of 1/99, more preferably 99/1 to 1/99, and further 70/30 to 1/99 are preferably used.

The method of introducing the α, β-unsaturated carboxylic acid or the derivative thereof into the ethylene / α-olefin rubber and the polypropylene resin is not particularly limited, and a known method of grafting to a polyolefin is used. be able to.

The graft amount of the α, β-unsaturated carboxylic acid or its derivative component is 0.1 to 1 with respect to the total amount of the ethylene / α-olefin rubber and the polypropylene resin.
It is 5% by weight, preferably 0.5 to 10% by weight. If the amount of the component is less than 0.1% by weight, the affinity with the styrene resin is insufficient and a composition in an intimate mixed state cannot be obtained, which is not preferable, while if the amount of the functional group-containing component exceeds 15% by weight, Stability of the modified polyolefin resin composition is lowered by the influence of side reactions, and problems such as gelation are likely to occur, which is not preferable.

The (B2) modified polyolefin resin composition in the present invention is prepared by a usual method. ethylene·
Polypropylene resin is mixed with α-olefin rubber, α, β-unsaturated carboxylic acid or its derivative is blended, and usually melted and kneaded at 120 to 300 ° C. using an extruder, Banbury mixer or the like to carry out a chemical reaction. How to do it is available. Even in this case, it is more preferable to add the organic peroxide together, because the graft reaction proceeds efficiently. Further, both the (B1) modified ethylene / α-olefin rubber and the polypropylene resin grafted with the α, β-unsaturated carboxylic acid or its derivative, which have been prepared in advance and individually modified by the same method, are melted. It can also be adjusted by kneading. In addition, the modified ethylene / α-olefin rubber and / or modified polypropylene resin having a high grafting ratio, which has been prepared in advance, has a non-modified ethylene / unmodified ethylene so that the grafting ratio falls within a preferable range.
It can also be adjusted by blending an α-olefin rubber and a polypropylene resin.

The modified vinyl polymer (C) containing an epoxy group (hereinafter abbreviated as a modified vinyl polymer) in the present invention means an epoxy group-containing vinyl monomer and another copolymerizable vinyl monomer. Is a copolymer consisting of The epoxy group-containing monomer is not particularly limited as long as it is a monomer having both an ethylenically unsaturated double bond and an epoxy group in the same molecule, for example, glycidyl acrylate,
Glycidyl methacrylate is preferably used. As the other copolymerizable vinyl monomer, aromatic vinyl, vinyl cyanide, α, β-unsaturated carboxylic acid and derivatives thereof are preferably used, and as the aromatic vinyl, styrene,
α-Methylstyrene is preferred. Examples of vinyl cyanide include acrylonitrile and methacrylonitrile. Of these, acrylonitrile is preferred. α, β-
As the unsaturated carboxylic acid and its derivative, an esterified product is preferably used, and methyl acrylate,
Examples thereof include ethyl acrylate, butyl acrylate, and methyl methacrylate.

As the copolymerization ratio of the (C) modified vinyl polymer, an epoxy group-containing monomer is preferably used in an amount of 0.1 to 80% by weight, more preferably 5 to 70% by weight. The copolymerizable vinyl monomer of is preferably 20 to 99.9% by weight, and more preferably 3
0 to 95% by weight is used.

The method for producing the modified vinyl polymer (C) is not particularly limited, and known methods such as bulk polymerization, solution polymerization, bulk-suspension polymerization, suspension polymerization and emulsion polymerization can be used.

The compounding ratio of the (A) styrene thermoplastic resin and the (B1) modified ethylene / α-olefin rubber in the present invention is a resin obtained when the amount of the (B1) modified ethylene / α-olefin rubber is small. Since the chemical resistance of the composition and the machined product deteriorates, and the rigidity decreases when the composition is large, the ratio by weight of the component (A) / the component (B1) is 50/50 as the lower limit, preferably 55/45. More preferably, 60/40 is used, and the upper limit is 95/5, preferably 92/8, more preferably 90/10.

When a polypropylene resin is used in place of a part of the ethylene / α-olefin rubber, the resin composition obtained by using a small amount of the (B2) modified polyolefin resin composition and a machined product are obtained. The chemical resistance deteriorates, and if too much, the rigidity decreases.
The blending amounts of the styrene-based thermoplastic resin component and the (B2) modified polyolefin resin composition component are (A) component / (B2)
The lower limit of the weight ratio of the components is 5/95, preferably 2
0/80, more preferably 30/70, and the upper limit is 95/5, preferably 90/10.

The blending amount of the (C) modified vinyl polymer is (A)
Styrenic thermoplastic resin, (B1) modified ethylene / α-
1 to 100 parts by weight, preferably 1 to 70 parts by weight, particularly preferably 1 to 5 parts by weight based on 100 parts by weight of the olefin rubber or the (B2) modified polyolefin resin composition.
0 parts by weight. If the amount of the modified vinyl polymer (C) is less than 1 part by weight, the impact resistance of the resin composition is poor, and if it exceeds 100 parts by weight, the impact resistance, tensile toughness and molding processability of the resin composition are inferior.

There is no particular limitation on the method for producing a resin composition from each component of the present invention. For example, (A) styrene thermoplastic resin, (B1) modified ethylene / α-olefin rubber, or (B2) modified. Examples of the method include melt-kneading the polyolefin resin composition or a mixture of the polyolefin resin composition and the modified vinyl polymer (C) with a Banbury mixer, a roll, an extruder, or the like.

The resin composition of the present invention may be any other thermoplastic polymer such as vinyl chloride resin, polymethylmethacrylate, polycaproamide (nylon 6), polyhexamethyleneadipamide, etc. within the range not impairing the object of the present invention. By mixing (nylon 66), polybutylene terephthalate, polyethylene terephthalate, polycarbonate, polyphenylene sulfide, etc., the performance as a molding resin can be improved.

Further, depending on purposes, reinforcing materials and fillers such as pigments and dyes, glass fibers, metal fibers, metal flakes and carbon fibers, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers. Agents, antistatic agents, flame retardants and the like can also be added.

The resin composition of the present invention is further heated and melted and molded to produce a resin processed product comprising the resin composition of the present invention. The molding method is not particularly limited, and injection molding, extrusion molding (tube, pipe, sheet, etc.), blow molding (direct blow, injection blow,
A resin processed product can be obtained by a molding method such as multi-layer blow), vacuum molding or compression molding, and can be used for various parts and products.

Further, adhesion, labeling, printing, painting,
Post-processing such as welding and cutting can be applied.

The application of these resin processed products is not particularly limited, but parts and materials for automobiles, chemical plants, aviation, space, machines, electric and electronic parts, especially interior materials for automobiles,
It can be used as a material for housing electrical and electronic products.

[0039]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples.

As an evaluation of impact resistance, 1/2 "Izod impact strength was measured according to ASTM D256-56. As an evaluation of rigidity, flexural modulus was determined according to ASTM D79.
It was measured according to 0. As an evaluation of tensile toughness, tensile elongation at break was measured according to ASTM D638. Chemical resistance is 23
The surface of the square plate was visually observed by immersing it at 24 ° C. for 24 hours. The following parts and% are parts by weight and% by weight, respectively.
Represents

Reference Example (1) Preparation of Styrenic Thermoplastic Resin A-1: Polybutadiene Latex (Rubber Particle Diameter 0.2
In the presence of 5 parts (gel content 80%) and 25 parts (solid content conversion), 75 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile was emulsion polymerized.

The obtained graft copolymer was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered and dried to prepare a powdery graft copolymer (A-1). The resulting graft copolymer had a butadiene structural unit of 25%, a styrene structural unit of 53%, and an acrylonitrile structural unit of 22%.
It was something that had.

A-2: Methyl methacrylate 15%, styrene 65%, acrylonitrile 2 in the presence of 15 parts (as solid content) of the polybutadiene latex used in A-1.
After emulsion-polymerizing 85 parts of a 0% monomer mixture, A
In the same manner as in -1, powdery graft copolymer (A-
2) was prepared. The obtained graft copolymer has a butadiene structural unit of 15% and a methyl methacrylate structural unit of 13%.
%, Styrene structural unit 55%, and acrylonitrile structural unit 17%.

A-3: Styrene was suspension polymerized alone.
The polymer obtained was filtered and then dried to prepare beaded polystyrene (A-3).

A-4: 80 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile was emulsion-polymerized in the presence of 20 parts (as solid content) of the polybutadiene latex used in A-1. The obtained graft copolymer was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered and dried to prepare a powdery graft copolymer (A-4).

The resulting graft copolymer had 20% butadiene structural units, 56% styrene structural units and 24% acrylonitrile structural units.

A-5: Methyl methacrylate 15%, styrene 65%, acrylonitrile 2 in the presence of 40 parts (as solid content) of the polybutadiene latex used in A-1.
After emulsion polymerization of 60 parts of a 0% monomer mixture, A
In the same manner as in -1, powdery graft copolymer (A-
5) was prepared. The obtained graft copolymer has a butadiene structural unit of 40% and a methyl methacrylate structural unit of 9%.
%, Styrene structural unit 39%, acrylonitrile structural unit 12%.

A-6: 20 parts of polybutadiene rubber was dissolved in 70 parts of styrene and 10 parts of acrylonitrile, and then bulk polymerization was carried out to prepare a graft copolymer (A-6). The obtained compound had a composition that maintained the mixing ratio.

(2) Preparation of modified ethylene / α-olefin rubber B-1: 100 parts of ethylene / propylene rubber (melt index 1.5 g / 10 minutes), maleic anhydride 3.5
Part, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane 0.5 part, using a twin screw extruder with a vent, melt-kneading at 180 ° C., discharging, cooling and pelletizing. The modified polyolefin copolymer rubber (B-1) was prepared. The obtained compound was the one in which the compounded maleic anhydride was completely reacted.

B-2: Ethylene propylene diene rubber (melt index 2.0 / 10 minutes) 100 parts, maleic anhydride 5.0 parts, 2,5-dimethyl-2,5-di (t-butylperoxy) ) A mixture of 0.5 parts of hexane was melt-kneaded at 180 ° C. using a twin screw extruder with a vent, discharged and cooled, and then pelletized to prepare a modified polyolefin copolymer rubber (B-2). The obtained compound was the one in which the compounded maleic anhydride was completely reacted.

B-3: The ethylene / propylene rubber used in B-1 was used as it was without modification.

(3) Preparation of modified polyolefin resin composition B-4: 60 parts of ethylene / propylene rubber (melt index 1.5 g / 10 minutes), polypropylene (melt index 5 g / 10 minutes) 40 parts, maleic anhydride 3 A mixture of 0.5 parts of 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane (0.5 parts) was melt-kneaded at 180 ° C. using a vented twin-screw extruder, and after discharge cooling Pelletized and modified polyolefin resin composition (B-
4) was adjusted. The resulting composition was one in which all the maleic anhydride compounded had reacted.

B-5: 30 parts of ethylene / propylene rubber used in B-1, 70 parts of polypropylene, 1 part of maleic anhydride, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane A pelletized modified polyolefin resin composition (B-5) was prepared in the same manner as B-4 using 0.2 part of the mixture. The resulting composition was one in which all the maleic anhydride compounded had reacted.

(4) Preparation of modified vinyl polymer C-1: 70 parts of styrene, 3 of glycidyl methacrylate
A modified vinyl polymer (C-1) was prepared by bulk polymerization of 0 part. The obtained polymer had a chemical structure that maintained the composition ratio of the monomers.

C-2: 65 parts of styrene, 15 parts of acrylonitrile and 20 parts of glycidyl methacrylate were bulk polymerized to prepare a modified vinyl polymer (C-2). The obtained polymer had a chemical structure that maintained the composition ratio of the monomers.

C-3: 50 parts of styrene and 50 parts of glycidyl methacrylate were bulk polymerized to prepare a modified vinyl polymer (C-3). The obtained polymer had a chemical structure that maintained the composition ratio of the monomers.

Examples 1 to 6 (A) Styrenic thermoplastic resin prepared in Reference Example, (B)
1) The modified ethylene / α-olefin rubber and the (C) modified vinyl polymer were mixed at the compounding ratio shown in Table 1, and the resin temperature was 230 ° C. in a vented 30 mmφ twin screw extruder.
Pellets were produced by melt-kneading and extruding with.

Then, using an injection molding machine, a test piece was molded at a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C., and its physical properties were measured.

Comparative Examples 1 to 6 (A) Styrenic thermoplastic resin prepared in Reference Example, (B)
2) The modified polyolefin rubber and the (C) modified vinyl polymer were melt-kneaded and molded at the compounding ratios shown in Table 1 in the same manner as in Examples, and the physical properties were measured.

The measurement results are shown in Table 2.

[0061]

[Table 1]

[Table 2]

From the above Examples and Comparative Examples, the following is clear.

That is, the resin composition of the present invention (Example 1)
All of 6 to 6) are excellent in impact resistance, rigidity, tensile toughness and chemical resistance.

On the other hand, those containing a small amount of the styrene-based thermoplastic resin (Comparative Examples 1 and 6) are inferior in rigidity, which is not preferable. Further, a compound containing a small amount of the modified ethylene / α-olefin rubber (Comparative Example 2) is inferior in chemical resistance and is not preferred.

The compound containing a small amount of the modified vinyl polymer (Comparative Example 3) is inferior in tensile toughness, and the compound containing a large amount of the modified vinyl polymer (Comparative Example 4) is also inferior in tensile toughness, which is not preferable.

Further, the one using the unmodified ethylene / α-olefin rubber (Comparative Example 5) is inferior in impact resistance and tensile toughness, which is not preferable.

Examples 7 to 12 The rubber-reinforced styrene thermoplastic resin (A), the modified polyolefin resin composition (B2), and the modified vinyl polymer (C) prepared in Reference Examples were mixed at the compounding ratios shown in Table 3. Mix and vent with a 30mmφ twin-screw extruder, resin temperature 230 ℃
Pellets were produced by melt-kneading and extruding with.

Then, a test piece was molded with an injection molding machine at a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C., and the physical properties were measured.

Comparative Examples 7 to 11 The rubber-reinforced styrene thermoplastic resin (A), the (B2) modified polyolefin resin composition and the (C) modified vinyl polymer prepared in Reference Examples were prepared at the compounding ratios shown in Table 3. Physical properties were measured by melt-kneading and molding in the same manner as in the examples.

The measurement results are shown in Table 4.

[0071]

[Table 3]

[Table 4]

That is, the resin composition of the present invention (Example 7)
Nos. 11 to 11) are all excellent in impact resistance, rigidity, tensile toughness and chemical resistance.

On the other hand, those containing a small amount of styrene-based thermoplastic resin (Comparative Examples 7 and 12) are not preferable because their rigidity is poor. Further, those containing a small amount of the modified polyolefin resin composition (Comparative Examples 8 and 11) are inferior in chemical resistance, which is not preferable.

A compound having a small amount of modified vinyl polymer (Comparative Example 9) is inferior in tensile toughness, and a compound having a large compounding amount of modified vinyl polymer (Comparative Example 10) is inferior in tensile toughness. .

[0075]

According to the present invention, a thermoplastic resin composition having good compatibility and excellent impact resistance, tensile toughness, chemical resistance and rigidity can be obtained.

Claims (6)

[Claims] 1. (A) Styrenic thermoplastic resin, (B1)
Ethylene / α-olefin-based rubber contains α, β-unsaturated carboxylic acid or its derivative in an amount of 0.1 to 1 relative to the rubber.
It is composed of a modified ethylene / α-olefin rubber grafted with 5% by weight and (C) a modified vinyl polymer containing an epoxy group, and has a weight compounding ratio (A) / (B1) of the component (A) and the component (B1). ) Is 50/50 to 95/5 parts by weight, and the total amount of component (A) and component (B2) is 100.
A thermoplastic resin composition in which the amount of component (C) is 1 to 100 parts by weight based on parts by weight. 2. A thermoplastic styrene resin (A), and a thermoplastic resin (B2).
Α, β-unsaturated carboxylic acid or its derivative in ethylene / α-olefin rubber and polypropylene resin,
A modified olefin resin composition grafted by 0.1 to 15% by weight with respect to the total amount of ethylene / α-olefin rubber and polypropylene resin, and (C) a modified vinyl polymer containing an epoxy group, (A)
And the blending ratio (A) / (B2) by weight of the component (B2) is 5/9
5 to 95/5, and the compounding amount of the component (C) is 1 to 1 with respect to 100 parts by weight of the components (A) and (B2) in total.
The thermoplastic resin composition is 00 parts by weight. 3. The thermoplastic resin composition according to claim 1, wherein the (A) styrene-based thermoplastic resin is a rubber-reinforced styrene-based thermoplastic resin. 4. The amount of the epoxy group-containing monomer in the modified vinyl polymer (C) containing an epoxy group is 0.1 to 80% by weight in the modified vinyl polymer. A thermoplastic resin composition selected from the following. 5. A structural unit other than the epoxy group-containing monomer in the modified vinyl polymer (C) containing an epoxy group, which is aromatic vinyl, vinyl cyanide, and α, β-unsaturated carboxylic acid or the same. The thermoplastic resin composition selected from any one of claims 1 to 4, which contains a structure derived from any of the derivatives. 6. A method for producing a resin processed product, which comprises melt-molding the thermoplastic resin composition according to any one of claims 1 to 5.