JPH0532876A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. which is excellent in chemical resistance and coatability and needs no priming before being coated. CONSTITUTION:A resin compsn. which is prepd. by compounding 100 pts.wt. compsn. comprising 10-90wt.% polycarbonate resin and 90-10wt.% ABS resin with 0.1-40 pts.wt. the sum of 95-5wt.% polyolefin-graft polymer and 5-95wt.% terpolymer prepd. from an olefin, an unsatd. carboxylic acid anhydride, and an alkyl unsatd. carboxylate. The graft polymer is prepd. by grafting a monomer mixture comprising 50-100wt.% arom. vinyl and 0-50wt.% monomer component consisting of a vinyl cyanide and/or an alkyl unsatd. carboxylate onto a crystalline polyolefin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a resin having excellent coatability, which is obtained by blending a composition comprising a polycarbonate resin and a rubber-reinforced styrene resin with a specific polyolefin graft polymer and a specific terpolymer. It relates to a composition.

[0002]

2. Description of the Related Art Polycarbonate resins have excellent mechanical and thermal properties and are widely used in various fields, but their molding temperature is high.
It has the disadvantages of poor fluidity and large impact strength thickness dependence. For this reason, AB
A composition prepared by blending a rubber-reinforced styrene resin such as an S resin has been proposed and has already been used as a vehicle or a light electric component.

However, the composition comprising a polycarbonate resin and a rubber-reinforced styrene resin has a problem that it is inferior in chemical resistance and paintability.

Regarding the improvement of chemical resistance to gasoline, dioctyl phthalate, etc., it has already been proposed to blend a polyamide resin as a third component, but since the compatibility is poor, it is not possible to blend a large amount of polyamide, and the resistance to polyamide is low. There is a limit to the improvement of chemical properties.

Further, the thinner used during coating has a stronger effect than gasoline or dioctyl phthalate, and therefore it is the actual situation that a primer treatment must be performed before coating.

Therefore, it is desired to develop a resin composition which is excellent not only in chemical resistance but also in coatability, and further, which is not subjected to a primer treatment before coating.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in view of the above problems, and as a result, have found that a composition comprising a polycarbonate resin and a rubber-reinforced styrene-based resin has a specific polyolefin graft polymer and a specific polyolefin graft polymer. By blending a ternary copolymer or a specific epoxy group-containing olefin copolymer in a specific amount in a specific ratio, chemical resistance as well as coating properties are excellent without sacrificing the original characteristics of the composition. The present invention has been accomplished by finding that a resin composition can be obtained.

That is, the first aspect of the present invention is that the polycarbonate resin (A) is 10 to 90% by weight, the rubbery polymer (b-1) and the aromatic vinyl monomer are 50 to 90% by weight,
A monomer (b-consisting of 50 to 10% by weight of a vinyl cyanide-based monomer and / or an unsaturated carboxylic acid alkyl ester-based monomer and 0 to 40% by weight of another copolymerizable vinyl-based monomer. The crystalline polyolefin (c-1) and the aromatic vinyl monomer 50 to 100 per 100 parts by weight of the composition composed of 90 to 10% by weight of the rubber-reinforced styrene resin (B) obtained by polymerizing Polyolefin graft polymer (C) obtained by polymerizing a monomer (c-2) consisting of 50% by weight of vinyl cyanide monomer and / or unsaturated carboxylic acid alkyl ester monomer of 50 to 0% by weight. ) And 50 to 98.5% by weight of an olefin, 0.5 to 10% by weight of an unsaturated dicarboxylic acid anhydride, and 1 to 40% by weight of an unsaturated carboxylic acid alkyl ester-based monomer as a total amount of a terpolymer (D) of 0.1. ~ 4 It will be parts by weight blended, and,
A resin composition having excellent coatability, characterized in that the polyolefin graft polymer (C) / terpolymer (D) is mixed in a weight ratio of 5/95 to 95/5. Is provided.

The second invention of the present invention is that the polycarbonate resin (A) is 10 to 90% by weight, and the rubber-like polymer (b-
1) and 50 to 90% by weight of an aromatic vinyl-based monomer, 50 to 10% by weight of a vinyl cyanide-based monomer and / or an unsaturated carboxylic acid alkyl ester-based monomer, and another vinyl-based copolymerizable monomer A crystalline polyolefin (100 parts by weight of a composition consisting of 90 to 10% by weight of a rubber-reinforced styrene resin (B) obtained by polymerizing a monomer (b-2) of 0 to 40% by weight of a monomer). c-1) and 50 to 100% by weight of an aromatic vinyl-based monomer, 50 to 0% by weight of a vinyl cyanide-based monomer and / or an unsaturated carboxylic acid alkyl ester-based monomer ( A combination of a polyolefin graft polymer (C) obtained by polymerizing c-2) and an unsaturated epoxy compound and an olefin, or an epoxy group-containing olefin copolymer (D) comprising them and an ethylenically unsaturated compound. 5 in 0.1 to 40 will be parts by weight blended, and polyolefin graft polymer (C) / epoxy group-containing olefin copolymer ratio by weight of (D)
The present invention provides a resin composition having excellent coatability, which is characterized by being mixed so as to be / 95 to 95/5.

The present invention will be described in detail below.

Examples of the polycarbonate resin (A) include aromatic polycarbonate, aliphatic polycarbonate, and aliphatic-aromatic polycarbonate. Generally, a polymer composed of bisphenols such as 2,2-bis (4-oxyphenyl) ankane type, bis (4-oxyphenyl) ether type, bis (4-oxyphenyl) sulfone, sulfide or sulfoxide type, or It is also possible to use a copolymer which is a copolymer and which uses a halogen-substituted bisphenol, or a branched polymer which is obtained by polymerization using a copolymer or a branching agent, depending on the purpose.

The molecular weight of the polycarbonate resin (A) is not particularly limited, but one having a viscosity average molecular weight of 10,000 to 100,000 is preferable. In addition, the manufacturing method is not limited, and the phosgene method,
A transesterification method or the like is used.

The rubber-reinforced styrenic resin (B) means the rubber-like polymer (b-1) and the aromatic vinyl-based monomer 50 to 90.
% By weight, vinyl cyanide type monomer and / or unsaturated carboxylic acid alkyl ester type monomer 50 to 10% by weight
And 0-40% by weight of other copolymerizable vinyl monomer
Is a resin obtained by polymerizing a monomer (b-2) consisting of the above, and is a graft weight obtained by polymerizing the monomer (b-2) in the presence of the rubber-like polymer (b-1). It is a mixture or a mixture of the graft polymer and a copolymer obtained by polymerizing the monomer (c-2).

Examples of the rubber-like polymer (b-1) include a polyene having a glass transition temperature of 0 ° C. or lower, a diene polymer such as a styrene-butadiene copolymer, an acrylonitrile-butadiene copolymer, and an ethylene-propylene copolymer. Examples thereof include a polymer, an ethylene-propylene-based copolymer such as an ethylene-propylene-non-conjugated diene-based copolymer, an acrylic acid ester-based copolymer, a chlorinated polyethylene and the like, and one or more kinds can be used. A diene polymer is particularly preferable.

These rubber-like polymers are produced by emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization and the like. The gel content of the rubber-like polymer in the case of production by emulsion polymerization is not particularly limited, but is preferably 0 to 95%.

Aromatic vinyl monomers are styrene,
α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene,
α-Methylvinyltoluene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromstyrene, dibromostyrene, vinylnaphthalene, etc. are exemplified, and one kind or two or more kinds can be used. Particularly preferred is styrene.

Examples of vinyl cyanide-based monomers include acrylonitrile, methacrylonitrile, and fumaronitrile, and one or more of them can be used. Acrylonitrile is particularly preferable.

Examples of the unsaturated acid carboxylic acid alkyl ester-based monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. More than one species can be used. Methyl methacrylate is particularly preferable.

Other copolymerizable vinyl-based monomers capable of constituting the rubber-reinforced styrene resin (B) together with the above-mentioned monomers include acrylic acid, methacrylic acid, maleic acid and maleic anhydride. Unsaturated carboxylic acids such as citraconic anhydride or unsaturated dicarboxylic acid anhydrides, maleimides, methylmaleimide, ethylmaleimide, N-phenylmaleimide, O-chloro-N-phenylmaleimide, and other maleimide compounds. Each of these can be used alone or in combination of two or more.

Aromatic vinyl monomer (i), vinyl cyanide monomer and / or unsaturated carboxylic acid alkyl ester monomer (ii) in monomer (b-2) and copolymerizable The composition ratio of the other vinyl-based monomer (iii) is (i) 50 to 90% by weight, (ii) 50 to 10% by weight.
And (iii) 0-40% by weight. Outside this range, the heat resistance and workability are poor, which is not preferable. Preferably, (i) 50 to 80% by weight, (ii) 50 to 20% by weight
And (iii) 0 to 30% by weight, and the monomer (b-2) using a vinyl cyanide-based monomer as (ii) is particularly preferable.

The rubber-like polymer (b-1) and the monomer (b-
The composition ratio with 2) is not particularly limited, but from the viewpoint of heat resistance, impact resistance and workability, the rubber-like polymer (b-1) 5 to 8 is used.
It is preferably 0% by weight and 95 to 20% by weight of the monomer (b-2).

A resin comprising a graft polymer having a graft ratio of 20 to 100% and a weight average particle diameter of 0.05 to 5 μm and a copolymer is particularly preferable.

The method for producing the rubber-reinforced styrenic resin (B) (graft polymer and copolymer) is not particularly limited, and known emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization or a combination thereof. Is used.

The polyolefin graft polymer (C) means the crystalline polyolefin (c-1), 50 to 100% by weight of an aromatic vinyl monomer, a vinyl cyanide monomer and / or an unsaturated carboxylic acid. It is a polymer obtained by polymerizing a monomer (c-2) consisting of 50 to 0% by weight of an alkyl ester monomer.

The crystalline polyolefin (c-1) means polyethylene and polypropylene, and in particular, acrylonitrile / styrene mixed monomer (25/75 weight ratio).
A crystalline polyolefin having a swelling degree with respect to (2 ° C., 1 hour immersion) of 2 to 80% by weight, particularly 2 to 60% by weight is preferable.

Polyethylene includes high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, and polypropylene includes homopolymers as well as random polymers and block polymers with ethylene and α-olefins. Named
One kind or two or more kinds can be used. Amorphous ethylene-propylene copolymers cannot achieve the object of the present invention.

As the aromatic vinyl-based monomer and the vinyl cyanide-based monomer, the monomers mentioned in the section of the rubber-reinforced styrene-based resin (B) are exemplified. Further, examples of the unsaturated carboxylic acid alkyl ester-based monomer include the monomers listed in the section of the rubber-reinforced styrene-based resin (B), glycidyl acrylate, and glycidyl methacrylate.

Aromatic vinyl monomers are styrene,
Acrylonitrile is preferred as the vinyl cyanide-based monomer, and glycidyl methacrylate and methyl methacrylate are preferred as the unsaturated carboxylic acid alkyl ester-based monomer.

The composition ratio of the aromatic vinyl type monomer (i), the vinyl cyanide type monomer and / or the unsaturated carboxylic acid alkyl ester type monomer (ii) in the monomer (c-2) is , (I) 50 to 100% by weight, (ii) 50 to 0
% By weight. Outside of this range, the chemical resistance is poor and it is not preferable. It is preferably (i) 50 to 90% by weight and (ii) 50 to 10% by weight.

The composition ratio of the crystalline polyolefin (c-1) and the monomer (c-2) is not particularly limited, but the crystalline polyolefin (c) is preferred in view of chemical resistance, paintability and impact resistance. -1) 100 parts by weight of monomer (c-2) 20
To 200 parts by weight are preferred, and especially monomer (c-2) 20
-100 parts by weight is preferred.

The method for producing the polyolefin graft polymer (C) is not particularly limited, and known emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization or a combination thereof may be used.

The terpolymer (D) in the first invention means 50 to 98.5% by weight of olefin, 0.5 to 10% by weight of unsaturated dicarboxylic acid anhydride, and 1 to 1 of unsaturated carboxylic acid alkyl ester monomer. It consists of 40% by weight.

Examples of the olefin include ethylene, propylene, butene-1, and 4-methylpentene-1, and ethylene and propylene are particularly preferable. Examples of unsaturated dicarboxylic acid anhydrides include maleic anhydride, citraconic anhydride, and aconitic anhydride, with maleic anhydride being particularly preferred. Examples of unsaturated carboxylic acid alkyl ester-based monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and hydroxymethyl (meth) acrylate, and particularly ethyl acrylate. Butyl acrylate is preferred.

If the olefin content is less than 50% by weight, the effect of improving the chemical resistance will not be exerted, and if it exceeds 98.5% by weight, the compatibility will be poor and the impact resistance will be reduced, or delamination of the molded article will occur. Occurs.

If the unsaturated dicarboxylic acid anhydride content is less than 0.5% by weight, the impact resistance is poor, and if it exceeds 10% by weight, the thermal stability and processability are deteriorated.

Further, if the unsaturated carboxylic acid alkyl ester monomer is less than 1% by weight, the compatibility becomes poor, and
If it exceeds 40% by weight, not only sufficient improvement in chemical resistance cannot be obtained, but also heat resistance, rigidity, etc. are deteriorated and the balance of mechanical properties is deteriorated.

Particularly, from the viewpoint of chemical resistance and impact resistance,
A terpolymer of 55 to 96% by weight of an olefin and 1 to 8% by weight of an unsaturated dicarboxylic acid anhydride and 3 to 37% by weight of an unsaturated carboxylic acid alkyl ester monomer is preferable.

The terpolymer (D) can be produced by various methods. For example, olefin is fed to the first zone of a cylindrical autoclave equipped with a blade-type stirrer, then olefin in the second zone, unsaturated dicarboxylic acid anhydride,
A monomer mixture of unsaturated carboxylic acid alkyl ester is supplied, and a radical initiator such as t-butyl 2-ethyl-perhexanoate dissolved in a hydrocarbon fraction is injected into the third zone to inject at 1000 to 2000 atm. There is a method of polymerizing under pressure.

The epoxy group-containing olefin copolymer (D) in the second invention is a copolymer composed of an unsaturated epoxy compound and an olefin, or those and an ethylenically unsaturated compound. The composition ratio of the epoxy group-containing olefin copolymer is not particularly limited, but the unsaturated epoxy compound 0.05
It is preferably about 95% by weight.

The unsaturated epoxy compound is a compound having an unsaturated group capable of copolymerizing with an olefin and an ethylenically unsaturated compound, and an epoxy group in the molecule.

For example, the following general formulas (I), (II) and
Unsaturated glycidyl esters represented by (III),
Unsaturated glycidyl ethers, epoxy alkenes, P
-Unsaturated epoxy compounds such as glycidyl styrenes.

[0042]

[Chemical 1]

[0043]

[Chemical 2]

[0044]

[Chemical 3]

Specifically, glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, butenecarboxylic acid esters, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-P-glycidyl ether, 3,4-epoxybutene, 3,4-epoxy-3-methyl-1-butene, 3,
4-epoxy-1-pentene, 3,4-epoxy-3-
Methyl pentene, 5,6-epoxy-1-hexene, vinyl cyclohexene monoxide, P-glycidyl styrene and the like can be mentioned, and one or more kinds can be used. Glycidyl acrylate or glycidyl methacrylate is particularly preferable.

Examples of the olefin include ethylene, propylene, butene, pentene and the like, and one or more kinds can be used. Particularly, ethylene and propylene are preferable.

As the ethylenically unsaturated compound, vinyl esters containing saturated carboxylic acid components C _{2 to} C ₆ ,
Examples thereof include acrylic acid and methacrylic acid esters and maleic acid esters containing C _{1 to} C ₈ in a saturated alcohol component, vinyl halides and the like.

When the unsaturated epoxy compound and the olefin are copolymerized, these ethylenically unsaturated compounds are copolymerized in an amount of 50% by weight or less, particularly 0.1 to 45% by weight, based on the total amount of the compounds.

Epoxy group-containing olefin copolymer (D)
Is a copolymerization of an unsaturated epoxy compound with an olefin and optionally an ethylenically unsaturated compound, or a grafting of an unsaturated epoxy compound in the presence of an olefin polymer or a copolymer of an olefin and an ethylenically unsaturated compound. It is manufactured by copolymerization.

Epoxy group-containing olefin copolymer (D)
Preferred examples of ethylene-glycidyl methacrylate copolymer, ethylene-vinyl acetate-glycidyl methacrylate copolymer, ethylene-methyl methacrylate glycidyl methacrylate copolymer, and polyethylene, polypropylene, poly-1-butene, poly-4-
Examples thereof include copolymers obtained by graft reaction of glycidyl methacrylate in the presence of olefin polymers such as methyl-pentene-1, ethylene-propylene copolymers and ethylene-propylene-diene copolymers.

Epoxy group-containing olefin copolymer (D)
As a method for producing the above, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, a solution polymerization method or a polymerization method combining these methods is used.

The resin composition according to the first aspect of the present invention is
10 to 90% by weight of the above polycarbonate resin (A),
The total amount of the polyolefin graft polymer (C) and the terpolymer (D) is 0.1 to 100 parts by weight per 100 parts by weight of the composition containing 90 to 10% by weight of the rubber-reinforced styrene resin (B).
40 parts by weight of a resin composition, and a resin composition obtained by adding the polyolefin graft polymer (C) / terpolymer (D) in a weight ratio of 5/95 to 95/5. Is.

The resin composition in the second invention is a polyolefin composition based on 100 parts by weight of a composition comprising 10 to 90% by weight of the above-mentioned polycarbonate resin (A) and 90 to 10% by weight of a rubber-reinforced styrene resin (B). Graft polymer (C) and epoxy group-containing olefin copolymer (D)
0.1 to 40 parts by weight in total, and the weight ratio of the polyolefin graft polymer (C) / epoxy group-containing olefin copolymer (D) is 5/95 to 95.
It is a resin composition formulated so that it becomes / 5.

In the first and second inventions, when the polycarbonate resin (A) is less than 10% by weight (per total of (A) and (B)), the heat resistance and the impact resistance are poor,
If it exceeds 90% by weight, the impact resistance is inferior, which is not preferable. Particularly, the polycarbonate resin (A) is 20 to 80% by weight, and the rubber-reinforced styrene resin (B) is 80 to 20% by weight.

In the first invention, if the total amount of the polyolefin graft polymer (C) and the terpolymer (D) is less than 0.1 parts by weight per 100 parts by weight of the total of (A) and (B), the durability of the final composition is low. The chemical properties and paintability are not sufficiently improved, and if it exceeds 40 parts by weight, layer peeling tends to occur, which is not preferable. From the viewpoint of the balance of physical properties of the final composition, the total of the polyolefin graft polymer (C) and the terpolymer (D) is
It is preferable to add 0.1 to 30 parts by weight. If the ratio of the polyolefin graft polymer (C) to the terpolymer (D) is out of the above range, the balance between chemical resistance and paintability is poor, which is not preferable. The range of 10/90 to 90/10 is particularly preferable.

In the second invention, when the total of the polyolefin graft polymer (C) and the epoxy group-containing olefin copolymer (D) is less than 0.1 parts by weight per 100 parts by weight of the total of (A) and (B), the final The chemical resistance and paintability of the composition are not sufficiently improved, and when it exceeds 40 parts by weight, delamination tends to occur, which is not preferable. From the viewpoint of balance of physical properties of the final composition, the total amount of the polyolefin graft polymer (C) and the epoxy group-containing olefin copolymer (D) is 0.1 to
It is preferable to add 30 parts by weight. If the ratio of the polyolefin graft polymer (C) and the epoxy group-containing olefin copolymer (D) is outside the above range, the balance between chemical resistance and paintability is poor, which is not preferable. Especially 10 / 90-90
The range of / 10 is preferable.

Mixing order of polycarbonate resin (A), rubber-reinforced styrene resin (B), polyolefin graft polymer (C) and terpolymer (D) or epoxy group-containing olefin copolymer (D) Also, there is no limitation on the state thereof, and the components (A), (B), (C) and (D) are simultaneously mixed together in the form of pellets, beads, powder or the like, and remain after pre-mixing specific components. A method of mixing the components is illustrated. As a mixing method, a known method such as a Banbury mixer, a roll or an extruder can be adopted.

When mixed, if necessary, an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a lubricant, a dye, a pigment, a plasticizer, a flame retardant, a release agent, a glass fiber, a metal fiber,
Additives such as carbon fibers and metal flakes, reinforcing agents, and fillers can be added. Further, a thermoplastic resin such as polyamide, polyacetal, polyester, polyphenylene oxide, polymethylmethacrylate, or polyvinyl chloride can be appropriately blended.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The number of parts and the percentage are shown on a weight basis.

Various resins used in Examples and Comparative Examples are as follows.

[0061]

Example Polycarbonate resin (A) PC: Aromatic polycarbonate having a viscosity average molecular weight of 25,000 and composed of 2,2bis- (4-hydroxyphenyl) propane and phosgene

Rubber-reinforced styrene resin (B) ABS-1: polybutadiene rubber latex (particle size: 0.
45 μ, gel 83%) 30 parts (solid content), styrene 50 parts and acrylonitrile 20 parts are polymerized by a known emulsion polymerization method, and after salting out, dehydration and drying, a graft ratio of 73
%, A resin having a rubber content of 30% was obtained.

ABS-2: Polybutadiene rubber latex (particle size 0.35 μ, gel 90%) 50 parts (solid content), styrene 35 parts and acrylonitrile 15 parts were polymerized by a known emulsion polymerization method. On the other hand, 55 parts of styrene, 30 parts of acrylonitrile and 15 parts of N-phenylmaleimide
Parts were polymerized by a known emulsion polymerization method. Then, after mixing the obtained polymer latex, it was salted out, dehydrated and dried to obtain a rubber content of 3 including a graft polymer having a graft ratio of 55%.
0% resin was obtained.

Polyolefin graft polymer (C) C-1: polyethylene (high-pressure polyethylene, density 0.91)
8g / cm ³ , melt flow rate 7g / 10min, swelling degree 23
%) 100 parts, 30 parts of styrene and 15 parts of acrylonitrilo are polymerized according to a known suspension polymerization method, and dehydration,
It was dried to obtain a graft polymer.

C-2: Polypropylene (density 0.89 g / c
m ³ , melt flow rate 1.2 g / 10 minutes, swelling degree 27
%) 100 parts, 40 parts of styrene and 15 parts of acrylonitrile are polymerized by a known suspension polymerization method, and dehydration,
It was dried to obtain a graft polymer.

C-3: Polypropylene (density 0.89 g / c
m ³ , melt flow rate 1.2 g / 10 minutes, swelling degree 27
%) 100 parts, styrene 40 parts, acrylonitrile 15
Parts and 10 parts of glycidyl methacrylate were polymerized by a known suspension polymerization method, dehydrated and dried to obtain a graft polymer.

C-i: 100 parts of ethylene-propylene-diene rubber (iodine value of 24, swelling degree of 100% or more), 40 parts of styrene and 15 parts of acrylonitrile are polymerized by a known suspension polymerization method, dehydrated and dried. Then, a graft polymer was obtained.

Polyamide PA: 6-nylon

Tertiary Copolymer (D-1 to 3) D-1 to 2: Ethylene-maleic anhydride-ethyl acrylate terpolymer Copolymer using a cylindrical autoclave equipped with a blade type stirrer. In the presence of t-butyl 2-ethylperhexanoate dissolved in the fraction, 185
The monomer mixture was polymerized at 1600 atm at 60 ° C to give a terpolymer D-1 containing ethylene 60% by weight, maleic anhydride 4.5% by weight and ethyl acrylate 35.5% by weight, and ethylene 92%.
A terpolymer D-2 having a weight% of 1.5% by weight of maleic anhydride and 6.5% by weight of ethyl acrylate was obtained.

D-3: Ethylene-maleic anhydride-butyl acrylate terpolymer In the same manner as in D-1 and D-2, 70% by weight of ethylene, 4% by weight of maleic anhydride and 26% by weight of butyl acrylate were added. An original copolymer was obtained.

Polycarbonate resin, rubber-reinforced styrene resin, polyolefin graft polymer, terpolymer, polypropylene and polyamide were mixed in the composition shown in Table 1 and melt-mixed using a 40 mm twin-screw extruder. Granulated. The physical properties of the obtained various compositions were measured by the following methods, and the results are shown in Table 1.

Chemical resistance: An ASTMI type dumbbell (1/8 inch thick, 217 mm in total length) formed by injection is fixed on an arc jig having stoppers at both ends. (The surface strain of the test piece is set to 1% or 1.5% based on the curvature of the jig). Kerosene is applied to the surface of the test piece and left at 60 ° C. for 24 hours. After that, check for breakage of the test piece and for cracks on the surface of the test piece. ○ No crack △ Crack present × Break

Paintability: An ASTMI type dumbbell (1/8 inch thick, 217 mm in total length) formed by injection is fixed on an arc-shaped jig having stoppers at both ends. (The surface strain of the test piece is set to 1% or 1.5% based on the curvature of the jig). Paint on the surface of the test piece and leave at 80 ° C. for 30 minutes. Then, the presence or absence of cracks on the surface of the test piece is confirmed. 〇 No cracks △ Micro cracks × Broken

Delamination property: After the test piece shown in the figure is prepared, it is bent at the film gate portion to confirm the presence or absence of layer delamination at the molded product portion when the steel portion is removed. Impact resistance:
Notched Izod impact strength (ASTM D-256) 1
/ 4 inch, 23 ° C

[0075]

[Table 1]

Epoxy group-containing olefin copolymer (D-
1-2) An epoxy group-containing olefin copolymer having the following composition was produced by the bulk polymerization method according to the polymerization conditions of high-pressure polyethylene using an autoclave type polyethylene production apparatus. D-1 ethylene-glycidyl methacrylate-vinyl acetate copolymer (composition ratio 90-7-3) D-2 ethylene-glycidyl methacrylate copolymer (composition ratio 90-10)

Polycarbonate resin, rubber-reinforced styrene resin, polyolefin graft polymer and epoxy group-containing olefin copolymer were mixed in the composition shown in Table 2 and mixed and mixed using a 40 mm twin-screw extruder. Grained. The physical properties of the obtained various compositions were measured, and the results are shown in Table 2.

[0078]

[Table 2]

[0079]

INDUSTRIAL APPLICABILITY The present invention has a significantly higher impact resistance than a conventionally known composition comprising a polycarbonate resin and a rubber-reinforced styrenic resin, as well as a composition comprising a polyamide resin added to such a composition. The present invention provides a composition having excellent chemical resistance and coatability, and expands the use of the resin composition and provides a coated product having excellent adhesion and appearance without applying a primer treatment during coating. It is a thing.

[Brief description of drawings]

FIG. 1 is a plan view of a test piece used for evaluating the presence or absence of delamination.

FIG. 2 is a sectional view of a test piece.

[Explanation of symbols]   Gate   Film gate   Molding   Sprue Bending direction

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C08L 55/02 LMF 7142-4J

Claims (2)

[Claims] 1. Polycarbonate resin (A) 10-90
% By weight, 50 to 90% by weight of rubbery polymer (b-1) and aromatic vinyl monomer, vinyl cyanide monomer and /
Or unsaturated carboxylic acid alkyl ester monomer 50
-10 wt% and other copolymerizable vinyl-based monomer 0
Crystalline polyolefin (c-1) per 100 parts by weight of a composition of 90 to 10% by weight of a rubber-reinforced styrene resin (B) obtained by polymerizing a monomer (b-2) of 40 to 40% by weight. And a vinyl vinyl cyanide monomer and / or unsaturated carboxylic acid alkyl ester monomer 50 to 0 wt% (c-2). And a polyolefin graft polymer (C) obtained by polymerizing 50% to 98.5% by weight of an olefin and an unsaturated dicarboxylic acid anhydride 0.5.
0.1 to 40 parts by weight in total of a terpolymer (D) composed of 10 to 10% by weight and an unsaturated carboxylic acid alkyl ester-based monomer 1 to 40% by weight, and a polyolefin graft polymer ( A resin composition characterized in that the ratio of C) / terpolymer (D) is 5/95 to 95/5 by weight. 2. Polycarbonate resin (A) 10-90
% By weight, 50 to 90% by weight of rubbery polymer (b-1) and aromatic vinyl monomer, vinyl cyanide monomer and /
Or unsaturated carboxylic acid alkyl ester monomer 50
-10 wt% and other copolymerizable vinyl-based monomer 0
Crystalline polyolefin (c-1) per 100 parts by weight of a composition of 90 to 10% by weight of a rubber-reinforced styrene resin (B) obtained by polymerizing a monomer (b-2) of 40 to 40% by weight. And a vinyl vinyl cyanide monomer and / or unsaturated carboxylic acid alkyl ester monomer 50 to 0 wt% (c-2). 0.1 to 40 parts by weight in total of a polyolefin graft polymer (C) obtained by polymerizing the above and an epoxy group-containing olefin copolymer (D) consisting of an unsaturated epoxy compound and an olefin or an ethylene unsaturated compound thereof. And the ratio of the polyolefin graft polymer (C) / epoxy group-containing olefin copolymer (D) is 5/95 by weight.
A resin composition characterized by being mixed so as to be 95/5.