JP3389652B2 - Thermoplastic resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to heat resistance, heat shock resistance,
The present invention relates to a thermoplastic resin composition that is excellent in rigidity, surface appearance of molded articles and chemical resistance.

[0002]

BACKGROUND ART Styrene resins such as ABS resins are used in a wide range of fields because of their excellent impact resistance, rigidity and surface appearance of molded products, but they are not sufficiently resistant to chemicals and heat and are used in many applications. There was a limit. On the other hand, polyolefins are generally used in various fields because of their excellent heat resistance and chemical resistance, but have the drawbacks of poor rigidity, dimensional stability, and surface appearance of molded products. It is conceivable to mix the two and maintain the excellent properties of both to eliminate the drawbacks, but the compatibility was so poor that it could not be put to practical use.

[0003]

The present invention has been made against the background of the above-mentioned problems of the prior art.
It is an object of the present invention to provide a thermoplastic resin composition which is excellent in rigidity, surface appearance of a molded article and chemical resistance and can be used in a wide range of applications.

[0004]

The present invention comprises (A) 5 to 80 parts by weight of a rubbery polymer, an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound. Graft polymer obtained by graft-polymerizing 95 to 20 parts by weight of monomer 10 to 94% by weight (B) Modified polyolefin having carboxyl group and / or acid anhydride group 3 to 20% by weight (C) Polyolefin resin 0 to 80 2% to 50% by weight of (D) aromatic vinyl compound group 40 to 79% by mole, maleimide compound group 20 to 50% by mole and unsaturated dicarboxylic acid anhydride compound group 1 to 20% by mole % (E) Polyamide 1 to 60% by weight A thermoplastic resin composition comprising the above (A) + (B) + (C) + (D) + (E).

(A) Component (A) of claim 1 98 to 8
7% by weight (B) 2 to 13% by weight of modified polyolefin having a carboxyl group and / or an acid anhydride group With respect to 100 parts by weight of (A) + (B), 1 to 80 parts by weight of (C) polyolefin resin ( F) Aromatic vinyl compounds, unsaturated acids and / or acid anhydride group-containing unsaturated compounds and / or hydroxyl group-containing unsaturated compounds, or other vinyl monomers copolymerizable with these monomers as required. Styrenic polymer consisting of a polymer 1 to 60 parts by weight (E) The component (E) of claim 1 1 to 60 parts by weight The above (A) + (B) + (C) + (F) + (E) A thermoplastic resin composition comprising:

(A) Component (A) 10 to 9 of claim 1
Modified Polyolefin Having 4% by Weight (G) Hydroxyl Group 3
-20% by weight (C) Polyolefin resin 1-80% by weight (F) Component (F) of claim 2 1-60% by weight (E) Component (E) of claim 1 1-60% by weight A thermoplastic resin composition comprising: A) + (G) + (C) + (F) + (E).

(A) Component (A) 10 to 9 of claim 1
4% by weight (H) Modified polyolefin 3 to 20 having at least one group selected from epoxy group, carboxyl group, acid anhydride group, hydroxyl group, amino group and oxazoline group
% By weight (C) Polyolefin resin 1-80% by weight (F) Component (F) of claim 2 1-60% by weight (I) Thermoplastic polyester 1-60% by weight Above (A) + (H) + ( The present invention provides a thermoplastic resin composition comprising C) + (F) + (I).

Examples of the rubber-like polymer used in the component (A) of the present invention include polybutadiene, polyisoprene,
Butyl rubber, styrene-butadiene copolymer (styrene content is preferably 5 to 60% by weight), styrene-isoprene copolymer, acrylonitrile-butadiene copolymer,
Ethylene-α-olefin copolymer, ethylene-α-olefin-polyene copolymer, silicone rubber, acrylic rubber, butadiene- (meth) acrylic acid ester copolymer, polyisoprene, styrene-butadiene block copolymer, styrene -Isoprene block copolymers, hydrogenated styrene-butadiene block copolymers, hydrogenated butadiene-based polymers, ethylene-based ionomers and the like. Also, a styrene-butadiene block copolymer,
The styrene-isoprene block copolymer includes AB type,
Those having an ABA type, a taper type, a radial teleblock type structure and the like are included. Further, the hydrogenated butadiene-based polymer is a hydride of the block copolymer of the styrene block and the styrene-butadiene random copolymer in addition to the hydride of the block copolymer, and the content of 1,2-vinyl bond in polybutadiene. Of 20% by weight or less and a hydride of a polymer comprising a polybutadiene block having a 1,2-vinyl bond content of more than 20% by weight.

In 100 parts by weight of the component (A), the above rubbery polymer is 5 to 80 parts by weight, preferably 10 to 70 parts by weight. If it is less than 5 parts by weight, the impact resistance is poor and exceeds 80 parts by weight. And rigidity and surface appearance of molded products are poor.

As the aromatic vinyl compound, styrene,
t-butylstyrene, α-methylstyrene, p-methylstyrene, civinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-P-aminoethylstyrene,
Examples include N, N-diethyl-P-aminomethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, ethylstyrene, vinylnaphthalene, and the like, particularly styrene and α-methyl. Styrene is preferred.

Other vinyl monomers which can be copolymerized with the aromatic vinyl compound used here include vinyl cyanide compounds, (meth) acrylic acid alkyl esters, maleimide compounds and the like, and these are one kind. Or it is used in two or more kinds. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, which may be used alone or in combination of two or more. Examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amino acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate and benzyl acrylate. Ethyl acrylate;
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amino methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate,
There are methacrylic acid esters such as benzyl methacrylate, and these are used alone or in combination of two or more.
Examples of the maleimide compound include maleimide, N-methylmaleimide, N-butylmaleimide, N- (P-methylphenyl) maleimide, N-phenylmaleimide, N-
One or two or more maleimide compounds of α, β-unsaturated dicarboxylic acid such as cyclohexylmaleimide are used.

The amount of the above-mentioned monomer or monomer mixture used is 95 to 20 parts by weight, preferably 90 to 30 parts by weight, based on 100 parts by weight of the component (A). When the amount is less than 20 parts by weight, the rigidity and the surface appearance of the molded product are inferior.

The component (A) of the present invention is a graft polymer obtained by graft-polymerizing the vinyl monomer in the presence of the rubbery polymer, and further in the absence of the rubbery polymer, the vinyl monomer is used. Also included are mixtures of polymers with (co) polymerized monomers. The component (A) of the present invention can be produced by known polymerization methods such as emulsion polymerization, solution polymerization, bulk polymerization, emulsion-bulk polymerization, emulsion-solution polymerization and suspension polymerization.

The modified polyolefin as the component (B) of the present invention is an olefin polymer modified with a carboxyl group and / or an acid anhydride group, and examples of the olefin polymer include ethylene, propylene and butene. -1,3-methylbutene-1,3-methylpentene-
Examples include α-olefin homopolymers such as 1,4-methylpentene-1 and copolymers thereof.

As the method for producing the component (B), for example,
After mixing an olefin polymer, a carboxyl group- or acid anhydride group-containing unsaturated compound and a small amount of an organic peroxide, the mixture is fed to a single-screw or twin-screw extruder,
Method of melt-kneading at a temperature of ° C., a method of dissolving an olefin polymer in a solvent, and adding the unsaturated compound and an organic peroxide to this to carry out a graft reaction in a solution state,
There are a method of directly oxidizing the polyolefin, a method of copolymerizing the unsaturated compound at the time of producing an olefin polymer, and the like, and any one obtained by any method can be used as the component (B) of the present invention. Examples of the acid anhydride group-containing unsaturated compound used here include maleic anhydride, itaconic anhydride, and citraconic anhydride. Examples of unsaturated acids include acrylic acid, methacrylic acid, itaconic acid and maleic acid. These are used alone or in combination of two or more.

The polyolefin resin as the component (C) is
Examples thereof include homopolymers of the above α-olefins and copolymers thereof. As a typical example, high density, medium density, low density polyethylene, linear low density polyethylene, ultra high molecular weight polyethylene, ethylene-vinyl acetate copolymer,
Polyethylene such as ethylene-ethyl acrylate copolymer, propylene homopolymer, propylene-ethylene block copolymer or random copolymer, polypropylene such as propylene-ethylene-gen compound copolymer,
Polybutene-1, poly-4-methylpentene-1 and the like can be mentioned, but among these, crystalline polyethylene and crystalline polypropylene are preferable, and crystalline polypropylene is particularly preferable.

The crystalline polypropylene is, for example, a crystalline isotactic propylene homopolymer, or a copolymerized portion composed of an ethylene-propylene random copolymer having a low ethylene unit content or a propylene homopolymer. A substantially crystalline propylene and ethylene commercially available as a so-called propylene block copolymer, which is composed of a homopolymerization portion and a copolymerization portion composed of an ethylene-propylene random copolymer having a relatively large content of ethylene units. And a block copolymer or a homopolymerization portion or copolymerization portion of the block copolymer, which is a substantially crystalline propylene-ethylene-containing copolymer of α-olefin such as butene-1
Preferable examples include α-olefin copolymers. The polyolefin resin used here preferably has a melt index (MI) in the range of 5 to 60 g / 10 minutes.

As the aromatic vinyl compound, maleimide compound and unsaturated dicarboxylic acid anhydride compound used as the component (D), all of the above-mentioned aromatic vinyl compounds, maleimide compounds and acid anhydride group-containing unsaturated compounds can be used. used. As a method for producing the present maleimide-based copolymer, a method of radically copolymerizing the above-mentioned monomer, and as another method, an aromatic vinyl compound, a copolymer obtained by copolymerizing an unsaturated dicarboxylic acid anhydride There is a method of reacting the combined product with ammonia or a primary amine to imidize the acid anhydride residue. The imidization reaction of a polymer substance having an acid anhydride residue in the polymer chain and an amine compound is known,
For example, Japanese Examined Patent Publication No. 61-26936 or 62-8.
According to the method disclosed in Japanese Patent No. 456, it is possible to react a polymer substance with an amine compound to produce a maleimide copolymer having an intended imide group.

Examples of primary amines used in the imide reaction include methylamine, ethylamine, propylamine,
Butylamine, hexylamine, decylamine, aniline, toluidine, naphthylamine, chlorophenylamine, dichlorophenylamine, bromophenylamine,
Examples include dibromophenylamine. The component (D) of the present invention may be copolymerized with the above-mentioned (meth) acrylic acid alkyl ester and vinyl cyanide compound. (D)
The amount of unsaturated dicarboxylic acid anhydride compound in the component is 1 to 20.
It is mol%, preferably 1 to 15 mol%, more preferably 2 to 10 mol%. If it deviates from this range, the impact resistance becomes poor.

The polyamide in the component (E) is usually a line represented by the following formula: H ₂ N- (CH ₂ ) _x -NH ₂ (wherein X is an integer of 4 to 12). and Jo diamine, the following _{formula: HO 2 C- (CH 2)} ( wherein, y is an integer from 2 to 12.) _y -CO ₂ H those produced by the condensation of linear carboxylic acids represented by Alternatively, those produced by ring-opening polymerization of lactam can be used.

Preferred examples of these polyamides include nylon 6,6, nylon 6,9 and nylon 6,1.
0, nylon 6,12, nylon 6, nylon 12, nylon 11, nylon 4,6 and the like. Also, nylon 6 / 6,6, nylon 6 / 6,10, nylon 6/1
2, nylon 6/6, 12, nylon 6/6, 6/6,
Copolyamides such as 10, nylon 6/6, 6/12 are also used. Furthermore, nylon 6/6, T (T;
(Terephthalic acid component), semi-aromatic polyamides obtained from aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid and metaxylenediamine, or alicyclic diamines, polyamides obtained from metaxylenediamine and the above linear carboxylic acid , Polyesteramide, etc. can also be used. The polyamide may be used alone or in combination of two or more. Further, a polyamide elastomer which is a block copolymer of polyethylene glycol, polypropylene glycol, polytetramethylene glycol or the like and the above polyamide can also be used.

As the aromatic vinyl compound, unsaturated acid and acid anhydride group-containing unsaturated compound used as the component (F), all of the above-mentioned ones are used. As the hydroxyl group-containing unsaturated compound, hydroxystyrene, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3- Hydroxy-2-methyl-1
-Propene, 2-hydroxyethyl acrylate, 2-
For example, hydroxyethyl methacrylate. Further, the above-mentioned (meth) acrylic acid alkyl ester, vinyl cyanide compound, maleimide compound and the like can be copolymerized. The amount of the unsaturated acid, the acid anhydride group-containing unsaturated compound, and the hydroxyl group-containing unsaturated compound in the component (F) of the present invention is in the range of 0.5 to 20% by weight to achieve the object of the present invention. It is preferable to do so.

The modified polyolefin having a hydroxyl group as the component (G) can be obtained by the same method as that for the component (B). As the hydroxyl group-containing unsaturated compound used here, all of those mentioned above are used. Further, the above-mentioned (B) component carboxyl group or acid anhydride group is esterified with a polyol component to form a hydroxyl group, and a modified polyolefin having an acid anhydride group and a general formula: NH ₂ —R—OH ( In the formula, those obtained by reacting R with a hydrocarbon having 2 to 30 carbon atoms) can also be used as the component (G) of the present invention.

The component (H) is a modified polyolefin having at least one group selected from an epoxy group, a carboxyl group, an acid anhydride group, a hydroxyl group, an amino group and an oxazoline group. The component (H) is the component (B) described above.
The component and the component (G) can be produced by the same method. As the unsaturated acid, the acid anhydride group-containing unsaturated compound, and the hydroxyl group-containing unsaturated compound used here, all of those described above are used. Examples of the epoxy group-containing unsaturated compound include glycidyl methacrylate and allyl glycidyl ether, and examples of the amino group-containing unsaturated compound include acrylic amine, aminomethyl methacrylate, aminoethyl methacrylate, aminopropyl methacrylate, aminostyrene, and acrylamide. , Methacrylamide, etc. Furthermore, examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline.

Examples of the thermoplastic polyester (I) include those obtained by condensing an aromatic dicarboxylic acid or its ester or ester-forming derivative with a diol by a known method. Examples of the aromatic dicarboxylic acid include naphthalene-
Naphthalene dicarboxylic acid such as 2,6-dicarboxylic acid,
Examples thereof include terephthalic acid, isophthalic acid, p-hydroxybenzoic acid, adipic acid, sebacic acid and the like, and ester-forming derivatives thereof can also be used as the thermoplastic polyester. Examples of the diol include polymethylene glycol having 2 to 6 carbon atoms such as ethylene glycol, 1,4-butanediol, and 1,6-hexanediol, 1,4-cyclohexanediol, bisphenol A and these. And ester-forming derivatives thereof.

Specific examples of the thermoplastic polyester thus obtained include polyethylene terephthalate (PET), polybutylene terephthalate (PBT),
Examples thereof include bisphenol A isophthalate, and among them, PBT is preferable. Further, a polyamide elastomer which is a block copolymer of the above polyester with polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or the like can also be used.

The compounding ratio of each component in the thermoplastic resin composition of claim 1 is shown below. The amount of the component (A) used in claim 1 is 10 to 60% by weight. The amount used is 10
When it is less than 60 % by weight, impact resistance, rigidity and surface appearance of the molded product are poor, and when it exceeds 60 % by weight, heat resistance and chemical resistance are poor.

The amount of the component (B) used is 3 to 20% by weight, preferably 3 to 15% by weight, more preferably 5 to 15% by weight. If it is less than 3% by weight, the impact resistance and the surface appearance of the molded product are poor, and if it exceeds 20% by weight, the surface appearance of the molded product is poor.

The amount of the component (C) polyolefin resin used is 5 to 80% by weight, preferably 10 to 50% by weight, and particularly preferably 10 to 40% by weight. If it exceeds 80% by weight, impact resistance, rigidity and surface appearance of the molded product are poor.

The amount of component (D) used in the present invention is 2 to 50% by weight, preferably 2 to 30% by weight, more preferably 5%.
-20% by weight, particularly preferably 5-15% by weight. Two
If it is less than 10% by weight, the impact resistance and the surface appearance of the molded product will be poor.
If it exceeds 50% by weight, impact resistance is poor.

The amount of the component (E) used is 2 to 30 % by weight, particularly preferably 5 to 20% by weight. If it is less than 2 % by weight, the impact resistance and the surface appearance of the molded product are poor, and if it exceeds 30 % by weight, the physical properties of the resin composition are deteriorated due to the influence of the deterioration of the physical properties during water absorption, which is not preferable.

The composition ratio of each component of the thermoplastic resin composition of claim 2 is shown below. The mixing ratio of the component (A) and the component (B) is (A) component / (B) component = 98 to 87/2 to 1
3% by weight, preferably 97 to 90/3 to 10% by weight. If the amount of the component (B) used is less than 2% by weight, the impact resistance and the surface appearance of the molded product are poor, and if it exceeds 13% by weight, the surface appearance of the molded product is poor.

The amount of component (C) used is (A) + (B) 1
1 to 80 parts by weight, preferably 5 to 8 parts by weight
The amount is 0 parts by weight, more preferably 10 to 80 parts by weight.
If the amount used is less than 1 part by weight, the chemical resistance is poor, and if it exceeds 80 parts by weight, the impact resistance, the rigidity and the surface appearance of the molded product are poor.

The amount of component (F) used is (A) + (B) 1
1 to 60 parts by weight, preferably 3 to 5 parts by weight with respect to 00 parts by weight
The amount is 0 parts by weight, more preferably 5 to 30 parts by weight. 1
If the amount is less than 60 parts by weight, the impact resistance and the surface appearance of the molded product are inferior.
If it exceeds the weight part, the impact resistance becomes poor.

The amount of component (E) used is (A) + (B) 1
It is 2 to 30 parts by weight with respect to 00 parts by weight . If it is less than 2 parts by weight, the impact resistance and the surface appearance of the molded product are poor, and if it exceeds 30 parts by weight, the physical properties of the resin composition are deteriorated due to the influence of the deterioration of the physical properties during water absorption, which is not preferable.

The composition ratio of each component of the thermoplastic resin composition of claim 3 is shown below. The amount of component (A) used is 10 to 9
It is 4% by weight, preferably 20 to 80% by weight, more preferably 30 to 70% by weight, and particularly preferably 40 to 60% by weight. If the amount used is less than 10% by weight, impact resistance,
The rigidity and surface appearance of the molded product are inferior, and when it exceeds 94% by weight, heat resistance and chemical resistance are inferior.

The amount of the component (G) used is 3 to 20% by weight, preferably 3 to 15% by weight, more preferably 5 to 15 parts by weight. If it is less than 3% by weight, the impact resistance and the surface appearance of the molded product are inferior, and if it exceeds 20% by weight, the surface appearance of the molded product is inferior.

The amount of component (C) used is 1 to 80% by weight, preferably 5 to 60% by weight, more preferably 10 to 50%.
%, Particularly preferably 10 to 40% by weight. If it is less than 1% by weight, there is no effect of improving the chemical resistance, and if it exceeds 80% by weight, impact resistance, rigidity and surface appearance of the green molded product are poor.

The amount of the component (F) used is 1 to 60% by weight, preferably 2 to 30% by weight, more preferably 5 to 20% by weight, and particularly preferably 5 to 15% by weight. If it is less than 1% by weight, the impact resistance and the surface appearance of the molded article are poor, and if it exceeds 60% by weight, the impact resistance is poor.

The amount of component (E) used is 1 to 60 parts by weight, preferably 2 to 50 parts by weight, more preferably 2 to 30% by weight, and particularly preferably 5 to 20% by weight. If it is less than 1% by weight, the impact resistance and the surface appearance of the molded article are poor, and if it exceeds 60% by weight, the physical properties of the resin composition are deteriorated due to the influence of the deterioration of the physical properties when absorbing water, which is not preferable.

The composition ratio of each component of the thermoplastic resin composition of claim 4 is shown below. The amount of component (A) used is 10 to 9
It is 4% by weight, preferably 20 to 80% by weight, more preferably 30 to 70% by weight, and particularly preferably 40 to 60% by weight. If the amount used is less than 10% by weight, impact resistance,
The rigidity and surface appearance of the molded product are inferior, and when it exceeds 94% by weight, heat resistance and chemical resistance are inferior.

The amount of the component (H) used is 3 to 20% by weight, preferably 3 to 15% by weight, more preferably 5 to 15% by weight. If it is less than 3% by weight, the impact resistance and the surface appearance of the molded product are poor, and if it exceeds 20% by weight, the surface appearance of the molded product is poor.

The amount of the component (C) used is 1 to 80% by weight, preferably 5 to 60% by weight, more preferably 10 to 50%.
%, Particularly preferably 10 to 40% by weight. If it is less than 1% by weight, there is no effect of improving the chemical resistance, and if it exceeds 80% by weight, impact resistance, rigidity and surface appearance of the green molded product are poor.

The amount of component (F) used is 1 to 60% by weight, preferably 2 to 30% by weight, more preferably 5 to 20% by weight, and particularly preferably 5 to 15% by weight. If it is less than 1% by weight, the impact resistance and the surface appearance of the molded article are poor, and if it exceeds 60% by weight, the impact resistance is poor.

The amount of component (I) used is 1 to 60 parts by weight, preferably 2 to 50 parts by weight, more preferably 2 to 30% by weight, and particularly preferably 5 to 20% by weight. If it is less than 1% by weight, the impact resistance and the surface appearance of the molded product are poor, and if it exceeds 60% by weight, the impact resistance is deteriorated.

The thermoplastic resin composition of the present invention includes glass fiber, carbon fiber, metal fiber, metal flake, glass beads, wollastonite, rock filler, calcium carbonate, talc, mica, glass flake, milled fiber, kaolin. Fillers such as barium sulfate, graphite, molybdenum disulfide, magnesium oxide, zinc oxide whiskers, and potassium titanate whiskers can be used alone or in combination. Among these fillers, the shape of glass fiber or carbon fiber is preferably one having a fiber diameter of 6 to 60 μm and a fiber length of μm or more. These fillers are added to 100 parts by weight of the composition of the present invention.
Usually, it is used in the range of 5 to 150 parts by weight.

In the composition of the present invention, known additives such as flame retardants, coupling agents, light stabilizers, antioxidants, plasticizers, colorants, lubricants, antistatic agents, silicone oils, foaming agents, etc. Can be blended. Further, by adding an antibacterial agent such as silver or a silver compound or a commercially available antifungal agent to the composition of the present invention, excellent antibacterial and antifungal properties can be imparted. The amount of such antibacterial agents and antifungal agents to be compounded is 0.01 to 30% by weight, preferably 0.05 to 2
It is 0% by weight. Furthermore, in the composition of the present invention, other polymers such as polysulfone, polyether sulfone, polyphenylene sulfide, liquid crystal polymer, fluororesin, styrene-vinyl acetate copolymer, polycarbonate, polyphenylene ether are added depending on the required performance. And the like can be appropriately blended.

The thermoplastic resin composition of the present invention can be obtained by kneading the components using various extruders, Banbury mixers, kneaders, rolls and the like. A preferred manufacturing method is a method using a twin-screw extruder. Moreover, when kneading each component, you may knead all components collectively, and you may knead them by a multistage addition system. The flame-retardant resin composition of the present invention thus obtained is molded into various molded articles by injection molding, sheet extrusion, vacuum molding, profile extrusion molding, blow molding, foam molding, injection press molding, gas injection molding, etc. can do. The various molded products obtained by the above-mentioned molding method utilize OA.
It can be used for various parts, housings, chassis, etc. in the fields of home appliances, electric / electronics, general goods, sanitary, automobiles, etc.

[0049]

EXAMPLES The present invention will be further described below with reference to examples. In the examples, parts and% are based on weight unless otherwise specified. Further, various evaluations in the examples are values measured as follows.

Vicat softening temperature was measured according to heat resistance ASTM D-1525. Impact resistance Izod impact strength was measured according to ASTM D256. The flexural modulus in accordance with rigidity ASTM D790 were measured. Surface appearance of molded product The surface of the flat plate injection molded product was visually evaluated according to the following evaluation criteria. ◯: Smooth and good appearance. Δ: Flow mark is visible or smoothness is slightly inferior. X: The surface has large irregularities and the appearance is poor. Chemical resistance The flat plate injection molded product was immersed in gasoline for 48 hours, and the surface of the test after taking it out was visually evaluated according to the following evaluation criteria.

[0051]Rubbery polymer (a) -1, (a) -2,
(A) -3 Rubber-like polymerization used in the (A) graft polymer of the present invention
The body shown in Table 1 was used.

[0052]

[Table 1]

Of graft polymers (A) -1 to (A) -4
Preparation In the presence of the rubbery polymers (a) -1 to (a) -3,
Resins obtained by polymerizing only the monomer component were obtained without the presence of a graft polymer obtained by graft-polymerizing various monomers and a rubbery polymer. The compositions of these polymers are shown in Table 2. Incidentally, (A) -1 is an emulsion polymerization, and (A) -2 to
(A) -4 was obtained by solution polymerization.

[0054]

[Table 2]

[0055]Modified polyolefin (B), (G),
(H)   Modified Polyolefin (B); Maleic Anhydride Modified Polyolefin
As propylene, you can use Sanyo Kasei Co., Ltd.
Cous^R1001 was used.   Modified polyolefin (G); Hydroxyl group-modified polyolefin
As propylene, you can use Sanyo Kasei Co., Ltd.
Cous^R1201 was used.   Modified polyolefin (H); manufactured by Mitsubishi Petrochemical Co., Ltd.
Lipropylene BC3 with 3 parts of glycidyl methacrylate
Dry blend a small amount of peroxide with a Henschel mixer
Melted and kneaded with an extruder with a vent, and then epoxy group-modified poly
Olefin (H) was obtained.

Polyolefin resin (C) Polypropylene J5100A manufactured by Toso Co., Ltd. was used.

Maleimide polymer (D) 100 parts of styrene was charged into an autoclave equipped with a stirrer, the system was replaced with nitrogen gas, and then heated to a temperature of 80 ° C. A solution prepared by dissolving 67 parts of maleic anhydride and 0.2 part of benzoyl peroxide in 300 parts of methyl ethyl ketone was added thereto over 8 hours. After addition, the temperature is 8
The mixture was stirred at 0 ° C for 4 hours to obtain a styrene-maleic anhydride copolymer. To this, 1.2 parts of triethylamine and 52 parts of aniline were added and reacted at 130 ° C. for 7 hours. The reaction solution was cooled to room temperature, precipitated in methanol, filtered, and dried to obtain a maleimide-based copolymer (D). ¹³ C
The composition of the polymer (D) quantified by NMR was as follows. Styrene: 59.5 mol% Phenylmaleimide: 33.0 mol% Maleic anhydride: 7.5 mol%

Polyamide (E) Nylon 6 Capron XA1767 manufactured by Allied Company was used.

Styrenic polymer (F) A polymer (F) consisting of styrene / acrylonitrile / 2-hydroxyethyl acrylate = 67.5 / 22.5 / 10% was obtained by emulsion polymerization.

Thermoplastic Polyester (I) Polybutylene terephthalate having an intrinsic viscosity of 1.0 (0-chlorophenol solvent, measured at 25 ° C.) obtained by condensation polymerization of dimethyl terephthalate and 1,4-butanediol was used.

The above-mentioned various polymers were mixed in the mixing ratio shown in Table 3, melt-kneaded at a barrel setting temperature of 220 ° C. by a twin-screw extruder, and pelletized. After thoroughly drying the pellets,
Using an injection molding machine, a test piece was prepared at a cylinder temperature of 240 ° C. and a mold temperature of 50 ° C., and evaluated by the above evaluation method.
The evaluation results are shown in Table 3.

[0062]

[Table 3]

Comparative Example 1 is an example in which the amount of the component (B) used in claim 1 is out of the scope of the invention, and the impact resistance and the surface appearance of the molded product are poor. Comparative Example 2 is an example in which the amount of the component (E) used in claim 1 is small outside the scope of the invention,
Poor impact resistance and surface appearance of molded products. Comparative Example 3 is an example in which the amount of the component (B) used in claim 2 is outside the scope of the invention, and the impact resistance and the surface appearance of the molded product are poor. Comparative Example 4 is an example in which the amount of the component (G) used in claim 3 is small outside the scope of the invention, and the impact resistance and the surface appearance of the molded product are poor. In Comparative Example 5, the amount of the component (C) used in claim 3 was small outside the scope of the invention, and the heat resistance and chemical resistance were poor. In Comparative Example 6, the amount of the component (H) used in claim 4 is small outside the scope of the invention, and the impact resistance and the surface appearance of the molded product are poor. In Comparative Example 7, the amount of the component (A) used in claim 4 is outside the scope of the invention, and the impact resistance, rigidity and surface appearance of the molded product are poor.

[0064]

INDUSTRIAL APPLICABILITY The thermoplastic resin composition of the present invention has a wide range of applications excellent in heat resistance, impact resistance, rigidity, surface appearance of molded articles and chemical resistance, for example, various interior and exterior parts of automobiles, OA. -It can be used for various parts, housings, chassis, etc. in the fields of home appliances, electric / electronics, miscellaneous goods, sanitary, etc.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kenki Furuyama 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Japan Synthetic Rubber Co., Ltd. (56) Reference JP-A-5-239277 (JP, A) JP-A 2-191664 (JP, A) JP-A-61-171751 (JP, A) JP-A-1-203446 (JP, A) JP-A-6-57049 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 51/04 C08L 23/00 C08L 23/26 C08L 35/00 C08L 77/00

Claims (4)

(57) [Claims] 1. A rubbery polymer (A) in an amount of 5 to 80 parts by weight,
Aromatic vinyl compound or other vinyl monomer copolymerizable with aromatic vinyl compound and aromatic vinyl compound 95
Graft polymer 1 obtained by graft polymerizing 20 to 20 parts by weight
0 to 60 % by weight (B) 3 to 20% by weight of modified polyolefin having a carboxyl group and / or an acid anhydride group (C) 5 to 80% by weight of polyolefin resin (D) 40 to 79% by mole of aromatic vinyl compound group, Maleimide-based copolymer consisting of 20 to 50 mol% of maleimide compound group and 1 to 20 mol% of unsaturated dicarboxylic acid anhydride compound group 2 to 50% by weight (E) Polyamide 2 to 30 % by weight (A) + ( A thermoplastic resin composition comprising B) + (C) + (D) + (E). 2. (A) Component (A) 98 to 8 according to claim 1.
7% by weight (B) 2 to 13% by weight of modified polyolefin having a carboxyl group and / or an acid anhydride group With respect to 100 parts by weight of the above (A) + (B), (C) 1 to 80 parts by weight of a polyolefin resin ( F) Aromatic vinyl compounds, unsaturated acids and / or acid anhydride group-containing unsaturated compounds and / or hydroxyl group-containing unsaturated compounds, or other vinyl monomers copolymerizable with these monomers as required. 1 to 60 parts by weight of a styrenic polymer (E) consisting of a monomer 2 to 30 parts by weight of the component (E) of the above item (A) + (B) + (C) + (F) + (E) A thermoplastic resin composition comprising: 3. (A) Component (A) according to claim 1
94% by weight (G) Modified polyolefin having hydroxyl group 3
˜20% by weight (C) Polyolefin resin 1 to 80% by weight (F) 1 to 60% by weight of component (F) of claim 2 (E) 1 to 60% by weight of component (E) of claim 1 A thermoplastic resin composition comprising: A) + (G) + (C) + (F) + (E). 4. (A) Components 10 to 9 of (A) according to claim 1.
4% by weight (H) Modified polyolefin 3 to 20 having at least one group selected from epoxy group, carboxyl group, acid anhydride group, hydroxyl group, amino group and oxazoline group
% Weight (C) Polyolefin resin 1 to 80% by weight (F) Component (F) 1 to 60% by weight of claim 2 (I) Thermoplastic polyester 1 to 60% by weight (A) + (H) + ( A thermoplastic resin composition comprising C) + (F) + (I).