JPH0753816A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the composition composed of a specified ratio of a specific thermoplastic resin, a specified rubber-modified thermoplastic resin, a polyamide, etc., and an ethylene-alpha-olefin-based copolymer, etc., excellent in heat resistance, impact resistance and moldability and useful for, e.g. interior and exterior decoration in the field of car vehicle. CONSTITUTION:This composition is composed of (A) 10-88.9wt.% thermoplastic resins made up by 20-90wt.% aromatic vinyl compound, 9.5-60wt.% unsaturated dicarboxylic acid imide compound and 0.5-20wt.% unsaturated carboxylic acid (anhydride), (B) 10-88.9wt.% polyamide and/or thermoplastic polyester, (C) l-50wt.% rubber-modified thermoplastic resin synthesized by conducting graft polymerization of an aromatic vinyl compound or a mixture of an aromatic vinyl compound and another vinyl compound copolymerizable therewith in the presence of an ethylene-alpha-olefin-based copolymer and/or a hydrogenated conjugated diene-based polymer and (D) 0.1-20wt.% ethylene-alpha-olefin-based copolymer and/or hydrogenated conjugated diene-based polymer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition having excellent heat resistance, impact resistance and moldability.

[0002]

2. Description of the Related Art A copolymer composed of styrene and an unsaturated dicarboxylic acid imide compound such as N-phenylmaleimide has high heat resistance, and is expected to be applied to various parts in the field used at high temperatures. However, such polymers have the drawback of poor moldability and impact resistance. A method of mixing with a polyamide has been proposed as a method of improving molding processability, and a method of further blending an ethylene-propylene copolymer modified with maleic anhydride or the like has been proposed as a method of improving impact resistance. However, such a composition does not have a sufficient balance of impact resistance, heat resistance and molding processability, and there are restrictions depending on the intended use.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and an object thereof is to provide a thermoplastic resin composition having excellent heat resistance, moldability and moldability. And

[0004]

The present invention provides a thermoplastic resin composition according to claims 1, 2 and 3 below. [Claim 1] 20 to 90% by weight of (A) aromatic vinyl compound, 9.5 to 60% by weight of unsaturated dicarboxylic acid imide compound and 0.5 to 20 of unsaturated carboxylic acid and / or unsaturated dicarboxylic acid anhydride 10 to 88.9% by weight of a thermoplastic resin, (B) a polyamide and / or a thermoplastic polyester of 10 to 88.9% by weight, (C) an ethylene-α-olefin copolymer and / or a conjugated diene system. 1 to 50 parts by weight of a rubber-modified thermoplastic resin obtained by graft-polymerizing an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound in the presence of a hydride of the polymer. %, (D) 0.1 to 20% by weight of hydride of ethylene-α-olefin copolymer and / or conjugated diene polymer, the above (A) + (B) + (C + (D) a thermoplastic resin composition characterized in that it consists of components.

[Claim 2] (A) 10 to 88.9% by weight of the component (A) of claim 1, (B) 10 to 88.9% by weight of the component (B) of claim 1, and (E) no component. 0.1 to 30% by weight of modified polyolefin having at least one functional group selected from saturated carboxylic acid, unsaturated dicarboxylic acid anhydride, and epoxy group-containing unsaturated compound, (F) aromatic in the presence of rubbery polymer Rubber-modified thermoplastic resin obtained by graft polymerization of an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound
79.9% by weight, 0 to 20% by weight of (G) olefin polymer, and the above-mentioned (A) + (B) + (E) + (F) + (G), which is a thermoplastic resin composition. object.

[Claim 3] (A) 10 to 88.9% by weight of the component (A) of claim 1, (B) 10 to 88.9% by weight of the component (B) of claim 1, and (E) Item (E) component 0.1 to 30.0 wt%, (G) Claim 2 (G) component 1 to 25 wt%, the above (A) + (B) + (E) + (G)
A thermoplastic resin composition comprising:

The present invention will be described in detail below. Description of Claim 1 As the aromatic vinyl compound used in the component (A) of the present invention, styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene. , P-
Examples thereof include t-butyl styrene, ethyl styrene, vinyl naphthalene, o-methyl styrene, and dimethyl styrene, and these can be used alone or in combination of two or more kinds. Among these aromatic vinyl compounds, styrene is preferably used. The amount of the aromatic vinyl compound used in the component (A) of the present invention is 20
-90% by weight, preferably 30-80% by weight, more preferably 35-80% by weight, particularly preferably 40-70%.
% By weight. If the amount used is less than 20% by weight, impact resistance is poor, and if it exceeds 90% by weight, heat resistance is poor.

Examples of the unsaturated dicarboxylic acid imide compound include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N-methylphenylmaleimide, N-hydroxyphenylmaleimide and N-methylphenylmaleimide.
There are -methoxyphenylmaleimide, N-chlorophenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-cyclohexylmaleimide, N-isopropylmaleimide and the like, among which N-phenylmaleimide is particularly preferable. These unsaturated dicarboxylic acid imide compounds can be used alone or in combination of two or more. (A) of the present invention
The amount of the unsaturated dicarboxylic acid imide compound used in the component is
It is 9.5 to 60% by weight, preferably 20 to 60% by weight, and more preferably 30 to 55% by weight. If the amount used is less than 9.5% by weight, heat resistance is poor, and if it exceeds 60% by weight, impact resistance is poor.

As the unsaturated carboxylic acid, acrylic acid,
There are α, β-unsaturated carboxylic acids such as methacrylic acid, maleic acid, fumaric acid and itaconic acid, which can be used alone or in combination of two or more. Examples of unsaturated dicarboxylic acid anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, and aconitic anhydride, which may be used alone or in combination of two or more. Particularly preferred among unsaturated carboxylic acids and / or unsaturated dicarboxylic acid anhydrides is maleic anhydride. Unsaturated carboxylic acid in component (A) of the present invention and /
Alternatively, the amount of the unsaturated dicarboxylic acid anhydride used is 0.5 to
20% by weight, preferably 1.0 to 15% by weight, more preferably 1.5 to 10% by weight, particularly preferably 3 to 8% by weight. If the amount used is less than 0.5% by weight, impact resistance is poor, and if it exceeds 20% by weight, moldability is poor.

The component (A) of the present invention may be further copolymerized with another copolymerizable vinyl monomer. Other vinyl monomers used here include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amino acrylate, hexyl acrylate, octyl acrylate,
Acrylic acid esters such as 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amino methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl Methacrylate, cyclohexyl methacrylate,
Methacrylic acid esters such as dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, and benzyl methacrylate; epoxy group-containing unsaturated compounds such as glycidyl methacrylate and allyl glycidyl ether; unsaturated carboxylic acid amides such as acrylamide and methacrylamide; acrylic amine, amino methacrylate Amino group-containing unsaturated compounds such as methyl, aminoethyl methacrylate, aminopropyl methacrylate, aminostyrene; 3-hydroxy-1-propene, 4-
Hydroxy-1-butene, cis-4-hydroxy-2-
Butene, trans-4-hydroxy-2-butene, 3-
Examples thereof include hydroxyl group-containing unsaturated compounds such as hydroxy-2-methyl-1-propene, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, and oxazoline group-containing unsaturated compounds such as vinyl oxazoline.

The component (A) of the present invention is obtained by copolymerizing the above various polymers by a known polymerization method, and a copolymer mainly composed of an aromatic vinyl compound and an unsaturated dicarboxylic acid anhydride. There is a method of imidizing after polymerization. Of both methods, the method of post-imidization is more preferable in terms of copolymerizability and economy. Examples of the primary amine used in the imidization reaction include alkylamines such as methylamine, ethylamine, propylamine and cyclohexylamine, and chloro- or bromo-substituted alkylamines thereof, aromatic amines such as aniline, tolylamyl and naphthylamine, and chloro- or bromo-amines. Substituted aromatic amines may be mentioned.

When the imidation reaction is carried out in a solution state or a suspension state, it is preferable to use an ordinary reaction vessel, for example, an autoclave, and when it is carried out in a bulk molten state, an extruder equipped with a devolatilization device is used. You may use. The temperature of the imidization reaction is about 80 to 350 ° C, preferably 100 to 300 ° C. If the temperature is lower than 80 ° C, the reaction rate is slow and the reaction takes a long time, which is not practical. On the other hand, 3
If it exceeds 50 ° C., the physical properties are deteriorated due to thermal decomposition of the polymer. A catalyst may be used in the imidization reaction, and in that case, a tertiary amine, for example, triethylamine is preferably used. The amount of component (A) used is
10-88.9% by weight, preferably 10-60% by weight,
More preferably 20 to 50% by weight, particularly preferably 3
It is 0 to 45% by weight. If it is less than 10% by weight, heat resistance is poor, and if it exceeds 88.9% by weight, impact resistance and molding processability are poor.

The component (B) of the present invention is a polyamide and / or a thermoplastic polyester, and is (B) of the present invention.
The polyamide component, usually the following _{formula: H 2 N- (CH 2)} ( wherein, X is 4-12 integer.) _X -NH _z and linear diamine represented by the following formula: HO ₂ C- (CH ₂₎ (wherein, y is an integer from 2 to 12.) _y -CO ₂ H and those produced by the condensation of linear carboxylic acids represented by the ring-opening polymerization of lactams A manufactured product 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 metaxylene diamine, or alicyclic diamines, polyads obtained from metaxylene diamine and the above linear carboxylic acid , Polyesteramide, etc. can also be used. The polyamide may be used alone or in combination with 2
It is also possible to use two or more species together.

Examples of the thermoplastic polyester include those obtained by condensing an aromatic dicarboxylic acid or its ester or ester-forming derivative and a diol by a known method. Examples of the aromatic dicarboxylic acid include naphthalene dicarboxylic acid such as naphthalene-2,6-dicarboxylic acid, terephthalic acid, isophthalic acid, p-hydroxybenzoic acid, adipic acid, sebacic acid, etc. Derivatives 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, or 1,
4-cyclohexanediol, bisphenol A and their ester-forming derivatives are mentioned.

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. The thermoplastic polyester preferably has an intrinsic viscosity ([η] 25 ° C, o-chlorophenol, unit dl / g) of 0.4 to 2 at 25 ° C in an o-chlorophenol solvent, and more preferably Is from 0.6 to 1.5. The amount of the component (B) used is 10 to 88.9% by weight, preferably 20 to 70%.
%, More preferably 30 to 60% by weight, particularly preferably 40 to 55% by weight. If it is less than 10% by weight, moldability is poor, and if it exceeds 88.9% by weight, impact resistance is poor.

In the ethylene-α-olefin polymer used as the component (C), the weight ratio of ethylene to α-olefin is 95/5 to 5/95, preferably 95/5.
20/80, more preferably 92/8 to 60/40. The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the ethylene-α-olefin copolymer is _{5 to 2} from the viewpoint of impact resistance.
00, preferably 5 to 100, more preferably 5 to 5
It is 0. The α-olefin used here is an unsaturated hydrocarbon compound having 3 to 20 carbon atoms, and specific examples thereof include propylene, butene-1, pentene-1,
Hexene-1, heptene-1, 4-methylbutene-1,
4-methylpentene-1 and the like can be mentioned. Particularly preferred are propylene and butene-1.

As the ethylene-α-olefin copolymer of the present invention, a copolymer obtained by copolymerizing ethylene and the above α-olefin with a diene compound and having an unsaturated group introduced therein can be used. . The unsaturated group preferably has a range of 4 to 40 in terms of iodine value. The types of dienes used are alkenyl norbornenes, cyclic dienes, and aliphatic dienes, preferably 5-ethylidene-2-norbornene and dicyclopentadiene. The ethylene-α-olefin-based copolymer is used alone or in combination of two or more.

The hydride of the conjugated diene polymer is a hydrogenated polymer obtained by hydrogenating a polymer composed of 0 to 50% by weight of an aromatic vinyl compound and 50 to 100% by weight of a conjugated diene compound. As the aromatic vinyl compound used in, all of the above-mentioned ones are used. Preferred is styrene. Further, as the conjugated diene compound, butadiene, isoprene, pentadiene, 2,3-
Examples thereof include dimethyl butadiene and the like, with butadiene being preferred. The diene polymer before hydrogenation is a random copolymer or block copolymer of a conjugated diene and a vinyl aromatic compound, a mixture thereof, a homopolymer of a conjugated diene, or the like. When the hydrogenated diene polymer is a mixture of different kinds of diene polymers, it may be mixed before hydrogenation and then hydrogenated, or may be mixed after water addition.

Hydrogenated block copolymers of an aromatic vinyl compound and a conjugated diene compound include those having an AB type, ABA type, taper type or radical teleblock type structure. Furthermore, the hydrogenated butadiene-based polymer is
In addition to the above block copolymers, hydrides of blocks of styrene blocks and styrene-butadiene random copolymers, blocks having a 1,2-vinyl bond content of 20% by weight or less in polybutadiene and 1,2-vinyl bonds Included are hydrides of polymers composed of polybutadiene blocks having a content of more than 20% by weight. The number average molecular weight of the diene polymer before hydrogenation is preferably 5,000 to 1,
, 000,000, more preferably 30,000 to 30
It is 10,000. These hydrogenated polymers may be used alone or in combination of two or more.

The ethylene-α-olefin-based copolymer and the hydride of the conjugated diene-based polymer may be used in combination. In the presence of a hydride of the above ethylene-α-olefin copolymer and / or conjugated diene polymer, an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound The component (C) of the present invention is obtained by subjecting the polymer to graft polymerization, and as the aromatic vinyl compound used here, all of the above-mentioned ones are used. Further, as the other vinyl monomer copolymerizable with the aromatic vinyl compound, the unsaturated dicarboxylic acid imide compound, unsaturated carboxylic acid, unsaturated dicarboxylic acid anhydride, vinyl cyanide compound, acrylic ester, methacrylic acid Esters, epoxy group-containing unsaturated compounds, unsaturated carboxylic acid amides, amino group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, oxazoline group-containing unsaturated compounds and the like are all used. The amount of hydride of the ethylene-α-olefin-based copolymer and / or the conjugated diene-based polymer in the component (C) is not particularly limited, but is 5 to 7
Used in the range of 0% by weight.

The component (C) of the present invention is the above-mentioned ethylene-α.
-Graft-polymerized in the presence of hydride of olefin-based copolymer and / or conjugated diene polymer, and in the absence of hydride of ethylene-α-olefin-based copolymer and / or conjugated diene-based polymer A mixture of the above-mentioned polymer and the polymer in an arbitrary ratio can also be used as the component (C) of the present invention. The amount of component (C) used is from 1 to
The amount is 50% by weight, preferably 5 to 40% by weight, more preferably 5 to 30% by weight. If it is less than 1% by weight, impact resistance is poor, and if it exceeds 50% by weight, heat resistance and molding processability are poor.

As the hydrogenated products of the ethylene-α-olefin copolymer and the conjugated diene polymer used as the component (D) of the present invention, all of those described above are used. The amount used is 0.5 to 20% by weight, preferably 1.0 to 1
It is 5% by weight, more preferably 1.0 to 10% by weight. If less than 0.5% by weight, the impact resistance is poor and
If it exceeds, the moldability and heat resistance will be poor.

Description of Claim 2 As the component (A) of the present invention, all those described in Claim 1 are used. The amount of component (A) used in the thermoplastic resin composition of the present invention is 10 to 88.9% by weight, preferably 10 to 60% by weight, more preferably 20 to 50% by weight, and particularly preferably 30 to 45% by weight. %. If it is less than 10% by weight, heat resistance is poor, and if it exceeds 88.9% by weight, impact resistance and molding processability are poor. As the component (B) of the present invention, all the components described in claim 1 are used.
The amount of the component (B) used is 10 to 88.9% by weight, preferably 20 to 70% by weight, more preferably 30 to 60% by weight, and particularly preferably 40 to 55% by weight. If it is less than 10% by weight, moldability is poor, and if it exceeds 88.9% by weight, impact resistance is poor.

As the unsaturated carboxylic acid, unsaturated dicarboxylic acid anhydride and epoxy group-containing unsaturated compound used in the component (E) of the present invention, all those described in claim 1 are used. All modified polyolefins modified with at least one of these functional group-containing unsaturated compounds are used as the component (E) in the present invention. As typical examples, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-maleic anhydride copolymer, ethylene-glycidyl methacrylate copolymer, propylene-
Maleic anhydride copolymer, ethylene-propylene-acrylic acid copolymer, ethylene-propylene-methacrylic acid copolymer, ethylene-propylene-maleic anhydride copolymer, ethylene-propylene-glycidyl methacrylate
Copolymer, ethylene-propylene copolymer-gr-maleic anhydride (gr indicates a graft, the same applies hereinafter),
Ethylene-propylene copolymer-gr-glycidyl methacrylate, ethylene-propylene copolymer-gr-methacrylic acid, ethylene-propylene copolymer-gr-acrylic acid, hydride of the butadiene-based polymer-gr-
The maleic anhydride or methacrylic acid or acrylic acid, or the above graft product can be obtained by reacting various monomers in the presence of various polyolefins and, if necessary, in the presence of peroxide. The amount of component (E) used is
0.1 to 30% by weight, preferably 0.5 to 20% by weight,
It is more preferably 0.5 to 4.5% by weight, and particularly preferably 1 to 4% by weight. If it is less than 0.1% by weight, impact resistance is poor, and if it exceeds 30% by weight, moldability is poor.

Examples of the rubbery polymer used in the component (F) of the present invention include polybutadiene, polyisoprene, and styrene-butadiene copolymer (styrene content of 5 to 5).
60% by weight is preferred. ), Styrene-isoprene copolymer, acrylonitrile-butadiene copolymer, ethylene-α-olefin copolymer, ethylene-α-olefin-polyene copolymer, acrylic rubber, silicone rubber, butadiene- (meth) acrylic acid Ester copolymer, polyisoprene, butyl rubber, styrene-butadiene block copolymer, styrene-isoprene block copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated butadiene-based polymer, ethylene-based ionomer and the like. .

The styrene-butadiene block copolymer and the styrene-isoprene block copolymer have A
Those having structures of B type, ABA type, taper type, radial teleblock type and the like are included. Further, the hydrogenated butadiene-based polymer has, in addition to the hydride of the block copolymer, a hydride of a block of a styrene block and a styrene-butadiene random copolymer, and a 1,2-vinyl bond content in polybutadiene. Included are hydrides of polymers composed of blocks of 20% by weight or less and polybutadiene blocks having a 1,2-vinyl bond content of more than 20% by weight. These rubber-like polymers are used alone or in combination of two or more. The content of rubbery polymer is
The component (A) is preferably 5 to 70% by weight, more preferably 5 to 50% by weight, particularly preferably 5 to 40% by weight.
Is.

As the aromatic vinyl compound and the other vinyl monomer copolymerizable with the aromatic vinyl compound used here, all those shown in the above-mentioned claim 1 are used. Furthermore, a mixture of a polymer obtained by (co) polymerizing a vinyl monomer mainly containing an aromatic vinyl compound in the absence of a rubbery polymer and the above component (F) is also used as the component (F) of the present invention. can do. The component (F) of the present invention can be produced by known polymerization methods such as emulsion polymerization, solution polymerization, bulk polymerization and suspension polymerization. The amount of the component (F) used in the thermoplastic resin composition of the present invention is 1 to 79.9% by weight, preferably 55% by weight, more preferably 1 to 40%.
%, Particularly preferably 5 to 30% by weight. If it is less than 1% by weight, impact resistance is poor, and if it exceeds 79.9% by weight, heat resistance is poor.

Examples of the olefin polymer as the component (G) of the present invention include polyethylene, polypropylene, ethylene-α-olefin copolymers, hydrides of conjugated diene polymers and the like. Ethylene used here
As the hydride of the α-olefin-based copolymer and the conjugated diene-based polymer, the above-mentioned ones are all used. (G)
The amount of the component used is 20% by weight or less, and preferably 1 to 15% by weight, more preferably 1 to 5% by weight in order to obtain the effect of adding impact resistance. If it exceeds 20% by weight, heat resistance, impact resistance and molding processability are deteriorated.

Description of Claim 3 As the component (A) used here, all the components (A) described in claim 1 are used. The usage is 1
0 to 88.9% by weight, preferably 10 to 60% by weight, more preferably 20 to 50% by weight, particularly preferably 30.
~ 45% by weight. If it is less than 10% by weight, heat resistance is poor, and if it exceeds 88.9% by weight, impact resistance and molding processability are poor. As the component (B) used in the present invention, all the components (B) described in claim 1 are used. The amount of the component (B) used is 10 to 88.9% by weight, preferably 20 to
70% by weight, more preferably 30 to 60% by weight, particularly preferably 40 to 55% by weight. If it is less than 10% by weight, moldability is poor, and if it exceeds 88.9% by weight, impact resistance is poor.

As the component (E) used in the present invention, all the components (E) described in claim 2 are used. The amount of component (E) used is 0.1 to 30% by weight, preferably 1 to 2
0% by weight, more preferably 1 to 4% by weight, and
If it is less than 1% by weight, impact resistance is poor, and if it exceeds 30.0% by weight, moldability is poor. As the component (G) used in the present invention, all the components (G) of claim 2 are used.
The amount of component (G) used is 1 to 25% by weight, preferably 1 to
20% by weight, more preferably 5 to 20% by weight,
If it is less than 1% by weight, impact resistance is poor, and if it exceeds 25% by weight, heat resistance, impact resistance and molding processability are poor.

Common Description of Claims 1, 2 and 3 The thermoplastic resin composition of the present invention comprises glass fiber,
Carbon fiber, metal fiber, glass beads, wollastonite,
Rock filler, calcium carbonate, talc, mica, glass ferry, kaolin, barium sulfate, graphite, molybdenum disulfide, magnesium oxide, zinc oxide whiskers,
Fillers such as potassium titanate whiskers can be used alone or in combination. Among these fillers, the shape of glass fiber or carbon fiber is 6 to 60.
Those having a fiber diameter of μm and a fiber length of μm or more are preferable. These fillers are usually used in the range of 5 to 150 parts by weight with respect to 100 parts by weight of the composition of the present invention.

Further, the composition of the present invention includes known coupling agents, antibacterial / antifungal agents, flame retardants, antioxidants, plasticizers, colorants, lubricants, weathering agents, antistatic agents, silicone oils, etc. Can be added. Further, the composition of the present invention has other polymers such as polyethylene, polypropylene, polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, liquid crystal polymer, polyvinylidene fluoride, and styrene-vinyl acetate depending on required performance. A copolymer, a polyamide elastomer, a polyester elastomer or the like can be appropriately blended.

The thermoplastic resin composition of the present invention can be obtained by kneading each component using various extruders, Banbury mixers, kneaders, rolls and the like. A preferred manufacturing method is a method using a twin-screw extruder. Also,
When kneading each component, each component may be kneaded together or may be kneaded by a multi-stage addition method. As a preferable kneading method, at least 30% by weight or more of the component (B) of the present invention is post-added and kneading is preferable from the viewpoint of impact resistance. More preferably, it is 50% by weight or more. The thermoplastic resin composition of the present invention thus obtained can be molded into various molded articles by injection molding, sheet extrusion, vacuum molding, profile molding, foam molding, or the like. Various molded products obtained by the above molding method are used for interior / exterior materials in the vehicle field, OA / home appliances field, housing / chassis in the electric / electronic field, various other parts, miscellaneous goods, etc. by utilizing their excellent properties. can do.

[0035]

EXAMPLES The present invention will be described in more detail 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.

Heat resistance According to ASTM D648, thickness 1/4 ", load 4.
The heat distortion temperature was measured at 6 kg / cm ² . Impact resistance According to ASTM D256, Izod impact strength was measured at a thickness of 1/4 ", with a notch and at an ambient temperature of 23 ° C. Molding processability Cylinder setting temperature of injection molding machine 260 ° C, injection pressure 1
The resin was injected into the mold at 000 kg / cm ² and the flow length of the resin flowing in the mold was measured.

Preparation of Polymers (A) -1 to (A) -6 Polymers (A) -1 to (A)-which are the components (A) of the present invention.
6 was prepared by the following method. Polymers (A) -1 to (A) -6 having the compositions shown in Table 1 were obtained by solution polymerization.

[0038]

[Table 1]

Preparation of Polymer (A) -7 After the autoclave with a stirrer was replaced with nitrogen, 51 parts of styrene and 50 parts of methyl ethyl ketone were charged and the temperature was raised to 85 ° C. A solution consisting of 49 parts of maleic anhydride, 0.15 parts of benzoyl peroxide and 250 parts of methyl ethyl ketone was continuously added over 8 hours. 2 hours after addition, 85 ℃
Kept the temperature to. Then, aniline and triethylamine as a catalyst were added, and the temperature was raised to 140 ° C. to imidize the acid anhydride. The polymer (A) -7 was recovered with methanol. As a result of measuring the composition ratio of the polymer (A) -7 by NMR analysis, it was found that styrene was 45%, N-phenylmaleimide was 50%, and maleic anhydride was 5%.

The following polymers are used as the component (B) of the present invention.
Using. Polymer (B) -1; manufactured by Allied Signal, nylon 6
As the capron XA1767 was used. Polymer (B) -2; manufactured by Kanebo Ltd., PBT as PBT
-120 was used.

Preparation of Polymers (C) -1 to (C) -8 The following are used as hydrides of the ethylene-propylene polymer and the butadiene polymer used in the production of the polymer (C) of the present invention. I was there. <Ethylene-Propylene Polymer> Polymer (D) -1; manufactured by Nippon Synthetic Rubber Co., Ltd., JSR
EP84 Polymer (D) -2; manufactured by Nippon Synthetic Rubber Co., Ltd., JSR
EP01 <Hydride of butadiene-based polymer> Polymer (D) -3; Shell Chemical Co., KRAT
ON G1650 Polymer (D) -4; polystyrene block (5%)
A-B-C type block copolymerization consisting of a random copolymer block (90%) consisting of 80 parts of styrene and 80 parts of butadiene and a taper block (5%) consisting of 5 parts of styrene and 3 parts of butadiene with gradually increasing styrene. A hydrogenated diene-based polymer having a combined hydrogenation rate of 99%. Polymer (D) -5 Polystyrene block (20%), polybutadiene block having a 1,2-vinyl content of 35% (55%) and polybutadiene block having a 1,2-vinyl content of 13% (25%) A -A hydrogenated diene polymer having a hydrogenation rate of 99% of a B-C type block copolymer. The polymer (D)-
The monomers shown in Table 2 were (grafted) copolymerized in the presence or absence of 1 to (D) -5. Polymer (C) -1 to
(C) -6 was obtained by solution polymerization.

[0042]

[Table 2]

The following polymers are used as the component (D) of the present invention.
Using. The polymers (D) -2 to (D) -5 were used.

Preparation of component (E) The polymers (D) -2, (D) -5, the monomer components shown in Table 3 and an organic peroxide are mixed, and the mixture is melted by heating and kneading with a uniaxial extractor. Then, a monomer is grafted onto the polymers (D) -2 and (D) -5, and modified polyolefin polymers (E) -1 to 5
Got The contents of the obtained polymers (E) -1 to 4 are shown in Table 3. The amount of added monomer was determined by infrared analysis.

[0045]

[Table 3]

Preparation of Component (F) As the component (F), a polymer (F) -1 comprising 30 parts (solid content) of polybutadiene latex (average particle size: 3500 Å), 51 parts of styrene, and 19 parts of acrylonitrile is emulsified. Obtained by polymerization. The polymers (C) -1 and (C) -4 were used as the component (F).

Preparation of component (G) As the component (G), the polymers (D) -2 and (D) -4 are used.
Was used.

Production of Thermoplastic Resin Composition The above-mentioned various polymers were mixed according to the formulation shown in Table 4 and melt-kneaded into pellets using a twin-screw extruder with a vent. During the kneading, only the component (B) was fed from the middle of the extruder. The obtained pellets were sufficiently dried and injection-molded to form test pieces for heat resistance, body impact resistance and measurement. The moldability was evaluated by the above evaluation method using dried pellets. The evaluation results are shown in Table 4.

Comparative Example 1 is an example in which the amount of unsaturated dicarboxylic acid anhydride in the component (A) of the present invention is out of the range of the present invention, and the moldability is poor. Comparative Example 2 is an example in which the amount of unsaturated dicarboxylic acid anhydride in the component (A) of the present invention is small outside the range of the present invention, and the impact resistance is poor. Comparative Example 3 is an example in which the amount of the component (A) used in the present invention is outside the scope of the invention and the amount of the component (B) used is outside the scope of the invention.
Poor impact resistance and moldability. Comparative Example 4 is an example in which the use amount of the component (C) of the present invention is outside the scope of the invention,
Inferior heat resistance. Comparative Example 5 is an example in which the amount of the component (D) of the present invention used is small outside the range of the invention, and the impact resistance is poor.
Comparative Example 6 is an example in which the amount of the component (D) used in the present invention is large outside the range of the invention, and the heat resistance and the moldability are poor. Comparative Example 7 is an example in which the use amount of the component (E) of the present invention is out of the range of the invention, and the moldability is poor. In Comparative Example 8, the amount of the component (E) used in the present invention is outside the range of the invention, and the impact resistance is poor. Comparative Example 9 is an example in which the use amount of the component (E) of the present invention is small outside the range of the invention, and the impact resistance is poor.

[0050]

[Table 4]

[0051]

The thermoplastic resin composition of the present invention has heat resistance,
Has excellent impact resistance and molding processability, and has a wide range of applications, such as interior / exterior fields in the vehicle field, OA / home appliances field, housings in the electric / electronic field, chassis, and various other parts.
It is useful for miscellaneous goods.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location C08L 35/06 LHS LJW 51/04 LKY 51/06 LLE 67/02 LNZ 77/00 LQR (72) Inventor Furuyama Kenki 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (3)

[Claims] 1. (A) 20 to 90% by weight of an aromatic vinyl compound, 9.5 to 60% by weight of an unsaturated dicarboxylic acid imide compound and 0.5 to 20 of an unsaturated carboxylic acid and / or an unsaturated dicarboxylic acid anhydride. 10 to 88.9% by weight of a thermoplastic resin composed of 10% by weight, (B) 10 to 88.9% by weight of a polyamide and / or a thermoplastic polyester,
(C) An aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with an aromatic vinyl compound in the presence of a hydride of an ethylene-α-olefin copolymer and / or a conjugated diene polymer. 1 to 50% by weight of a rubber-modified thermoplastic resin obtained by graft polymerizing a monomer,
(D) 0.1-20% by weight of hydride of ethylene-α-olefin-based copolymer and / or conjugated diene-based polymer, consisting of the components (A) + (B) + (C) + (D) A thermoplastic resin composition comprising: 2. (A) Ingredients (A) 10-8 of claim 1.
8.9% by weight, (B) 10 to 8 component (B) of claim 1.
8.9% by weight, (E) 0.1 to 30% by weight of modified polyolefin having at least one functional group selected from unsaturated carboxylic acid, unsaturated dicarboxylic acid anhydride, and epoxy group-containing unsaturated compound, ( F) A rubber-modified thermoplastic resin obtained by graft-polymerizing an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with an aromatic vinyl compound in the presence of a rubbery polymer 1-79. 9
%, (G) 0 to 20% by weight of olefin polymer, and the thermoplastic resin composition comprising (A) + (B) + (E) + (F) + (G). 3. (A) Ingredients (A) 10 to 8 according to claim 1.
8.9% by weight, (B) 10 to 8 component (B) of claim 1.
8.9% by weight, (E) 0.1 to 3 of the (E) component of claim 2.
A thermoplastic resin composition comprising 0.0% by weight, (G) 1 to 25% by weight of the component (G) of claim 2, and (A) + (B) + (E) + (G). object.