JP2000001596A - Thermoplastic resin composition - Google Patents

Abstract

(57) [Summary] (Modifications) [PROBLEMS] To provide a thermoplastic resin composition having a molded article having a low head impact index, high heat deformation resistance, and excellent appearance and moldability. An aromatic vinyl compound and an acrylic ester copolymer (I) obtained by polymerizing a monomer copolymerizable therewith, a maleimide monomer, an alkyl (meth) acrylate, and an aromatic vinyl compound , Vinyl cyanide compounds,
And 15 to 80 parts by weight of a maleimide copolymer (II) obtained by polymerizing a monomer copolymerizable therewith, a rubber polymer (A), an aromatic vinyl compound, (meth) acrylate, cyan A graft copolymer (III) obtained by polymerizing a vinyl compound and a monomer mixture of a monomer copolymerizable therewith, comprising 20 to 85 parts by weight, and having a rubber polymer content of 5 to 50% by weight. To 100 parts by weight of the resin composition, 0.01 to 5 parts by weight of at least one of the following stabilizers (a), (b), and (c) and / or 0.05 of the following lubricant (d) A thermoplastic resin composition comprising up to 8 parts by weight. (A) hindered amine stabilizer. (B) Fight stabilizer. (C) Hindered phenol compounds. (D) Ester-based lubricants.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having a molded article having a low head impact index (HIC), a high thermal deformation resistance, and excellent moldability. .

[0002]

2. Description of the Related Art Styrene resins, especially ABS resins, have excellent rigidity, impact resistance, heat deformation resistance, moldability, etc., and are therefore used for various goods, interior and exterior materials of automobiles, jar rice cookers, microwave ovens. Are widely used for housing parts of home electric appliances such as vacuum cleaners and housings and parts of OA equipment such as telephones and facsimile machines.

In recent years, particularly in interior and exterior materials of automobiles, in addition to characteristics such as dimensional stability and surface appearance at high temperatures, characteristics relating to collision safety have been improved as seen in side collision regulations in the United States and other countries. Is desired. That is, as the interior / exterior resin material in the side collision control, a molded article has a low head impact index (HIC), a high impact resistance, a high thermal deformation resistance, an appearance property (surface property), and moldability. Demands for excellent resins. H in FMVSS
IC is defined as the maximum value of the integrated value of the acceleration change for a certain period of time.

[0004] Various studies have been made to satisfy these characteristics, but none of them has yet been obtained having sufficient characteristics. For example, Japanese Patent Application Laid-Open No. 59-20346 discloses a method of adding a specific plasticizer to a rubber-reinforced styrene-based resin. However, such a method is not satisfactory because of low heat deformation resistance and volatilization of the plasticizer. The use of a polypropylene resin having a specific composition is also being studied, but has the drawback of poor appearance of the molded product surface due to sink marks, poor dimensional stability due to warpage, and poor adhesion to other materials.

Further, a composition of an ABS resin and an acrylic ester copolymer has been disclosed in Japanese Patent Application Laid-Open No. Sho 58-17925.
No. 7 discloses a composition comprising a rubber-containing styrenic resin and an acrylic ester copolymer having a high gel content, and JP-A-63-17954 discloses a composition comprising a rubber-containing maleimide-styrene copolymer and an ABS resin. It is described that a composition comprising an acrylic ester copolymer improves chemical resistance, but these compositions have high HIC values, low impact resistance, and poor surface appearance. A resin having a low HIC value, high impact resistance, high heat deformation resistance, excellent appearance (surface properties), and excellent moldability is not obtained.

Further, a composition comprising a rubber-containing maleimide-styrene copolymer, an ABS resin and an acrylate ester copolymer described in JP-A-63-17954 or JP-A-8-027336 is disclosed. The composition comprising a rubber-containing maleimide-styrene-based copolymer and an acrylate-based copolymer described above also has an HIC
Resins having low values, high impact resistance, and excellent appearance (surface properties) have not been obtained.

The molding processability of maleimide A
As for the BS resin, JP-A-62-236844 describes improvement of thermal stability by using a combination system of a hindered phenol compound and a phosphite compound, but an acrylic ester such as the thermoplastic resin of the present invention is used. In the case of an alloy comprising a copolymer (I), a maleimide copolymer (II), and a graft copolymer (III), no stabilizer, an effective stabilizer for a lubricant, or a lubricant has been proposed.

[0008]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems and provides a molded article having a low head impact index (HIC), high impact resistance, high thermal deformation resistance, and appearance. It is an object of the present invention to provide a resin composition having excellent surface properties and moldability.

[0009]

In order to reduce the HIC value, increase the impact resistance, enhance the heat deformation resistance, and improve the appearance (surface properties) and moldability, a rubber-containing maleimide copolymer is required. The matrix in the composition consisting of the union and the acrylate-based copolymer has a polymer alloy structure in which the maleimide-based copolymer and the acrylate-based copolymer are microphase-separated and matches the microphase-separated matrix. It is necessary to find a graft copolymer obtained (reinforced component). Further, it is necessary to find a stabilizer and a lubricant having high thermal stability while maintaining a microphase separation structure, having a polymer composition having low thermal decomposability, excellent mold contamination, and high thermal stability.

The present inventors have conducted intensive studies on this problem and found that the acrylate copolymer (I) having a low Tg and a low gel content, the maleimide copolymer (II) having a high Tg, and a graft copolymer. A thermoplastic resin composition using a specific stabilizer and a lubricant in an alloy made of the polymer (III) has a low HIC value, a high impact resistance, a high thermal deformation resistance, and an appearance (surface property). It has been found that the moldability is excellent, and the present invention has been achieved.

That is, the present invention relates to an acrylic ester of 40 to 85% by weight, a vinyl cyanide compound of 15 to 40% by weight, an aromatic vinyl compound of 45% by weight or less, and a monomer copolymerizable therewith with 0 to 30% by weight. % (Total 100% by weight) of an acrylic ester-based copolymer (I) having a Tg (glass transition temperature) of 20 ° C. or less and a gel content of 10% by weight or less, and maleimide 5 to 50% by weight of a system monomer, 0 to an alkyl (meth) acrylate
50% by weight, 0 to 85% by weight of an aromatic vinyl compound, 0 to 40% by weight of a vinyl cyanide compound, and 0 to 20% by weight of a monomer copolymerizable therewith (total 100% by weight). Maleimide copolymer (II) 15 to 80 parts by weight, volume average particle diameter of 50 to 1000 nm at least selected from diene rubber polymer, olefin rubber polymer, acrylic rubber polymer, silicon rubber polymer In the presence of 10 to 90 parts by weight of one type of rubber polymer (A), at least one type of monomer selected from 10 to 90% by weight of an aromatic vinyl compound, a (meth) acrylate, and a vinyl cyanide compound 10 to 90% by weight of a monomer mixture of 10 to 90% by weight and 0 to 30% by weight of a monomer copolymerizable therewith (total 100% by weight) are polymerized, and the graft ratio is 10 to 70% by weight. % And a graft copolymer (III)
A resin composition comprising 20 to 85 parts by weight, and having a reduced viscosity (30 ° C., in N, N-dimethylformamide solution) of a methyl ethyl ketone soluble component in the resin composition, of 0.3 to 1.2 dl. / G, and 100 parts by weight of a resin composition having a rubber polymer content of 5 to 50% by weight,
At least one selected from the following (a), (b), and (c)
The thermoplastic resin composition comprises 0.01 to 5 parts by weight of a stabilizer and / or 0.05 to 8 parts by weight of the following lubricant (d). (A) a molecular weight of 450 or more having an ester group in the molecule;
And a hindered amine stabilizer having a melting point of 50 ° C. or more (b) a phosphite stabilizer having a molecular weight of 550 or more and a melting point of 100 ° C. or more (c) an ester group or a cyanurate group having a molecular weight of 500 or more and a melting point of 50 ° C. or more Hindered phenol compound (d) An ester lubricant having two or more ester groups in the molecule and having a molecular weight of 600 or more.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The acrylate copolymer (I) of the present invention is a portion used for lowering the HIC value and increasing the impact resistance. It is preferably from 50 to 80% by weight, more preferably from 55 to 75% by weight from the viewpoint of weight%, HIC value and impact resistance. 15 to 40% by weight of the vinyl cyanide compound,
From the viewpoint of impact resistance, it is preferably 20 to 35% by weight, more preferably 20 to 30% by weight.
The content is 45% by weight, preferably 0 to 30% by weight, more preferably 2 to 25% by weight from the viewpoint of processability. The monomer copolymerizable therewith is 0 to 30% by weight, preferably 0 to 2%.
0 parts by weight, more preferably 0 to 10 parts by weight (total 100 parts by weight)
% By weight).

When the acrylate is less than 40% by weight, the HIC value is high and the impact resistance is low. When it exceeds 85% by weight, the heat resistance is low and the film is easily peeled. Also,
If the amount of the vinyl cyanide compound is less than 15% by weight, it is easy to peel off and the HIC value is high. If it exceeds 40% by weight, it is easy to peel off, the HIC value is high and the impact resistance is low. On the other hand, when the content of the aromatic vinyl compound exceeds 45% by weight, the impact resistance is low and the HIC value is high. The Tg of the acrylate copolymer (I) is at most 20 ° C, preferably at most 0 ° C, more preferably at most -10 ° C from the viewpoint of the HIC value. If it exceeds 20 ° C., the HIC value increases.

The gel content of the acrylate copolymer (I) [gel content refers to methyl ethyl ketone, 2%
The solution was allowed to stand at 23 ° C. for 24 hours, filtered through a 100-mesh wire gauze, and the filtration residue was dried. The value was expressed by (weight of filtration residue / original weight) × 100%. ] Is 10% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less from the viewpoint of processability. If it exceeds 10% by weight, the moldability will be reduced.

The reduced viscosity of the methyl ethyl ketone soluble portion of the acrylate copolymer (I) (30
C, in N, N-dimethylformamide solution)
-1.2 dl / g, preferably 0.4-1.0 dl / g
g, more preferably 0.45 to 0.9 dl / g.
If it is less than 0.3 dl / g, the impact resistance is reduced, and if it exceeds 1.2 dl / g, the workability is reduced.

The acrylate used in the acrylate copolymer (I) includes methyl acrylate, ethyl acrylate, butyl acrylate, 2-acrylate,
Ethylhexyl acrylate, lauryl acrylate,
Examples include stearyl acrylate, 2-hydroxylethyl acrylate, and glycidyl acrylate. Of these, butyl acrylate is preferred from an industrial point of view. These may be used alone or in combination of two or more.

Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile and the like. Of these, acrylonitrile is preferred from an industrial viewpoint. These may be used alone or in combination of two or more. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, vinylnaphthalene, chlorostyrene, and bromostyrene. Of these, styrene is preferable from an industrial viewpoint. These may be used alone or in combination of two or more.

Examples of the monomer copolymerizable with the compound include acrylic acid, methacrylic acid, maleimide,
N-phenylmaleimide and the like can be mentioned. The maleimide-based copolymer (II) of the present invention comprises a maleimide-based monomer 5 to
50% by weight, preferably 10 to 45% by weight, more preferably 13 to 42% by weight, alkyl (meth) acrylate 0 to 50% by weight, preferably 5 to 45% by weight, more preferably 10 to 42% by weight, aromatic Group vinyl compound 0-85
% By weight, preferably 5 to 80% by weight, more preferably 1% by weight.
0 to 74% by weight, 0 to 40% by weight of the vinyl cyanide compound, preferably 5 to 35% by weight, more preferably 7 to 3% by weight.
3% by weight, and 0 to 20% by weight, preferably 0 to 10% by weight, more preferably 0 to 10% by weight of monomers copolymerizable therewith.
It is a copolymer obtained by polymerizing a monomer mixture consisting of 7% by weight (total 100% by weight).

In the maleimide-based copolymer (II), if the amount of the maleimide-based monomer is less than 5% by weight, the heat resistance is reduced, and if it exceeds 50% by weight, the processability is reduced. The alkyl (meth) acrylate is important for controlling the microstructure of the matrix of the thermoplastic resin composition of the present invention, and is preferably used in an amount of 5% by weight or more from the viewpoint of impact resistance and workability. When the content of the alkyl (meth) acrylate exceeds 50% by weight, the heat resistance decreases. Vinyl cyanide compound is 4
If the content exceeds 0% by weight, the processability is increased.
If it exceeds 5% by weight, the impact resistance is reduced. The content of the alkyl (meth) acrylate and / or the aromatic vinyl compound in the monomer mixture is preferably 49 mol% or more, more preferably 50 mol%, from the viewpoint of heat stability, impact resistance, and mold contamination resistance. Mol% or more.

The maleimide copolymer (II) has a Tg of 100 to 200 ° C., preferably 110 to 200, from the viewpoint of heat resistance.
180 ° C, more preferably 115-170 ° C. The maleimide copolymer (II) preferably has a reduced viscosity (30 ° C., in an N, N-dimethylformamide solution) of methyl ethyl ketone-soluble component in the range of 0.3 to 1.2 dl from the viewpoint of impact resistance and processability. / G, more preferably 0.35 to
1.0 dl / g, particularly preferably 0.40 to 0.9 d
1 / g.

The maleimide monomers of the maleimide copolymer (II) used in the present invention include maleimide, N
-Methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- (p-methylphenyl) maleimide and the like, as alkyl (meth) acrylates, methyl methacrylate, ethyl methacrylate, Examples thereof include butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, and stearyl acrylate.

As the aromatic vinyl compound, styrene,
α-methylstyrene, p-methylstyrene, p-isopropylstyrene, chlorostyrene, bromostyrene, vinylnaphthalene, etc., as vinyl cyanide compounds,
Acrylonitrile, methacrylonitrile and the like can be mentioned. From an industrial point of view, maleimide monomers include N-
Methyl methacrylate is particularly preferable as phenylmaleimide and alkyl (meth) acrylate, acrylonitrile as vinyl cyanide compound, and styrene and α-methylstyrene as aromatic vinyl compound. These can be used alone or in combination of two or more.

Examples of the copolymerizable monomer include (meth) acrylic acid and its (meth) acrylate derivatives such as 2-hydroxyethyl and glycidyl. These may be used alone or in combination of two or more. The rubber polymer in the graft copolymer (III) is a diene rubber polymer, an olefin rubber polymer,
It is at least one rubber polymer selected from an acrylic rubber polymer and a silicon rubber polymer, and has a volume average particle size of 50 to 1000 nm, preferably 100 to 900.
0 nm, more preferably 150 to 800 nm.

Specific examples of the rubber polymer include diene rubber polymers such as polybutadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, butadiene-acrylate rubber, hydrogenated styrene-butadiene rubber, and ethylene-propylene rubber. Olefin polymers such as ethylene-propylene-diene rubber; acrylic rubber polymers such as polyacrylate rubber and ethylene-acrylate rubber;
It can be used in combination of more than one kind.

The rubber polymer is an acid group-containing latex (S)
At least one produced by the hypertrophy method using
It is preferred to use a rubber polymer containing more than one species. The acid group-containing latex (S) contains 5 to 50% by weight of an unsaturated acid (c) of at least one of acrylic acid, methacrylic acid, itaconic acid and crotonic acid, and the alkyl group has 1 to 1 carbon atoms.
2) at least one (meth) alkyl acrylate (d) in an amount of 50 to 95% by weight, and 0 to 40% of a monomer copolymerizable with (c) and (d) by emulsion polymerization. it can.

In particular, an unsaturated acid (c) of at least one of acrylic acid, methacrylic acid, itaconic acid and crotonic acid is 5 to 25% by weight, and the alkyl group has 1 to 12 carbon atoms.
At least one alkyl acrylate (d)
0% by weight, 80 to 20% by weight of alkyl methacrylate (e) having 1 to 12 carbon atoms in the alkyl group, (c),
(D), an aromatic vinyl monomer copolymerizable with (e) and / or a monomer having two or more polymerizable functional groups in a molecule, and / or 0 to 40% of a vinyl cyanide compound. HIC value, impact resistance,
It is preferable from the viewpoint of appearance (surface properties). The acid group-containing latex (S) is used in an amount of 0.1 to 15 parts by weight (solids) with respect to 100 parts by weight (solids) of rubber latex to perform coagulation and hypertrophy. , Impact resistance,
It is preferable in terms of appearance (surface properties) and production stability.

Examples of the unsaturated acid (c) used in the acid group-containing latex (S) include acrylic acid, methacrylic acid, itaconic acid and crotonic acid, and acrylic acid and methacrylic acid are particularly preferred. As the alkyl acrylate, an ester of acrylic acid and an alcohol having a linear or side chain having 1 to 12 carbon atoms is used, such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. And an alkyl group having 1 to 8 carbon atoms is particularly preferable.
These can be used alone or in combination of two or more.

The alkyl methacrylate (d) includes
Esters of methacrylic acid and an alcohol having a linear or side chain having 1 to 12 carbon atoms are used, and examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and the like. Those having 1 to 8 carbon atoms in the alkyl group are preferred. These can be used alone or in combination of two or more.

Examples of monomers copolymerizable with these monomers include aromatic vinyl monomers such as styrene, α-methylstyrene and p-methylstyrene and vinyl cyanide such as acrylonitrile and methacrylonitrile. Compound.
These can be used alone or in combination of two or more. or,
Still other copolymerizable monomers, allyl methacrylate, polyethylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanurate,
Monomers having two or more polymerizable functional groups in the molecule, such as triallyl trimellitate, may be mentioned. These can be used alone or in combination of two or more.

The graft copolymer (III) of the present invention is used in an amount of 10 to 90 parts by weight, preferably 20 to 80 parts by weight, preferably 10 to 90 parts by weight, preferably 15 to 85 parts by weight of an aromatic vinyl compound in the presence of a rubber polymer. %, More preferably 20-80
% By weight, at least one of (meth) acrylic acid ester and vinyl cyanide compound, 10 to 90% by weight, preferably 15 to 90% by weight.
85% by weight, more preferably 20 to 80% by weight, and a monomer copolymerizable therewith with 0 to 30% by weight, preferably 0 to 20% by weight, more preferably 0 to 15% by weight The mixture (100% by weight in total) is obtained by polymerizing 90 to 10 parts by weight, more preferably 80 to 20 parts by weight. If the (meth) acrylate, the vinyl cyanide compound, the aromatic vinyl compound, and the graft ratio are outside the above ranges, the HIC value, impact resistance, appearance (surface properties), and workability are reduced.

Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate.
Acrylate, glycidyl (meth) acrylate and the like can be mentioned. Of these, methyl methacrylate is preferred from an industrial point of view. These may be used alone or in combination of two or more.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and examples of the aromatic vinyl compound include styrene, α-methylstyrene and p-methyl styrene.
Methylstyrene, p-isopropylstyrene, chlorostyrene, bromostyrene, vinylnaphthalene and the like are preferred from an industrial viewpoint. Further, acrylonitrile is particularly preferred as the vinyl cyanide compound, and styrene is particularly preferred as the aromatic vinyl compound. These may be one kind or two or more kinds.

Examples of the copolymerizable monomer include (meth) acrylic acid, maleimide, N-phenylmaleimide and the like. These may be one kind or two or more kinds. The graft copolymer (III) is from 10 to 90 parts by weight, preferably from 20 to 85 parts by weight, and more preferably from the viewpoint of HIC value, impact resistance, appearance (surface properties), and processability. Is obtained by polymerizing 10 to 90 parts by weight, preferably 15 to 80 parts by weight, more preferably 20 to 70 parts by weight of the monomer mixture in the presence of 30 to 80 parts by weight.
The graft copolymer (III) has a graft ratio of 10 to 70% by weight, preferably 20 to 60% by weight, more preferably 2 to 60% by weight.
5 to 55% by weight. If the graft ratio is outside the above range, the HIC value, impact resistance, appearance (surface properties), and workability will be reduced.

If the composition within the scope of the present invention is obtained, the acrylate copolymer (I), the maleimide copolymer (II) and the graft copolymer (III) can be prepared by any polymerization method.
Those produced using an initiator, a chain transfer agent, and a surfactant may be used. For example, a known bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, an emulsion-suspension polymerization method, an emulsion-bulk polymerization method, and the like can be produced by any polymerization method as long as the composition can be controlled within the scope of the present invention. May be done.

From the viewpoint of controlling the microstructure of the matrix and controlling the graft ratio of the graft copolymer (III), the above polymerization method is preferably an emulsion polymerization method. In addition, from the viewpoint of control of the microstructure of the matrix and affinity between the graft copolymer and the matrix, it is preferable to blend one or more latexes. Further, at least one of an acrylic ester-based copolymer (I), a maleimide-based copolymer (II), and a graft copolymer (III) is used in the same system (polymerization machine).
And a method of continuously polymerizing in the presence of another polymer.

Further, as long as it is within the scope of the present invention, any one produced using any initiator, chain transfer agent or emulsifier may be used. Known initiators such as a thermal decomposition initiator such as potassium persulfate and a redox initiator such as Fe-reducing agent-organic peroxide can be used as the initiator. Further, known chain transfer agents such as n-octyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, α-methylstyrene dimer, terpinolene and the like can be used. Examples of the emulsifier include fatty acid metal salt-based emulsifiers such as sodium oleate, sodium palmitate, and sodium rosinate, metal sulfonic acid salts such as sodium dodecylbenzenesulfonate, sodium alkylsulfonate having 12 to 20 carbon atoms, and sodium dioctyl sulfosuccinate. A known emulsifier such as an emulsifier can be used.

The thermoplastic resin composition of the present invention contains 5 to 65 parts by weight, preferably 8 to 55 parts by weight, more preferably 10 to 45 parts by weight of the acrylate copolymer (I).
Maleimide copolymer (II) 15 to 80 parts by weight, preferably 18 to 70 parts by weight, more preferably 20 to 65 parts by weight, graft copolymer (III) 20 to 85 parts by weight, preferably 23 to 80 parts by weight Parts, more preferably 25 to 75 parts by weight (total 100 parts by weight).

When the acrylate copolymer (I) is 5
If the amount is less than 65 parts by weight, the heat resistance and the impact resistance decrease. When the maleimide-based copolymer (II) exceeds 80 parts by weight, the HIC value increases,
If the amount is less than 20 parts by weight, the heat resistance is reduced. When the amount of the graft copolymer (III) is less than 20 parts by weight, the HIC value becomes high, and the impact resistance is lowered.
It is not preferable because the fluidity decreases.

The thermoplastic resin composition of the present invention has the following composition based on a total of 100 parts by weight of the acrylate copolymer (I), the maleimide copolymer (II), and the graft copolymer (III). It is obtained by adding 0.01 to 5 parts by weight of at least one of stabilizers (a), (b) and (c) and 0.05 to 8 parts by weight of the following lubricant (d). (A) a molecular weight of 450 or more having an ester group in the molecule;
And a hindered amine stabilizer having a melting point of 50 ° C. or more (b) a phosphite stabilizer having a molecular weight of 550 or more and a melting point of 100 ° C. or more (c) an ester group or a cyanurate group having a molecular weight of 500 or more and a melting point of 50 ° C. or more Hindered phenol compound (d) An ester lubricant having two or more ester groups in the molecule and having a molecular weight of 600 or more.

Specifically, as a hindered amine compound having a molecular weight of 450 or more and having a melting point of 50 ° C. or more having an ester group in the molecule of (a), bis (2,2,6,6
-Tetramethyl-4-piperidinyl) sebacate, 1,
2,3,4-tetrakis (2,2,6,6-tetramethyl-4-piperidyloxycarbonyl) butane, dimethyl-1- (2-hydroxyethyl) 4-hydroxy-2,2,6,6 succinate -Tetramethylpiperidine polycondensate, bis (1,2,2,2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate
6,6-pentamethyl-4-piperidyl), 1,2,2
3,4-butane-tetracarboxylic acid and 1,2,2,6
6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,
Polycondensate of 4,8,10-tetraoxospiro [5,5] undecane, 1- (3,5-di-t-butyl-4-hydroxyphenyl) -1,1-bis (2,2,6 , 6-tetramethyl-4-piperidyloxycarbonyl) pentane and the like. These can be used alone or in combination of two or more. These hindered amine compounds are effective for mold contamination, weather resistance, and thermal stability.

(B) a molecular weight of 550 or more and a melting point of 10
Examples of the phosphite compound at 0 ° C. or higher include 2,2-methylbis (4,6-di-t-butylphenyl) octyl phosphite and bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite. , Screw (2,
6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis-nonylphenylpentaerythritol diphosphite and the like. These can be used alone or in combination of two or more. These phosphite compounds are effective for mold contamination, weather resistance, and thermal stability.

As the hindered phenolic compound having a molecular weight of 500 or more and a melting point of 50 ° C. or more having an ester group or a cyanurate group in the molecule of (c), n-octadecyl-3- (4-hydroxy 3 ′, 5′- Di-t-butylphenol) propionate, tetrakis [methylene-3 (3 ′, 5′-di-t-butyl-4′-hydroxyphenylpropionate) methane, 3,9-bis [1,
1, -dimethyl-2- {β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy}
Ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,3,5-tris (3 ′,
5'-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (2 ', 6'-dimethyl-4'-tert-butyl-3-hydroxybenzyl) isocyanurate, 1, 3,5-tris [β-
(3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate and the like. These can be used alone or in combination of two or more. These hindered phenol compounds are effective in mold contamination, weather resistance and thermal stability.

As the ester lubricant having two or more ester groups in the molecule (d) and having a molecular weight of 600 or more,
Esters of polyhydric alcohols and carboxylic acids such as pentaerythritol tetrastearate, pentaerythritol tristearate, trimethylolpropane tristearate, hardened tallow, fatty acid esters of polyglycerin,
Examples thereof include esters and ester oligomers of polyhydric alcohol and polycarboxylic acid.

The thermoplastic resin composition of the present invention may further contain, if necessary, an antioxidant, a heat stabilizer, an ultraviolet absorber, a pigment, an antistatic agent and a lubricant, as well as the above stabilizer and / or lubricant. Can be used as appropriate. For example, phenol-based, sulfur-based, phosphorus-based, hindered amine-based stabilizers, antioxidants, benzophenone-based, benzotriazole-based ultraviolet absorbers and organopolysiloxanes used in styrene-based resins, aliphatic hydrocarbons, higher fatty acids and Internal lubricants and external lubricants such as esters of higher alcohols, amides or bisamides of higher fatty acids and modified products thereof, amide oligomers composed of polyamines and polycarboxylic acids, and metal salts of higher fatty acids. These stabilizers can be used alone or in combination of two or more.

The thermoplastic resin composition of the present invention may further comprise another styrene resin, for example, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-styrene-α-methylstyrene copolymer, acrylonitrile-α
-Methylstyrene copolymer, acrylonitrile-methylmethacrylate-α-methylstyrene copolymer, styrene-maleimide copolymer, styrene-maleic anhydride copolymer, styrene-methyl methacrylate copolymer, etc. Preferably, they can be mixed and used at 40% by weight or less.

Further, it is also possible to mix polycarbonate resin, polyvinyl chloride resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyamide resin and the like. The resin mixture of the acrylate copolymer (I), the maleimide copolymer (II), and the graft copolymer (III) of the present invention varies depending on the production method. It can be manufactured by mixing in a state of a solution, a powder, a pellet or the like or a combination thereof.

When polymer powder is recovered from the latex of the acrylate copolymer (I), the latex of the maleimide copolymer (II) and the latex of the graft copolymer (III) after polymerization, Methods, such as calcium chloride, magnesium chloride,
The latex was coagulated by adding an alkaline earth metal salt such as magnesium sulfate, an alkali metal salt such as sodium chloride and sodium sulfate, and an inorganic acid and an organic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, and acetic acid. Thereafter, it can be carried out by a method of dehydrating and drying. Also, a spray drying method can be used. A part of the amount of the stabilizer used may be added in the form of a dispersion to a latex or slurry of these resins.

The thermoplastic resin composition of the present invention can be prepared from an acrylate copolymer (I), a maleimide copolymer (II), a graft copolymer (III) alone or a mixture of two or more of these. The above-mentioned stabilizer, if necessary, a lubricant, a pigment and the like are blended with the resulting powder and pellets, and can be kneaded with a known melt kneader such as a Banbury mixer, a roll mill, a single-screw extruder, or a twin-screw extruder. . The thermoplastic resin composition of the present invention can be molded by a known molding method such as injection molding, extrusion molding, blow molding, and vacuum molding.

[0049]

EXAMPLES Hereinafter, the present invention will be described with reference to specific examples, but these examples do not limit the present invention. In the examples, "parts" indicates parts by weight, and "%" indicates% by weight. Examples and Comparative Examples Production of Acrylic Ester Copolymer (I) Production of Copolymer (Ia) 250 parts of pure water in a reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer inlet, and a thermometer. 1.0 part sodium dioctylsulfosuccinate, 0.5 part sodium formaldehyde sulfoxylate, EDTA
0.01 parts and 0.0025 parts of ferrous sulfate were charged.

The reactor was stirred at 65 ° C. under a nitrogen stream.
Temperature. After reaching 65 ° C, 75 parts of BA, AN
23 parts, St 2 parts, tDM 0.32 parts, CHP
0.4 part of the mixture was added dropwise continuously over 7 hours. Also,
Sodium dioctyl sulfosuccinate was added in an amount of 0.5 part at 1 hour of polymerization time and 0.5 part at 3 hours. After completion of the dropwise addition, stirring was continued at 65 ° C. for 1 hour to terminate the polymerization, thereby producing a copolymer (Ia). The polymerization conversion, reduced viscosity, gel content, and glass transition temperature (Tg) were measured and the results are shown in Table 1.

Polymerization of Copolymer (Ib) In the same manner as for the copolymer (Ia), the monomer was converted to BA 2
7 parts, 2EHA 25 parts, MMA 5 parts, AN 33
Part, St10 part and tDM 0.25 part, CHP 0.
As 4 parts, a copolymer (Ib) was produced. Similarly, Table 1 shows the results.

[0052]

[Table 1]

2. Production of maleimide-based copolymer (II) Production of copolymer (II-a) 250 parts of pure water, dioctyl in a reactor equipped with a stirrer, reflux condenser, nitrogen inlet, monomer inlet, and thermometer Sodium sulfosuccinate 1.0 part, sodium formaldehyde sulfoxylate 0.5 part, EDTA
0.01 parts and 0.0025 parts of ferrous sulfate were charged.

85 ° C. under a nitrogen stream while stirring the reactor
Temperature. After reaching 65 ° C, 15 parts of PMI, AN
24 parts, 31 parts of St, 30 parts of MMA (the amount of St + MMA in the monomer mixture is 53 mol%), tDM 0.
A mixture of 35 parts and 0.4 parts of CHP was continuously added dropwise over 7 hours. Also, 0.5 part of sodium dioctyl sulfosuccinate was added at the first hour of polymerization time and 0.5 part at the third hour. After completion of the dropwise addition, stirring was continued at 65 ° C. for 1 hour to terminate the polymerization, thereby producing a copolymer (II-a). Table 2 shows the results.

Polymerization of copolymer (II-b) In the same manner as for copolymer (II-a), the monomer was
30 parts, AN 15 parts, St 25 parts, MMA 25
Parts, BA 5 parts (St + MMA amount in the monomer mixture is 5 parts
0 mol%), and 0.26 parts of tDM, CHP 0.4
As a part, a copolymer (II-b) was produced. Similarly, Table 2
Shows the results.

Polymerization of copolymer (II-c) In the same manner as for copolymer (II-a), 20 parts of PMI,
A copolymer (II-c) was produced by using 25 parts of AN, 55 parts of St (the amount of St in the monomer mixture was 48 mol%), 0.31 part of tDM, and 0.4 part of CHP. Similarly, Table 2 shows the results.

[0057]

[Table 2]

3. Production of Rubber Polymer Production of Rubber Polymer (B-1) As a first step, an unexpanded rubber polymer (B-1) required for enlarging the rubber polymer (A-1) was produced.
In a 100 L polymerization machine, 230 parts of pure water, potassium persulfate
0.2 parts and 0.15 parts of tDM were charged.

After removing the air in the polymerization machine with a vacuum pump,
0.6 part of sodium oleate, 2 parts of sodium rosinate and 100 parts of butadiene were charged. The temperature of the system was raised to 60 ° C. to initiate polymerization. The polymerization was completed in 25 hours. The polymerization conversion was 96%, and the unexpanded rubber polymer (B
The particle size in -1) was 83 nm. Production of Rubber Polymer (B-2) In a reactor equipped with a stirrer, reflux condenser, nitrogen inlet, monomer inlet, and thermometer, 200 parts of pure water, 0.2 part of sodium palmitate, and sodium formaldehyde sulfo were added. 0.5 parts of xylate, 0.01 parts of sodium ethylenediaminetetraacetate, 0.0025 of ferrous sulfate
The department was charged. While stirring the reactor, 55
The temperature was raised to ° C. After reaching 55 ° C, 85 parts of BA, B
MA 10 parts, 2EHA 5 parts, TAC 1.5 parts, CHP
0.3 parts of the monomer mixture was added dropwise over 7 hours. 1 drop of sodium palmitate during 7 hours of monomer mixture
0.3 parts after 3 hours, 0.5 parts after 3 hours and 0.5 parts after 5 hours. After completion of the dropwise addition, stirring was continued at 55 ° C. for 1 hour to terminate the polymerization. The polymerization conversion was 98%, and the particle size of the unexpanded rubber polymer (B-2) was 110 nm.

Production of Rubber Polymer (A-1) As a second step, the acid group-containing latex (S) necessary for enlarging the unexpanded rubber polymer (B) to the rubber polymer (A) is as follows: It was manufactured as follows. 200 parts of pure water, 0.6 parts of sodium dioctylsulfosuccinate, 0.5 parts of sodium formaldehyde sulfoxylate, 0.5 parts of ethylenediamine 0.01 parts of sodium acetate and 0.0025 parts of ferrous sulfate were charged.

The reactor was stirred at 70 ° C. under a nitrogen stream.
Temperature. After reaching 70 ° C., 2EHMA 25
Parts, BA 5 parts, tDM 0.1 parts, CHP 0.15
Part of the monomer mixture was added dropwise over 2 hours, and then BMA
50 parts, 2EHA 4 parts, MAA 16 parts, tDM
0.25 part and 0.15 part of CHP were added dropwise over 4 hours. After completion of the addition, stirring was continued at 70 ° C. for 1 hour to terminate the polymerization, thereby obtaining an acid group-containing latex (S-1). Table 3 shows the results.

[0062]

[Table 3]

As a third step, a rubber polymer (A-1) was produced by using the previously produced unexpanded rubber polymer (B-1) and the acid group-containing latex (S-1). To 100 parts (solid content) of the latex of the unexpanded rubber polymer (B-1), 3.5 parts (solid content) of the acid group-containing latex (S-1) was added at 60 ° C.
After the addition, stirring was continued for one hour to enlarge the rubber, thereby producing a rubber polymer (A-1). The particle size of the rubber polymer (A-1) was 420 nm.

Production of Rubber Polymer (A-2) Using the monomer mixture shown in Table 3 in the same manner as for the acid group-containing latex (S-1), the acid group-containing latex (S-2)
Was manufactured. Rubber polymer (A-2), except that 2.0 parts (solid content) of acid group-containing latex (S-2) is used.
It was produced in the same manner as for the rubber polymer (A-1). After adding 2 parts (solid content) of the acid group-containing latex (S-2) at 60 ° C. to 100 parts (solid content) of the latex of the unexpanded rubber polymer (B-1), stirring was continued for 1 hour to enlarge. , And a rubber polymer (A-2). Rubber polymer (A-
The particle size of 2) was 640 nm.

Production of rubber polymer (A-3) Using the unexpanded rubber polymer (B-2) and the acid group-containing latex (S-1) produced earlier, the rubber polymer (A-3) was prepared. Manufactured. Latex 1 of unexpanded rubber polymer (B-2)
2. An acid group-containing latex (S-1) is added to 00 parts (solid content).
After adding 2 parts (solid content) at 60 ° C., stirring was continued for 1 hour to enlarge the product, thereby producing a rubber polymer (A-3). The particle size of the rubber polymer (A-3) was 360 nm.

4. Production of Graft Copolymer (III) Production of Graft Copolymer (III-a) 280 parts of pure water, rubber in a reactor equipped with a stirrer, reflux condenser, nitrogen inlet, monomer inlet, and thermometer 65 parts (solid content) of polymer (A-1), 0.3 parts of sodium formaldehyde sulfoxylate, EDTA 0.0
1 part and 0.0025 part of ferrous sulfate were charged. The reactor was heated to 60 ° C. under a nitrogen stream while stirring. 6
After reaching 0 ° C., AN 8 parts, St 14 parts, MMA 13
, CHP 0.3 part was dropped continuously over 5 hours. After completion of the dropwise addition, stirring was continued at 60 ° C. for 2 hours to terminate the polymerization, thereby obtaining a graft polymer (III-a). Table 4 shows the results.

Production of Graft Copolymer (III-b) In the same manner as for the graft copolymer (III-a), 70 parts of the rubber polymer (A-2) was added to 8 parts of AN, 22 parts of St,
HP was polymerized in 0.3 part, and the graft copolymer (III
-B) was prepared. Table 4 shows the results. Production of Graft Copolymer (III-c) In the same manner as for the graft copolymer (III-a), 60 parts of the rubber polymer (A-3) was added to 10 parts of AN, 10 parts of St,
Polymerization was carried out with 20 parts of MMA and 0.3 parts of CHP to produce a graft copolymer (III-c). Table 4 shows the results.

Production of Graft Copolymer (III-d) In the same manner as for the graft copolymer (III-a), 50 parts of the rubber polymer (B-1) were added to 10 parts of AN, 25 parts of St,
Polymerization was carried out with 15 parts of MMA and 0.3 parts of CHP to produce a graft copolymer (III-d). Table 4 shows the results. Production of Graft Copolymer (III-e) In the same manner as for the graft copolymer (III-a), 50 parts of the rubber polymer (B-2) was added to 10 parts of St and MMA 40
Part and CHP 0.3 part to produce a graft copolymer (III-e). Table 4 shows the results.

[0069]

[Table 4]

5. Production of thermoplastic resin composition 1. latex of copolymers (Ia) and (Ib) produced in Maleimide copolymer (II-
3. latexes of a), (II-b) and (II-c) and Graft copolymers (III-a), (III-b) produced in
The latexes (III-c), (III-d), and (III-e) were mixed at a predetermined ratio shown in Table 5, and after adding a phenolic antioxidant, calcium chloride was added for coagulation. The coagulated slurry was heat-treated, dehydrated and dried to obtain a resin composition powder of a mixture of an acrylate copolymer (I), a maleimide copolymer (II) and a graft copolymer (III). Next, the obtained resin was added with a predetermined stabilizer shown in Table 5,
A lubricant was blended and uniformly blended with a 20 L blender manufactured by Tabata Co., Ltd. Further, the mixture was melt-kneaded at 250 ° C. with a 40 m / m uniaxial vent extruder manufactured by Tabata Co., Ltd. to produce pellets of a thermoplastic resin composition (Examples 1 to 1).
6).

In the same manner as described above, a powder of a resin composition containing a copolymer (Ia), a copolymer (II-c), and a graft copolymer (III-a) is obtained. And a lubricant, and pellets of the thermoplastic resin composition were obtained in the same manner as described above (Comparative Example-1 to Comparative Example-4). Comparative Example 2 could not be powdered during solidification and heat treatment, and was not subjected to the subsequent tests. The properties of each thermoplastic resin composition were evaluated, and the results are shown in Table 5.

[Calculation of Tg (Glass Transition Temperature)] The Tg of the copolymer (I) was calculated from the Tg of the homopolymer of each component (described in “Polymer Handbook”) using the Fox equation. [Measurement of Gel Content] Calcium chloride was added to the latex of the copolymer (I) to coagulate it. The coagulated slurry was heat-treated, dehydrated and dried to obtain a 2% methyl ethyl ketone solution, left at 23 ° C. for 24 hours, filtered through a 100-mesh wire gauze, dried, and measured.
(Weight of filtration residue / original weight) × 100%. [Measurement of Reduced Viscosity] Calcium chloride was added to the latex of the copolymer (I) or the copolymer (II) for coagulation. The reduced viscosity was measured at 30 ° C. as a 0.3 g / dl N, N-dimethylformamide solution of a resin powder obtained by subjecting the coagulated slurry to heat treatment and dehydration drying. [Graft Ratio of Graft Copolymer] The powder of the graft copolymer (III) was dissolved in methyl ethyl ketone and centrifuged to obtain a soluble portion and an insoluble portion of methyl ethyl ketone. The graft ratio was specified from the ratio of the insoluble component to the soluble component. [Particle size of rubber polymer] For rubber polymer latex,
The measurement was performed using a Microtrac particle size analyzer manufactured by Nikkiso Co., Ltd.

[Conversion rate at the time of polymerization] The conversion rate at the time of polymerization was calculated from the solid concentration and the amount of solids relative to the amount of the added monomer. [Characteristics of Thermoplastic Resin Composition] The HIC value of the molded article shown in FIG.
The change in acceleration-time when a load was applied was measured and calculated [index]. In addition, the presence or absence of cracks on the top surface of the molded body after the test was evaluated as ◎ (no cracks at all), ○ (cracked without penetrating), ×
(With cracks penetrated).

The impact resistance was evaluated by IZOD impact strength. The IZOD impact strength is based on the ASTM D-256 standard (1
/ 4 inch thickness) at 23 ° C. (unit: kgcm / cm). Tensile strength (unit: kg / cm
2) The tensile elongation (unit:%) was evaluated at 23 ° C. using a No. 1 dumbbell according to ASTM D638 standard.

Heat resistance (HDT) is as per ASTM D648
Was evaluated at a heat deformation temperature of 18.6 kg / cm2 load.
(Unit: ° C.) The fluidity was measured using a FAN100B injection molding machine manufactured by FANUC CORPORATION at a cylinder temperature of 250 ° C. and an injection pressure of 135.
The flow length (unit: mm) of the resin in a spiral mold having a thickness of 3 mm at 0 kg / cm 2 was evaluated.
The smaller the HIC value and the larger the other characteristics, the better the other characteristics. The test pieces used for the above-mentioned IZOD impact strength, tensile strength, tensile elongation, bending strength, flexural modulus and heat resistance are FAS100B manufactured by FANUC Corporation.
Using an injection molding machine, molding was carried out at a cylinder temperature of 250 ° C., and it was subjected to evaluation.

The appearance of the molded product is 2 mm (thickness) × 100
（(extremely good), ○ (good), × for burnt, uneven color, flow mark, and dirt on a flat plate of mm x 150 mm
(Evil), comprehensive evaluation.

[0077]

[Table 5]

[Abbreviation] BA: butyl acrylate 2EHA: 2-ethylhexyl acrylate MMA: methyl methacrylate AN: acrylonitrile St: styrene tDM: t-dodecylmercaptan CHP: cumene hydroperoxide PMI: N-phenylmaleimide 2EHMA: 2-ethylhexyl methacrylate MAA: methacrylic acid BMA: butyl methacrylate i-1: MARK LA-77 manufactured by Adeka Argus; melting point 81-86 ° C, molecular weight 480, bis (2,2,6,6)
-Tetramethyl-4-piperidinyl) sebacate i-2: MARK LA-57 manufactured by Adeka Argus; melting point 132 ° C, molecular weight 790, 1,2,3-tetrakis (2,2,6,6-tetramethyl-4-) Piperidyloxycarbonyl) butane i-3: TINUVIN 622L manufactured by Ciba Geigy
D; softening point 55-70 ° C., molecular weight 3000 or more, dimethyl succinate-1- (2-hydroxylethyl) -4-hydroxy-2,2,6,6-tetramethyl-4-piperidine polycondensate; 4: TINUVIN 144 manufactured by Ciba-Geigy; melting point 146-150 ° C, molecular weight 685, bis (1,2,2,2- (3,5-di-t-butyl-4-hydroxybenzyl-2-n-butylmalonate) 6,6-pentamethyl-
4-piperidyl) a-5: Sanol LS744 manufactured by Sankyo; melting point 95-9
8 ° C., molecular weight 260, 2,6-dimethyl-4-piperidyl benzoate ro-1: MARK HP-10 manufactured by Adeka Argus Co .; melting point 148 ° C., molecular weight 566, 2,2,2-methylenebis (4,6-di-t -Butylphenyloctyl) phosphite b-2: MARK PEP-24 manufactured by Adeka Argus
G; melting point 165 ° C., molecular weight 604, bis (2,4-di-
t-butylphenyl) pentaerythritol diphosphite b-3: MARK PEP-36 manufactured by Adeka Argus Co .;
Melting point 237 ° C, molecular weight 633, bis (2,6-di-t-
Butyl-4-methylphenyl) pentaerythritol diphosphite b-4: MARK C manufactured by Adeka Argus Co .;
Molecular weight 346, diphenyloctyl phosphite C-1: MARK AO-20 manufactured by Adeka Argus; melting point 221 ° C, molecular weight 784, 1,3,5-tris (3 ′, 5′-di-t-butyl-4-hydroxy) Benzyl) isocyanurate C-2: MARK AO-50 manufactured by Adeka Argus; melting point 50 ° C, molecular weight 531, n-octadecyl-3-
(4'-hydroxy-3 ', 5'-t-butylphenol) propionate C-3: MARK AO-60 manufactured by Adeka Argus Co .; melting point 120 ° C, molecular weight 1178, tetrakis [methylene-
3 (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane ha-4: MARK AO-80 manufactured by Adeka Argus; melting point 125 ° C, molecular weight 741,3,9-bis [1 , 1-Dimethyl-2- {β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxyethyl}
2,4,8,10-tetraoxaspiro [5,5] undecane ha-5: Yoshitomi Pharmaceutical Yoshinox 250;
Molecular weight 234, 2,6-di-t-butyl-4-ethylphenol d-1: UNISTAR H-476 manufactured by NOF Corporation, melting point 63
° C, molecular weight 1192, pentaerythritol tetrastearate d-2: Riken Vita liquemar AZ-01; melting point 5
3 ° C., molecular weight 697 or more, stearic acid ester of polyglycerin d-3: Riken Vitamin Riquemar SL-800; melting point 53-59 ° C., molecular weight 538, stearyl stearate.

[0079]

From the results shown in Table 5, it can be seen that the thermoplastic resin compositions of the present invention represented by Examples 1 to 6 have particularly low HIC values of shaped bodies, have no cracks, and have high heat deformation resistance. High, excellent in moldability, and very good in appearance.

[Brief description of the drawings]

FIG. 1 is a plan view showing a molded body used for measuring an HIC value.

FIG. 2 is a sectional view taken along line AA of FIG.

[Explanation of symbols]

 1 body 2 vertical rib 3 horizontal rib

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08K 5/524 C08K 5/524 C08L 33/08 C08L 33/08 35/00 35/00 51/04 51/04 F-term (Reference) 4J002 AE055 BC04X BC04Y BC08X BC08Y BC09X BC09Y BC11X BC11Y BG04X BG04Y BG05X BG06X BG07Y BG10X BK00X BN03W BN06W BN12W BN14W BN15W BN16W CD19Y CM024 EH0066 EL126 EU057 EB14F EB14

Claims (5)

[Claims] 1. An acrylic acid ester of 40 to 85% by weight, a vinyl cyanide compound of 15 to 40% by weight, an aromatic vinyl compound of 45% by weight or less and a monomer copolymerizable therewith.
Tg obtained by polymerizing ３０30% by weight (total 100% by weight)
Is 20 ° C. or less and has a gel content of 10% by weight or less, 5 to 65 parts by weight of an acrylate-based copolymer (I), 5 to 50% by weight of a maleimide-based monomer, and 0 to 0% of an alkyl (meth) acrylate. 50% by weight, aromatic vinyl compound 0 to 85
% By weight, 0 to 40% by weight of a vinyl cyanide compound, and 0 to 20% by weight of a monomer copolymerizable therewith (total 100%).
% By weight) of a maleimide copolymer (II) 1
5 to 80 parts by weight, at least one rubber polymer (A) selected from diene rubber polymers, olefin rubber polymers, acrylic rubber polymers, and silicon rubber polymers having a volume average particle diameter of 50 to 1000 nm. 10) to 90% by weight of an aromatic vinyl compound, 10 to 90% by weight of at least one monomer selected from a (meth) acrylate ester and a vinyl cyanide compound in the presence of 10 to 90% by weight; 0 to 30% by weight of a monomer copolymerizable with
A resin composition comprising 20 to 85 parts by weight of a graft copolymer (III) having a graft ratio of 10 to 70% by weight obtained by polymerizing 10 to 90 parts by weight of a monomer mixture (0% by weight); And a reduced viscosity (30 ° C., in an N, N-dimethylformamide solution) of the methyl ethyl ketone soluble component in the resin composition is 0.3 to 1.2 dl / g, and a rubber polymer content is 5
To 50 parts by weight of the resin composition, and 0.01 to 5 parts by weight of at least one of the following stabilizers (a), (b) and (c) and / or the following lubricant (d) ) 0.
A thermoplastic resin composition comprising 0.05 to 8 parts by weight. (A) a molecular weight of 450 or more having an ester group in the molecule;
And a hindered amine stabilizer having a melting point of 50 ° C. or higher (b) a phosphite stabilizer having a molecular weight of 550 or higher and a melting point of 100 ° C. or higher (c) an ester group or a cyanurate group in the molecule having a molecular weight of 500 or higher and a melting point of 50 ° C. or higher Hindered phenol compound (d) An ester lubricant having two or more ester groups in the molecule and having a molecular weight of 600 or more. 2. The thermoplastic resin composition according to claim 1, wherein the maleimide-based copolymer (II) is a copolymer containing an aromatic vinyl compound and / or an alkyl (meth) acrylate in an amount of 49 mol% or more. 3. The maleimide-based copolymer (II) has a Tg of 100.
The thermoplastic resin composition according to claim 1, which is a copolymer at a temperature of from 200 to 200C. 4. An acrylic ester copolymer (I), a maleimide copolymer (II) and a graft copolymer (II)
2. The thermoplastic resin composition according to claim 1, wherein I) is a copolymer obtained by polymerization by an emulsion polymerization method. 5. A maleimide-based copolymer (II) comprising 5 to 50% by weight of a maleimide-based monomer, 5 to 50% by weight of an alkyl (meth) acrylate, 0 to 85% by weight of an aromatic vinyl compound, and vinyl cyanide. The thermoplastic resin composition according to claim 1, which is a copolymer obtained by polymerizing 0 to 40% by weight of a compound and 0 to 20% by weight of a monomer copolymerizable therewith (total 100% by weight).