JP2000212373A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having damping property and excellent in moldability (surface appearance). SOLUTION: This thermoplastic resin composition comprises (a) a (meth) acrylate-based copolymer having a glass transition temperature Tg A and (b) other copolymer having a glass transition temperature Tg B, and has at least one of tan δ peaks C other than the peaks of the Tgs A and B in a region of -30 to 100 deg.C in a viscoelastic spectrum.

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 vibration damping properties and excellent moldability (surface appearance).

[0002]

2. Description of the Related Art In recent years, noise and vibration in the living environment has become a social problem.
In the field of OA equipment, reduction of noise and vibration is required. For example, there is a need for materials that reduce vibration of radiator fans and engines in the automobile field, noise from motors such as refrigerators, washing machines, and vacuum cleaners in the home appliance field, and materials that reduce vibration of copiers, printers, and optical disks in the OA equipment field.

As means for imparting vibration damping properties, Japanese Unexamined Patent Publication No.
Japanese Patent No. 41443, Tg having 0 ° C. or higher (meth)
A combination of an acrylic ester copolymer and a thermoplastic resin, as disclosed in JP-A-9-249784,
A combination of a (meth) acrylate-based copolymer, a glutaric anhydride-based copolymer and a thermoplastic resin having a temperature of −40 ° C. or higher and lower than 0 ° C. has been proposed, while maintaining vibration damping properties. A molded article excellent in moldability (appearance surface properties) has not been obtained.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems and to provide a molded article having vibration damping properties and excellent moldability (surface appearance).

[0005]

Means for Solving the Problems In order to improve the molding processability (appearance surface properties), the present inventors have proposed a (meth) acrylic resin having a glass transition temperature of Tg (A). Acid ester copolymer (a) and glass transition temperature is Tg
In the composition comprising the other copolymer (B) (B),
It was considered necessary to have one or two or more tan δ peaks (C) in the viscoelastic spectrum different from the Tg (A) and Tg (B) peaks in the range of −30 to 100 ° C.

Further, in order to give a peak different from the peaks of Tg (A) and Tg (B), it is necessary to use a (meth) acrylate-based copolymer (a) and another copolymer (b)
It is thought that it is necessary to have a special phase structure in which the microphase separation of the matrix consisting of delicately controlled.

The present inventors have conducted intensive studies in order to obtain a molded article having vibration damping properties and excellent moldability (appearance surface properties) from the above viewpoint, and as a result, have completed the present invention.

That is, according to the present invention, the glass transition temperature is T
g (A) of a (meth) acrylate-based copolymer (a) and another copolymer (b) having a glass transition temperature of Tg (B), and peaks of Tg (A) and Tg (B) Tanδ peak (C) of viscoelastic spectrum different from
A thermoplastic resin composition having one or two or more in the range of 30 to 100 ° C. (Claim 1), and another copolymer (B),
Styrene resin, vinyl chloride resin, acrylic resin,
2. The method according to claim 1, comprising at least one of a polycarbonate resin, an amide resin, an ester resin and an olefin resin.
Thermoplastic resin composition (Claim 2), 10 to 90 parts by weight of a (meth) acrylate-based copolymer (a), 10 to 90 parts by weight of another copolymer (b), and a graft copolymer (C) The tan δ peak (C) of the viscoelastic spectrum which is composed of 0 to 80 parts by weight (total 100 parts by weight) different from the peaks of Tg (A) and Tg (B) is -30 to 100 ° C
The thermoplastic resin composition according to claim 1 having one or two or more in the range of (claim 3), and having a viscoelastic spectrum ta.
4. The thermoplastic resin composition according to claim 1, wherein the intensity of the peak (C) of nδ is 0.1 or more, wherein Tg (A) is 0 ° C. or less and Tg (B) is 80. ℃ or higher, and (meth) acrylic ester copolymer (a)
Is (meth) acrylic acid ester 40 to 85% by weight, vinyl cyanide compound 15 to 40% by weight, aromatic vinyl compound 0 to 45% by weight and other monomers copolymerizable therewith 0 to 30% by weight (Total 100% by weight) is a copolymer having a gel content of 10% by weight or less, and the other copolymer (b) is composed of 10 to 40% by weight of a vinyl cyanide compound and a maleimide-based monomer. A copolymer obtained by polymerizing 5 to 50% by weight of a polymer, 10 to 85% by weight of an aromatic vinyl compound, and 0 to 30% by weight (total 100% by weight) of other monomers copolymerizable therewith; The graft copolymer (c) is
A rubber polymer (A) comprising at least one of a diene rubber polymer, an olefin rubber polymer and an acrylic rubber polymer having a volume average particle diameter of 100 to 1000 nm, and 10 to 90% by weight of an aromatic vinyl compound; ) At least one of acrylic acid ester and vinyl cyanide compound
0% by weight and other monomers 0 to 3 copolymerizable therewith.
0% by weight (total 100% by weight) of the monomer mixture (B) is a graft copolymer having a graft ratio of 10 to 80% by weight, which is obtained by polymerizing a graft portion, and
The reduced viscosities (30 ° C., 0.3 g / dl N, N-dimethylformamide solution) of the methyl ethyl ketone soluble portion of the (meth) acrylic acid ester-based copolymer (a) and the other copolymer (b) are respectively The thermoplastic resin composition according to claim 1, 2, 3 or 4, wherein the content is 0.3 to 1.2 dl / g and the content of the rubber polymer (A) is 5 to 50% by weight in the resin. Item 5), wherein the rubber polymer (A) of the graft copolymer (C) is 5 to 50% by weight of an unsaturated acid (c) composed of at least one of acrylic acid, methacrylic acid, itaconic acid and crotonic acid; 50 to 95% by weight of one or more alkyl (meth) acrylates having 1 to 12 carbon atoms (d) and 0 to 40% by weight of other monomers copolymerizable with (c) and (d). Coagulation enlargement method using acid group-containing latex (S) obtained by polymerization The thermoplastic resin composition (Claim 6) according to Claim 3, 4 or 5, wherein the rubber polymer (A) is a rubber polymer produced and the content of the rubber polymer (A) is 5 to 50% by weight in the resin. Combined (c) rubber polymer (A)
Is 5 to 25% by weight of an unsaturated acid (c) composed of at least one of acrylic acid, methacrylic acid, itaconic acid and crotonic acid;
5 to 30% by weight of one or more alkyl acrylates (d-1) having 1 to 12 carbon atoms in the alkyl group, and 20 to 30% by weight of one or more alkyl methacrylates (d-2) having 1 to 12 carbon atoms in the alkyl group. 80% by weight and (c), (d-
1) an aromatic vinyl compound copolymerizable with (d-2),
Coagulation enlargement method using a monomer having two or more polymerizable functional groups in the molecule and an acid group-containing latex (S) obtained by polymerizing 0 to 40% by weight of at least one kind of a vinyl cyanide compound. The rubber polymer is a manufactured rubber polymer.
Or the thermoplastic resin composition according to claim 6 (claim 7), the (meth) acrylic ester copolymer (a) and the other copolymer (b), After polymerizing about 80% by weight, the (meth) acrylate copolymer (a) is polymerized, and then the remaining 20 to 100% by weight of the other copolymer (b) is polymerized. 1, 2,
The present invention relates to a thermoplastic resin composition according to claim 3, 4, 5, 6, or 7 (claim 8).

[0009]

DETAILED DESCRIPTION OF THE INVENTION The most important thing in the thermoplastic resin composition of the present invention is that a (meth) acrylate-based copolymer (a) having a glass transition temperature (hereinafter simply referred to as Tg) of Tg (A). (Hereinafter also referred to as copolymer (a)) and T
g is composed of another copolymer (b) of Tg (B) (hereinafter also referred to as copolymer (b)), and the tan δ peak of the viscoelastic spectrum different from the peaks of Tg (A) and Tg (B) (C) (hereinafter also simply referred to as peak (C)) is -30
One or two or more in the range of -100 ° C. The peak (C) may have at least one kind,
Two or more kinds may be present. Also, Tg (A), Tg
As a method for distinguishing the peak derived from the copolymer (B), that is, the peak derived from the copolymer (A) or the copolymer (B), from the peak (C) different from the peak (C), the copolymer (A) or the copolymer (B) By comparing the viscoelastic spectrum of the thermoplastic resin composition of the present invention with the peak of the viscoelastic spectrum obtained when each of the viscoelastic spectra is measured alone and the value of Tg determined from the Fox formula described below, Those skilled in the art can easily judge. In particular, in the case of the composite copolymer (d) described below, the value of Tg determined by the Fox equation may be referred to.

Unlike the peaks of Tg (A) and Tg (B), the peak (C) observed in the range of −30 to 100 ° C., preferably −20 to 90 ° C., more preferably −10 to 80 ° C. This is considered to be a peak generated by the refinement of the phase structure between the copolymer (a) and the copolymer (b). Observed temperature of peak (C) is less than -30 ° C or 100 ° C
Above this, vibration damping cannot be obtained.

[0011] More preferably, the intensity of the peak (C) is 0.1 or more, more preferably 0.2 or more. When the strength is less than 0.1, the vibration damping property tends to decrease.

The intensity of the peak (C) can be determined by directly evaluating peaks appearing on the chart of the viscoelastic spectrum (even if there are overlapping peaks, waveform separation is not performed).

The copolymer (a) is a component used for exhibiting vibration damping properties.

The Tg (A) of the copolymer (a) determined from the Fox equation is 0 ° C. or lower, and −
It is preferably at most 10 ° C, particularly preferably at most -20 ° C. When the temperature exceeds 0 ° C., the vibration damping property tends to decrease.

Gel content of copolymer (a) [Gel content is defined as 23% of a 2% solution using methyl ethyl ketone as a solvent.
At 24 ° C. for 24 hours, and filtered through a 100-mesh wire gauze to dry the filtration residue. (Weight of filtration residue / original weight) × 10
Is 0% or less, more preferably 5% or less, and particularly preferably 3% or less, from the viewpoint of moldability and appearance. If it exceeds 10%, the moldability and appearance tend to decrease.

Further, the reduced viscosity of the methyl ethyl ketone soluble portion of the copolymer (a) (30 ° C., 0.3 g / dl N, N
-Dimethylformamide solution) is 0.3-1.2 dl
/ G, more preferably 0.4 to 1.0 dl / g, especially 0.1 to 1.0 dl / g.
It is preferably from 45 to 0.9 dl / g. 0.3dl
/ G, the impact resistance tends to decrease,
If it exceeds 1.2 dl / g, the moldability and appearance tend to be reduced.

The copolymer (a) is not particularly limited. For example, (meth) acrylic acid esters 40 to 85
%, More preferably 50 to 80%, especially 55 to 75%, 15 to 40% of the vinyl cyanide compound, furthermore 20 to 35%
%, Especially 20 to 30%, and the aromatic vinyl compound is 0 to
45%, more preferably 0 to 30%, especially 2 to 25% and 0 to 30% of other monomers copolymerizable therewith, more preferably 0 to 20 parts, especially 0 to 10 parts (total 100% ) Is preferred. When the amount of the (meth) acrylate is less than 40%, the vibration damping property tends to decrease, and when it exceeds 85%, the heat resistance and the moldability tend to decrease, and the film tends to peel off. When the content of the vinyl cyanide compound is less than 15%, the vibration damping property is reduced and the film tends to be easily peeled off, and when it exceeds 40%, the film tends to be easily peeled. If the amount of the aromatic vinyl compound exceeds 45%, the impact resistance tends to decrease.

Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate. , 2-hydroxylethyl (meth) acrylate, glycidyl (meth) acrylate and the like. These are used alone or in combination of two or more. Of these, butyl (meth) acrylate is preferred from an industrial point of view.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.
These are used alone or in combination of two or more. Of these, acrylonitrile is preferred from an industrial point of view.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, vinylnaphthalene, chlorostyrene, bromostyrene and the like. These are used alone or in combination of two or more. Of these, styrene is preferred from an industrial point of view.

The other monomers include acrylic acid, methacrylic acid, maleimide, N-phenylmaleimide and the like.

The copolymer (b) is a component used to develop the characteristics required for a material molded article actually used.

The Tg (B) of the copolymer (b) determined from the Fox equation is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, particularly preferably 100 ° C. or higher, from the viewpoint of heat resistance. If the temperature is lower than 80 ° C., the heat resistance tends to decrease.

The copolymer (b) is prepared from the reduced viscosity (30 ° C., 0.3 g / dl N, N-dimethylformamide) of methyl ethyl ketone soluble component in view of impact resistance, molding processability and appearance. Solution) is 0.3 to 1.2 dl / g, more preferably 0.35 to 1.0 dl / g, particularly 0.40 to dl / g.
It is preferably 0.9 dl / g. The same applies to the reduced viscosity of the composite copolymer (d) described later.

Examples of the copolymer (b) include thermoplastic resins such as styrene resins, vinyl chloride resins, acrylic resins, polycarbonate resins, amide resins, ester resins, and olefin resins. These are used alone or in combination of two or more.

The styrene resins include polystyrene, styrene-acrylonitrile copolymer, α-methylstyrene-acrylonitrile copolymer, styrene-α-
Methylstyrene-acrylonitrile copolymer, styrene-maleimide copolymer, styrene-maleimide-acrylonitrile copolymer, styrene-α-stilstyrene-
Maleimide-acrylonitrile copolymer, styrene-maleic anhydride copolymer and the like can be mentioned. As the styrene-based resin, from the viewpoint of impact resistance and processability, at least one monomer of a vinyl cyanide compound, an aromatic vinyl compound, a (meth) acrylate ester, and a maleimide compound (however, an aromatic vinyl compound And the reduced viscosity of the methyl ethyl ketone soluble matter (30 ° C., 0.3 g /
dl of N, N-dimethylformamide solution)
1.2 dl / g, further 0.35 to 1.0 dl / g,
In particular, those having 0.4 to 0.9 dl / g are preferable.

Examples of the vinyl chloride resin include polyvinyl chloride, a copolymer of not less than 80% of vinyl chloride and not more than 20% of another copolymerizable vinyl monomer such as ethylene, and post-chlorinated vinyl chloride. Is raised. The degree of polymerization of the vinyl chloride resin is from 300 to 2, from the viewpoint of impact resistance and processability.
000, even 400-1500, especially 450
It is preferably from 1,300.

Examples of the acrylic resin include a methyl methacrylate-ethyl acrylate copolymer and a methyl methacrylate-methacrylic acid copolymer having a Tg (Tg (B)) different from the Tg (A) of the copolymer (a). And methyl methacrylate-butyl acrylate copolymer. Among these, from the viewpoint of impact resistance and workability, the reduced viscosity of the methyl ethyl ketone soluble component (30
C, 0.3 g / dl N, N-dimethylformamide solution) in the range of 0.3 to 1.2 dl / g,
1.0 dl / g, particularly preferably 0.4 to 0.9 dl / g, is preferred.

Examples of the polycarbonate resin include bisphenol A polycarbonate.
In terms of impact resistance and workability, the number average molecular weight is 1,000.
~ 100,000, even 5,000 ~ 80,00
It is preferably 0, especially 10,000 to 60,000.

Examples of the ester resin include polyethylene terephthalate and polybutylene terephthalate. From the viewpoints of impact resistance and workability, the number average molecular weight is 1,000 to 100,000, and more preferably 5,000 to
80,000, particularly preferably 10,000 to 60,000.

As the amide resin, nylon 6,
Nylon 6, 6, nylon 12, and the like. In terms of impact resistance and workability, the number average molecular weight is 1,000 to 1
It is preferably from 000, more preferably from 5,000 to 80,000, especially from 10,000 to 60,000.

Examples of the olefin resin include polypropylene, polyethylene, and cyclic polyolefin.

Further, a polymer alloy using one or more thermoplastic resins of the above-mentioned styrene resin, vinyl chloride resin, acrylic resin, polycarbonate resin, amide resin, ester resin, and olefin resin, for example, styrene Alloys of acrylonitrile copolymer and vinyl chloride resin, alloys of styrene-acrylonitrile copolymer and polycarbonate, alloys of styrene-acrylonitrile copolymer and nylon 6, alloys of polyethylene terephthalate and polycarbonate, polystyrene and polyphenylene Alloys with oxides can also be used.

The copolymer (b) is a vinyl cyanide compound at 10 to 40%, further 15 to 35%, a maleimide monomer at 5 to 50%, further 10 to 45%, an aromatic vinyl compound. 10 to 85%, more preferably 20 to 75% and 0 to 30% of other monomers copolymerizable therewith, furthermore 0 to 20% (total 100%), and the aromatic vinyl compound is 49 mol%. It is preferably a copolymer (b-A) obtained by polymerizing the monomer mixture contained above. When the content of the vinyl cyanide compound is less than 10%, the vibration damping property is reduced to 40%.
%, The molding processability and appearance are less than 5% when the maleimide monomer is less than 50%, and the heat resistance is more than 50%.
When the amount of the aromatic vinyl compound is less than 10%, the molding processability and appearance tend to decrease, and when the amount exceeds 85%, the impact resistance tends to decrease.

The ratio of the aromatic vinyl compound in the monomer mixture in the copolymer (b-A) is important, and the content in the monomer mixture is at least 49 mol%, more preferably at least 50 mol%. It is preferred that When the ratio of the aromatic vinyl compound is less than 49 mol%, the thermal stability, impact resistance, moldability, and appearance tend to decrease.

Acrylonitrile and methacrylonitrile are examples of vinyl cyanide compounds constituting the monomer mixture in the copolymer (II-A), and maleimide and N-methylmaleimide are examples of maleimide-based monomers.
N-ethylmaleimide, N-propylmaleimide, N-
Butylmaleimide, N-phenylmaleimide, N- (p
And (meth) acrylic acid and its methyl, ethyl,
(Meth) acrylic acid ester monomers such as propyl, butyl, 2-hydroxyethyl, 2-ethylhexyl, and glycidyl are used as aromatic vinyl compounds, such as styrene, α-methylstyrene, p-methylstyrene, and p-methylstyrene.
Isopropylstyrene, chlorostyrene, bromostyrene, vinylnaphthalene and the like can be mentioned. These are used alone or in combination of two or more. Among these, from an industrial point of view, acrylonitrile is used as a vinyl cyanide compound and N is used as a maleimide-based monomer.
Styrene is particularly preferred as the phenylmaleimide and the aromatic vinyl compound.

The graft copolymer (c) used in the present invention is obtained by graft copolymerizing a rubber polymer and a monomer, and is a component used for improving impact resistance. It is necessary to compatibilize with the coalescence (a) and / or the copolymer (b).

As the rubber polymer in the graft copolymer (C), the volume average particle diameter is 100 to 1000 nm, more preferably 100 to 900 nm, especially 150 to 800 nm.
The rubber polymer (A) is preferably composed of at least one of a diene rubber polymer, an olefin rubber polymer and an acrylic rubber polymer. If the volume average particle diameter of the rubber polymer (A) is less than 100 nm, the impact resistance tends to decrease, and if it exceeds 1000 nm, the impact resistance tends to decrease.

The rubber polymer (A) may be a mixture of two or more kinds having different volume average particle diameters.

The rubber polymer (A) is further added to 100 parts (solid content) of the rubber latex by an unsaturated acid (c) comprising at least one of acrylic acid, methacrylic acid, itaconic acid and crotonic acid. %, The number of carbon atoms of the alkyl group is 1 to 12
At least one alkyl (meth) acrylate (d) 50
To 95% and an acid group-containing latex (S) obtained by polymerizing 0 to 40% of another monomer copolymerizable with (c) and (d), and acrylic acid, methacrylic acid, itaconic acid, crotone Unsaturated acid (c) 5 comprising at least one acid
25%, 5 to 30% by weight of at least one alkyl acrylate (d-1) having 1 to 12 carbon atoms in the alkyl group, and at least one alkyl methacrylate (d-2) having 1 to 12 carbon atoms in the alkyl group. ) 20-80% and (c), (d-
1) an aromatic vinyl compound copolymerizable with (d-2),
It was manufactured by an agglomeration enlargement method using an acid group-containing latex (S) obtained by polymerizing a monomer having two or more polymerizable functional groups in a molecule and at least one kind of a vinyl cyanide compound at 0 to 40%. Rubber polymers are preferred.

Examples of the alkyl (meth) acrylate (d) having 1 to 12 carbon atoms in the alkyl group constituting the acid group-containing latex (S) include methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate. Examples thereof include alkyl methacrylates having 1 to 12 carbon atoms (d-2) such as alkyl acrylates having 1 to 12 carbon atoms (d-1), methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate. These are used alone or in combination of two or more. Also,
Other monomers copolymerizable with (c) and (d) include aromatic vinyl compounds such as styrene, α-methylstyrene and p-methylstyrene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; Monomers having two or more polymerizable functional groups in the molecule, such as triallyl cyanurate and allyl methacrylate. These are used alone or in combination of two or more.

Specific examples of the rubber polymer (A) include diene rubber polymers such as polybutadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, butadiene-acrylate rubber, hydrogenated styrene-butadiene rubber, and ethylene. Using olefin rubber polymers such as propylene rubber and ethylene-propylene-diene rubber, acrylic rubber polymers such as polyacrylate rubber and ethylene-acrylate rubber, and using these with acid group-containing latex (S). Examples include those that have been enlarged by the coagulation enlargement method, and may be used alone or in combination of two or more.

The graft copolymer (C) comprises the rubber polymer (A) and the aromatic vinyl compound in an amount of 10 to 90%, more preferably 15 to 85%, particularly 20 to 80%, and a (meth) acrylic acid ester and cyanide. 10 to 90%, more preferably 15 to 85%, especially 20%
~ 80% and other monomers copolymerizable therewith.
0%, preferably 0 to 20%, particularly 0 to 15% (total 100% by weight), and the graft ratio comprising the grafted portion obtained by polymerizing the monomer mixture (B) is 10 to 80%.
%, More preferably 20 to 70%, especially 25 to 65%, of the graft copolymer (c) (I). If the proportion and the graft ratio of the (meth) acrylate, vinyl cyanide compound and aromatic vinyl compound are out of the above ranges, impact resistance, molding processability, and appearance (surface properties) tend to decrease.

The (meth) acrylate constituting the monomer mixture (B) includes methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, -Hydroxylethyl (meth) acrylate, glycidyl (meth) acrylate and the like.
These are used alone or in combination of two or more. Of these, methyl methacrylate is preferred from an industrial point of view. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, p-isopropylstyrene, chlorostyrene, bromostyrene, and vinylnaphthalene. Is raised. These are used alone or in combination of two or more. Among them, acrylonitrile is preferable as the vinyl cyanide compound, and styrene is preferable from the industrial viewpoint as the aromatic vinyl compound. Other monomers include (meth) acrylic acid, maleimide, N-phenylmaleimide, and the like. These are used alone or in combination of two or more.

The graft copolymer (C) is a rubber polymer (A) from the viewpoint of impact resistance, molding processability, and appearance (surface properties).
10 to 90 parts, furthermore 20 to 85 parts, especially 30 to
80 parts, 10 to 90 parts of the monomer mixture (B), and 1
Those obtained by polymerizing 5 to 80 parts, particularly 20 to 70 parts (total 100 parts) are preferable.

The ratio of the copolymer (a) to the copolymer (b) of the thermoplastic resin composition of the present invention is Tg (A), Tg
The peak (C) of tan δ of the viscoelastic spectrum different from that of (B) may be in a range where one or two or more peaks are observed in a range of −30 to 100 ° C., and there is no particular limitation.
10 to 90 parts of copolymer (a), further 10 to 80 parts,
The amount of the copolymer (b) is preferably 10 to 90 parts, more preferably 20 to 90 parts (total 100 parts). Copolymer (a)
Is less than 10 parts, there is a tendency that the vibration damping property is reduced,
If the amount exceeds 90 parts, the heat resistance and the moldability tend to decrease. When the amount of the copolymer (b) exceeds 90 parts, the vibration damping property tends to decrease.
There is a tendency that the moldability decreases.

When the thermoplastic resin composition of the present invention contains the graft copolymer (c), the ratio of the copolymer (a), the copolymer (b) and the graft copolymer (c) Is 10 to 90 parts, more preferably 25 to 80 parts, especially 35 to 70 parts of the copolymer (a), 10 to 90 parts, more preferably 10 to 65 parts, particularly 15 to 50 parts of the copolymer (b). Parts, the graft copolymer (c) is preferably 0 to 80 parts, more preferably 10 to 65 parts, particularly preferably 15 to 50 parts (total 100 parts). When the amount of the copolymer (a) is less than 10 parts, the vibration damping property tends to decrease, and when it exceeds 90 parts, the heat resistance and the moldability tend to decrease. When the amount of the copolymer (b) exceeds 90 parts, the vibration damping property tends to decrease. When the amount is less than 10 parts, the heat resistance and the moldability tend to decrease. When the amount of the graft copolymer (c) exceeds 80 parts, the moldability and appearance tend to be reduced.

When the graft copolymer (c) is contained, the content of the rubber polymer (A) is contained in the resin, that is, the copolymer (a) constituting the thermoplastic resin composition of the present invention, Copolymer (b) and graft copolymer (c)
5% to 50%, and more preferably 5% to 40%, of the total 100%.

The thermoplastic resin composition of the present invention is a known thermoplastic resin and has an affinity for at least one of copolymer (a), copolymer (b) and graft copolymer (c). some stuff,
For example, polyester elastomer, silicone elastomer, polyurethane elastomer, polyolefin elastomer, styrene elastomer, etc.
To 50 parts, preferably 0 to 40 parts, more preferably 0
Up to 30 parts may be blended. If it exceeds 50 parts, the vibration damping property tends to decrease.

If the composition within the range of the present invention is obtained, the copolymer (a), the copolymer (b) and the graft copolymer (c) can be prepared by any polymerization method, initiator, chain transfer agent, surfactant May be used. For example, a known bulk polymerization method, solution polymerization method, suspension polymerization method, emulsion polymerization method, emulsion-
As long as the composition can be controlled within the scope of the present invention, such as a suspension polymerization method or an emulsion-bulk polymerization method, any one produced by any polymerization method may be used.

The method for producing the copolymer (a) and the copolymer (b) includes production stability (control of generation of scale and adhesion to a polymerization machine), separation of microphase (peak control of a viscoelastic spectrum). ), Copolymer (a) and copolymer (b)
From 0 to 80% of the copolymer (b), furthermore from 1 to 50
%, Particularly 2 to 30%, and then the copolymer (a) is polymerized, and then the remaining 2% of the copolymer (b)
0-100%, even 50-99%, especially 70-
A production method in which 98% is polymerized to obtain a composite copolymer (d) is preferred. According to this production method, generation of scale derived from the copolymer (a) and adhesion to the polymerization machine can be controlled. Further, from an industrial viewpoint, an emulsion polymerization method is preferred.

As a method for producing the graft copolymer (c), an emulsion polymerization method is preferred because the graft ratio can be easily controlled.

Further, as long as the one within the scope of the present invention can be obtained, any initiator, chain transfer agent or emulsifier may be used. For example, known initiators such as thermal decomposition initiators such as potassium persulfate, redox initiators such as Fe-reducing agent-organic peroxide, t-dodecyl mercaptan, n-dodecyl mercaptan, α-methylstyrene dimer, terpinolene, etc. Known chain transfer agents, fatty acid metal salt-based emulsifiers such as sodium oleate, sodium palmitate, and sodium rosinate, sulfonic acids such as sodium dodecylbenzenesulfonate, sodium alkylsulfonate having 12 to 20 carbon atoms, and sodium dioctylsulfosuccinate Known emulsifiers such as a metal salt emulsifier can be used.

The thermoplastic resin composition of the present invention comprises a generally well-known antioxidant, heat stabilizer, ultraviolet absorber, pigment,
Antistatic agents and lubricants can be used as needed. Phenol, sulfur, phosphorus, hindered amine stabilizers, antioxidants,
Benzophenone-based, benzotriazole-based UV absorbers and organopolysiloxanes, aliphatic hydrocarbons, esters of higher fatty acids with higher alcohols, amides or bisamides of higher fatty acids and their modified products, oligoamides, metal salts of higher fatty acids, etc. Lubricants, outer lubricants, and the like can be used as molding resins for higher performance. These can be used alone or in combination of two or more.

The resin composition comprising the copolymer (a) and the copolymer (b), or comprising the copolymer (a), the copolymer (b) and the graft copolymer (c) is prepared by the production of Depending on the method, these may be latex,
It can be manufactured by mixing in the form of a slurry, a solution, a powder, a pellet, or a combination thereof.

When polymer powder is recovered from the latex of the copolymer (a), the latex of the copolymer (b) and / or the latex of the graft copolymer (c) after polymerization, a usual method such as latex Add alkaline earth metal salts such as calcium chloride, magnesium chloride and magnesium sulfate, alkali metal salts such as sodium chloride and sodium sulfate, and inorganic and organic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and acetic acid After that, the latex is coagulated and then dehydrated and dried. Also, a spray drying method can be used.

A part of the used amount of a stabilizer or the like can 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 used in the form of powder, pellets, etc. consisting of the copolymer (a), the copolymer (b), the graft copolymer (c) alone or a mixture of two or more of these. On the other hand, the above-mentioned stabilizer, lubricant, pigment, etc. are blended, and a Banbury mixer, a roll mill, a single screw extruder,
Kneading can be performed by a known melt kneader such as a shaft 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.

[0060]

EXAMPLES Hereinafter, the present invention will be described with reference to specific examples, but these examples do not limit the present invention. In addition, the raw materials and evaluation methods used in the following Examples and Comparative Examples are summarized below.

BA: butyl acrylate 2EHA: 2-ethylhexyl acrylate AN: acrylonitrile St: styrene tDM: t-dodecyl mercaptan CHP: cumene hydroperoxide PMI: N-phenylmaleimide αMSt: α-methylstyrene BMA: butyl methacrylate MAA: methacryl Acid MMA: Methyl methacrylate TAC: Triallyl cyanurate EDTA: Disodium ethylenediaminetetraacetate Composite copolymer (D-1): Stirrer, reflux condenser, nitrogen inlet, monomer inlet, thermometer installed A reactor was charged with 250 parts of pure water, 1.0 part of dioctyl sodium sulfosuccinate, 0.5 part of sodium formaldehyde sulfoxylate, 0.01 part of EDTA, and 0.0025 part of ferrous sulfate.

While stirring the reactor, 65
The temperature was raised to ° C. After reaching 65 ° C., the first-stage monomer mixture PMI 1.5 parts, AN 2.4 parts, St 3.1
Parts, αMSt 3.0 parts (the amount of the aromatic vinyl compound in the monomer mixture is 50 mol%), tDM 0.035 parts, C
0.03 parts of HP was continuously added dropwise over 1 hour, and after completion of the addition, stirring was continued at 65 ° C. for 1 hour to partially polymerize the copolymer (b). Thereafter, 0.5 parts of sodium dioctylsulfosuccinate was added, and the second-stage monomer mixture BA 4
5.6 parts, AN 14.4 parts, tDM 0.21 parts, C
0.18 parts of HP was continuously dropped in 6 hours. After completion of the dropwise addition, stirring was continued at 65 ° C. for 1 hour to polymerize the copolymer (a). Further, 0.5 part of sodium dioctyl sulfosuccinate was added, and a third-stage monomer mixture PMI was added.
5 parts, AN 7.2 parts, St 9.3 parts, αMSt
9.0 parts (the amount of the aromatic vinyl compound in the monomer mixture is 5
0 mol%), 0.105 parts of tDM, 0.09 of CHP
Was continuously added dropwise over 3 hours. After completion of the dropwise addition, stirring was continued at 65 ° C. for 1 hour to polymerize the remaining components of the copolymer (b), and the polymerization was terminated to obtain a composite copolymer (d-1). Was evaluated. Table 1 shows the composition and the results.

Composite copolymer (d-2): The composite copolymer (d-1) was obtained except that the monomer mixture, composition and additional time (time for dropping the monomer mixture) shown in Table 1 were used. A composite copolymer (d-2) was produced and evaluated in the same manner as described above. Table 1 shows the results.

[0064]

[Table 1]

Copolymers (a-1) to (a-4): The same as the first stage of the composite copolymer (d-1) except that the monomer mixture, composition and additional time shown in Table 2 were used. Copolymers (a-1) to (a-4) were produced and evaluated in the same manner. Table 2 shows the results.

[0066]

[Table 2]

Copolymers (B-1) to (B-3): The same as the first stage of the composite copolymer (D-1) except that the monomer mixture, composition and additional time shown in Table 3 were used. Copolymers (B-1) to (B-3) were produced and evaluated in the same manner. Table 3 shows the results.

[0068]

[Table 3]

Rubber polymer (A-1): As the first step,
An unexpanded rubber polymer (B) required for enlarging the rubber polymer (A-1) was produced.

A 100 L polymerization machine was charged with 230 parts of pure water, 0.2 parts of potassium persulfate and 0.2 parts of tDM.

After the air in the polymerization machine was removed by 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 is 96.
%, The particle size of the unexpanded rubber polymer (B) was 85 nm.

In the second step, the unexpanded rubber polymer (B)
The acid group-containing latex (S) necessary for enlarging the rubber polymer (A) from the polymer was produced as follows.

A reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer inlet, and a thermometer was charged with pure water 20.
0 parts, sodium dioctyl sulfosuccinate 0.6
Parts, sodium formaldehyde sulfoxylate
0.5 parts, sodium ethylenediaminetetraacetate 0.0
1 part and 0.0025 part of ferrous sulfate were charged.

The reactor was stirred under a stream of nitrogen
The temperature was raised to ° C. After reaching 70 ° C., 25 parts of BMA,
A mixture of 5 parts of BA, 0.1 part of tDM, and 0.15 part of CHP was added dropwise over 2 hours, and then 50 parts of BMA,
BA 4 parts, MAA 16 parts, tDM 0.5 part, CH
0.15 parts of P was added dropwise over 4 hours.
Stirring was continued at 0 ° C. for 1 hour to terminate the polymerization, to obtain an acid group-containing latex (S-1), and the polymerization conversion was measured. Table 4 shows the composition and the results.

As a third step, 3.5 parts (solid content) of an acid group-containing latex (S-1) was added at 60 ° C. to 100 parts (solid content) of the previously produced unexpanded rubber polymer (B) latex. After the addition, stirring was continued for 1 hour to enlarge the rubber, thereby producing a rubber polymer (A-1). The particle size of the rubber polymer (A-1) was 450 nm.

Rubber Polymer (A-2): An acid group-containing latex (S-
An acid group-containing latex (S-2) was produced in the same manner as in 1). The rubber polymer (A-2) was produced in the same manner as the rubber polymer (A-1) except that 2.0 parts (solid content) of the acid group-containing latex (S-2) was used. That is, after adding 2 parts (solid content) of the acid group-containing latex (S-2) to 100 parts (solid content) of the latex of the unexpanded rubber polymer (B) at 60 ° C., stirring is continued for 1 hour to enlarge the product. Production of a rubber polymer (A-2) was performed. Rubber polymer (A-
The particle size of 2) was 620 nm.

Production of rubber polymer (A-3): As a first step, an unexpanded rubber polymer (C) necessary for enlarging the acrylate rubber polymer (A-3) was produced. .

A reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer inlet, and a thermometer was charged with pure water 20.
0 parts and 0.55 part of sodium palmitate were charged. The reactor was heated to 60 ° C. under a nitrogen stream while stirring. After heating, 0.3 parts of sodium formaldehyde sulfoxylate, 0.0025 parts of ferrous sulfate,
0.01 part of disodium ethylenediaminetetraacetate was charged. Furthermore, 98.5 parts of BA, 1.5 parts of TAC,
A mixture of 0.3 parts of CHP was added dropwise over 6 hours, and after completion of the addition, stirring was continued at 60 ° C. for 1 hour to complete the polymerization. 1.5 hours after the addition of the mixture, sodium palmitate was added.
3 parts of sodium palmitate 0.3 hours after dropping 4 hours.
Five parts were each added. The polymerization conversion was 98%, and the particle size of the unexpanded rubber polymer (C) was 92 nm.

In the second step, the unexpanded rubber polymer (C)
After adding 3.5 parts (solid content) of the acid group-containing latex (S-1) to 60 parts (solid content) of the latex at 60 ° C., stirring was continued for one hour to enlarge the rubber polymer (A-3). ) Was manufactured. The particle size of the rubber polymer (A-3) is 350
nm.

Table 4 shows the composition of the acid group-containing latex and the polymerization conversion.

[0082]

[Table 4]

Graft copolymer (c-1): 280 parts of pure water, rubber polymer (A-A) were placed in a reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer inlet, and a thermometer.
1) 65 parts (solid content), 0.3 part of sodium formaldehyde sulfoxylate, 0.01 part of EDTA, and 0.0025 part of ferrous sulfate were charged.

The reactor was stirred at 60 ° C. under a nitrogen stream.
Temperature. After reaching 60 ° C, 11 parts of AN, St
A mixture of 24 parts and 0.2 parts of CHP 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 and obtain a graft copolymer (C-1).
The polymerization conversion and the graft ratio were measured. Table 5 shows the composition and the results.

The graft copolymers (c-2) to (c)
5): Except for the rubber polymer, monomer mixture, and composition shown in Table 5, the same method as for the graft copolymer (C-1) was used.
A graft copolymer (C-2) was produced, and the same measurement was performed. Table 5 shows the composition and the results.

[0086]

[Table 5]

Polymer (e-1): polycarbonate (number average molecular weight: 23,000, Tg (value described in Polymer Handbook): 145 ° C.) Polymer (e-2): polyethylene terephthalate (number average molecular weight: 20) 000, Tg (value described in Polymer Handbook): 70 ° C) Polymer (e-3): Nylon 6 (number average molecular weight: 25,
000, Tg (value described in Polymer Handbook): 7
0 ° C) Polymer (e-4): polyvinyl chloride (polymerization degree 600, T
g (value described in Polymer Handbook): 80 ° C)

Examples 1 to 13 and Comparative Examples 1 to 4 Copolymer (a), copolymer (b), composite copolymer (d)
And the terax of the graft copolymer (c) are shown in Tables 6 and 7
And the phenolic antioxidant was added, and then calcium chloride was added for coagulation. The coagulated slurry is heat-treated, dehydrated and dried, and (a), (b), (c),
(D) Powder of the mixed resin composition was obtained. One part of ethylenebisstearylamide was blended and uniformly blended with a 20 L blender manufactured by Tabata Co., Ltd. Further, the mixture was melt-kneaded at 240 ° C. with a 40 m / m single screw extruder manufactured by Tabata Co., Ltd.
Pellets of the thermoplastic resin composition were produced. Using the obtained pellets, each property shown in [Characteristics of thermoplastic resin composition] described later was evaluated. The results are shown in Tables 6 and 7.

[0089]

[Table 6]

[0090]

[Table 7]

Examples 14 to 17 and Comparative Examples 5 to 8 The latex and the copolymer (e) of the copolymer (a), the copolymer (b) and the graft copolymer (c) were prepared according to the compositions shown in Table 8. After mixing, Example 14, Comparative Example 5 was 285 ° C, Examples 15 and 16, Comparative Examples 6 and 7 were 270 ° C, Example 17,
In Comparative Example 8, the temperature of a 40 m / m single screw extruder manufactured by Tabata Co., Ltd. was set to 180 ° C., and Examples 14 and 15, Comparative Example 5,
No. 6, 1 part of stearyl stearate was blended in place of ethylene bis stearyl amide.
A pellet of a thermoplastic resin composition was produced in the same manner as in Example 1 except that 1 part of dioctyltin maleate polymer, 3 parts of dibutyltin mercapto, and 2 parts of stearyl stearate were added instead of ethylene bisstearylamide, evaluated. Table 8 shows the results.

[0092]

[Table 8]

[Calculation of Tg] The Tg of the copolymer (a) and the copolymer (b) is calculated from the Tg of the homopolymer of each component (described in the polymer handbook or technical data of commercially available products) (however, PMI Uses 360 ° C) Fox
It was calculated using the equation.

[Measurement of Molecular Weight and Degree of Polymerization] The viscosity average degree of polymerization of polyvinyl chloride (Polymer (e-4)) was measured based on JIS standards. Polycarbonate (Polymer (Ho
1)), polyethylene terephthalate (polymer (ho
2)) and Nylon 6 (polymer (e-3)) were the values (number average molecular weight) of technical data of commercially available products.

[Measurement of Gel Content] Calcium chloride was added to the latex of the copolymer (a), the copolymer (b) or the composite copolymer (d) 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, and the filtration residue was dried. Weight) × 100.

[Measurement of Reduced Viscosity] Calcium chloride was added to the latex of the copolymer (a), the copolymer (b) or the composite copolymer (d) to coagulate it. The resin powder obtained by heat-treating, dehydrating and drying the coagulated slurry was used to obtain a resin powder having a concentration of 0.3 g / dl.
Was measured at 30 ° C. as an N, N-dimethylformamide solution.

[Graft Ratio of Graft Copolymer] The powder of the graft copolymer (c) 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.

[Volume Average Particle Diameter of Rubber Polymer] The latex of the rubber polymer (A) was measured using a Nicomp particle size analyzer manufactured by Pacific Science Corporation.

[Polymerization conversion rate] The conversion rate during polymerization was calculated from the solid content concentration.

[Scale Amount at the Time of Polymerization] Copolymer (A)
The latex of the copolymer (b) or the composite copolymer (d) was filtered with a 100-mesh sieve, and the scale amount was specified from the ratio of the remaining scale amount (dried) to the charged amount.

[Scale attached state at the time of polymerization] The easiness of peeling of the scale attached to the reactor was confirmed by rubbing with a finger.
Those that were easy to peel were evaluated as ○ (good), those that hardly peeled were evaluated as Δ, and those that hardly peeled were evaluated as x (bad).

[Characteristics of Thermoplastic Resin Composition] Impact resistance was evaluated by IZOD impact strength. The IZOD impact strength was measured at 23 ° C. by the method of ASTM D-256 standard (1/4 inch thickness) (unit: kgcm / cm).

The tensile strength (unit: kg / cm ² ) and tensile elongation (unit:%) were evaluated at 23 ° C. using a No. 1 dumbbell according to ASTM D638 standard.

The flexural strength (unit: kg / cm ² ) and flexural modulus (unit: kg / cm ² ) were evaluated at 23 ° C. by the method of ASTM D790.

The heat resistance (HDT) was evaluated at the heat deformation temperature of 18.6 kg / cm ² load according to ASTM D648 (unit: ° C.).

Test pieces used for the above-mentioned IZOD impact strength, tensile strength, tensile elongation, bending strength, flexural modulus and heat resistance were molded at a cylinder temperature of 250 ° C. using a FAS100B injection molding machine manufactured by FANUC CORPORATION. And subjected to evaluation.

The fluidity was measured by FAS10 manufactured by FANUC Co., Ltd.
Flow length (unit: mm) of resin in a 3 mm-thick spiral-shaped mold using a 0B injection molding machine at a cylinder temperature of 250 ° C. and an injection pressure of 1350 kg / cm ² .
Was evaluated.

The appearance of the molded article is shown in FIGS. 1 and 2 (the longitudinal rib 2 and the horizontal rib 3
Pillar cover for automobiles, the unit of numbers in the figure is m
m) Color unevenness, flow mark visually, ○ (good), △
(Slightly poor) and x (bad) were evaluated.

[Measurement of Viscoelastic Spectrum] 2 mm Thickness ×
2mm thickness x from 100mm x 150mm flat plate
Create a 5mm x 50mm strip and use it as Seiko Electronics Co., Ltd.
Mode, frequency 10Hz using DMS110
Was measured in the range of −100 to 200 ° C., and the peak temperature was evaluated.

The damping property was represented by a peak intensity of tan δ at a temperature of 25 ° C. A larger value indicates better damping.

[0111]

According to the results of Tables 6, 7 and 8, Examples 1 to 1 were obtained.
The thermoplastic resin composition of the present invention represented by No. 7 has particularly excellent vibration damping properties, high impact resistance, high heat deformation resistance, and excellent moldability.

[Brief description of the drawings]

FIG. 1 is a schematic view of an injection-molded article used for evaluating appearance of a molded article in Examples.

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 F-term (reference) 4J002 BB03X BB12X BC03X BC04X BC06X BC09X BD04X BD06X BG04W BG04X BG05W BG05X BG06W BG07W BH01X BH02X BN123 BN143 BN153 BN163 CD19W CF06X CF07X CG01CL

Claims (8)

[Claims] 1. A (meta) glass transition temperature of Tg (A)
An acrylic ester-based copolymer (a) and another copolymer (b) having a glass transition temperature of Tg (B);
(A) A thermoplastic resin composition having one or two or more tan δ peaks (C) in a viscoelastic spectrum different from the Tg (B) peak in the range of −30 to 100 ° C. 2. The method according to claim 1, wherein the other copolymer (b) comprises at least one of a styrene resin, a vinyl chloride resin, an acrylic resin, a polycarbonate resin, an amide resin, an ester resin and an olefin resin. Item 10. The thermoplastic resin composition according to Item 1. 3. A (meth) acrylate-based copolymer (a) in an amount of 10 to 90 parts by weight and another copolymer (b) in an amount of 10 to 9
0 parts by weight and 0 to 80 parts by weight (total 100 parts by weight) of the graft copolymer (c), and Tg (A), Tg
One or two peaks (C) of tan δ in the viscoelastic spectrum different from the peaks of (B) are in the range of −30 to 100 ° C.
The thermoplastic resin composition according to claim 1, which has at least one resin. 4. The tan δ peak (C) of the viscoelastic spectrum has an intensity of 0.1 or more.
The thermoplastic resin composition according to the above. 5. Tg (A) is 0 ° C. or less and Tg (B) is 8
0 ° C. or higher, and the (meth) acrylate-based copolymer (a) contains (meth) acrylate 40 to 85% by weight, a vinyl cyanide compound 15 to 40% by weight, and an aromatic vinyl compound 0 to 45% % By weight and other copolymerizable monomers 0 to 30% by weight (total 100% by weight) are copolymers having a gel content of 10% by weight or less. (B) a vinyl cyanide compound 10
To 40% by weight, 5 to 50% by weight of a maleimide monomer, 10 to 85% by weight of an aromatic vinyl compound and 0 to 30% by weight of other monomers copolymerizable therewith (total 100% by weight). Wherein the graft copolymer (c) is made of at least one of a diene rubber polymer, an olefin rubber polymer and an acrylic rubber polymer having a volume average particle diameter of 100 to 1000 nm. 10 to 90% by weight of the polymer (A) and the aromatic vinyl compound, 10 to 90% by weight of at least one of the (meth) acrylate and the vinyl cyanide compound, and 0 to 10 of other monomers copolymerizable therewith. 30% by weight (total 100% by weight) of a monomer mixture (B) is a graft copolymer having a graft ratio of 10 to 80% by weight comprising a graft portion,
And (meth) acrylate copolymer (a),
The reduced viscosity (30 ° C., 0.3 g / dl N, N-dimethylformamide solution) of the methyl ethyl ketone soluble portion of the other copolymer (b) is 0.3 to 1.2 dl / g, respectively.
And the content of the rubber polymer (A) is 5 to 50% by weight in the resin.
The thermoplastic resin composition according to claim 1, 2, 3, or 4. 6. The rubber copolymer (A) of the graft copolymer (C) is 5 to 50% by weight of an unsaturated acid (c) comprising at least one of acrylic acid, methacrylic acid, itaconic acid and crotonic acid. 50 to 95% by weight of one or more alkyl (meth) acrylates having 1 to 12 carbon atoms in the alkyl group and 0 to 40% by weight of other monomers copolymerizable with (c) and (d) 4. A rubber polymer produced by an agglomeration enlargement method using an acid group-containing latex (S) obtained by polymerizing the polymer, wherein the content of the rubber polymer (A) is 5 to 50% by weight in the resin. 6. The thermoplastic resin composition according to 4 or 5. 7. The rubber copolymer (A) of the graft copolymer (c) is 5 to 25% by weight of an unsaturated acid (c) comprising at least one of acrylic acid, methacrylic acid, itaconic acid and crotonic acid; 5 to 30% by weight of one or more alkyl acrylates (d-1) having 1 to 12 carbon atoms in the alkyl group, and 20 to 30% by weight of one or more alkyl methacrylates (d-2) having 1 to 12 carbon atoms in the alkyl group. 80% by weight and (c), (d-
1) an aromatic vinyl compound copolymerizable with (d-2),
Coagulation enlargement method using a monomer having two or more polymerizable functional groups in the molecule and an acid group-containing latex (S) obtained by polymerizing 0 to 40% by weight of one or more vinyl cyanide compounds. The rubber polymer is a manufactured rubber polymer.
Or the thermoplastic resin composition according to 6. 8. A (meth) acrylic ester-based copolymer (a) and another copolymer (b) are combined with another copolymer (b).
Is polymerized from 0 to 80% by weight, and then the (meth) acrylate-based copolymer (A) is polymerized, and then the remaining 20 to 100% by weight of the other copolymer (B) is polymerized. The thermoplastic resin composition according to claim 1, 2, 3, 4, 5, 6, or 7.