JP2003049042A - Thermoplastic resin composition excellent in matting property and molded article using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having a high level of matting property, impact resistance, and weather resistance, and particularly to heat capable of exhibiting good matting properties under a wide range of temperature conditions. Provided are a plastic resin composition and a molded article using the same. SOLUTION: A graft copolymer (A) in which a vinyl polymer is grafted onto a (meth) acrylate rubber polymer (G) which has been enlarged by an acid group-containing copolymer latex (K). ) 10 to 98 parts by mass, 2 to 50 parts by mass of a hydroxyl group-containing acrylic copolymer (B), and 0 to 80 parts by mass of another thermoplastic resin (F) [component (A),
(A total of 100 parts by mass of (B) and (F)); and a molded article using the same.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent matting properties, impact resistance, and weather resistance,
Particularly, it relates to a thermoplastic resin composition having a good matting property under a wide molding temperature condition.

[0002]

2. Description of the Related Art Improving the impact resistance of a resin material has a great industrial utility, such as expanding the use of the material and making it possible to reduce the thickness and size of molded products. . Therefore, various methods for improving the impact resistance of resin materials have been studied.

Among these materials, ABS resin, high-impact polystyrene resin, modified PPE resin, MBS resin reinforced polyvinyl chloride resin, etc. are examples of materials which have improved impact resistance by combining a rubber-like polymer with a hard resin. Has already been used industrially.

Particularly, as a resin material having good weather resistance by using a saturated rubber component such as (meth) acrylic acid alkyl ester rubber in a rubber-like polymer, for example, an ASA resin which is a weather resistant ABS resin has been proposed. It has been used for outdoor electrical equipment such as exterior parts for automobiles, vending machines and housing parts of radio wave meter bases.

In such a field in which the requirement of material specifications becomes stricter year by year, in JP-B-6-45663 and JP-B-3-66329, a diene rubber and a (meth) acrylate ester rubber are used. A thermoplastic resin containing a rubber-like polymer compounded with is a rubber-like polymer obtained by compounding a specific polyorganosiloxane and a (meth) acrylic acid ester-based rubber in JP-A-08-041149. Thermoplastic resin compositions containing coalesce have been proposed, and these were characterized by being excellent in impact resistance, weather resistance, and surface appearance.

However, recently, mainly in the fields of automobile interior parts such as dashboards and resin-made building materials for houses, there is an increasing demand for materials with significantly reduced gloss, so-called matting materials.

As a conventional matting method, a matte thermoplastic resin composition containing a graft polymer having a hydroxyl group has been proposed in JP-A Nos. 7-166021 and 7-173360. ing.

Further, Japanese Patent No. 2958232 proposes a thermoplastic resin composition containing a hydroxyl group-containing crosslinked acrylic polymer.

[0009]

[Patent Document 1] Japanese Patent Application Laid-Open No. 7-16602
The surface gloss of the thermoplastic resin composition obtained by the method proposed in Japanese Patent Application Laid-Open No. 1-173360 and Japanese Patent Application Laid-Open No. 7-173360 is an insufficient level for the matting property required in recent years, and a wider temperature condition is used. In particular, the phenomenon that the gloss value rises is observed in molding at high temperature.

Further, Japanese Patent No. 2958232 does not refer to any means capable of satisfying all the problems of the present invention in the embodiments.

The object of the present invention is to provide a high level of mattness,
It is to provide a thermoplastic resin composition having impact resistance and weather resistance, and particularly to provide a thermoplastic resin composition that exhibits good mattness under a wide temperature condition and a molded article using the same. is there.

[0012]

Means for Solving the Problems In the present invention, a polymer latex (K) containing an acid group is subjected to enlargement treatment (meta).
Graft copolymer (A) in which a vinyl polymer is grafted to an acrylic ester rubber polymer (G) 10
98 parts by mass, hydroxyl group-containing acrylic copolymer (B) 2 to
50 parts by mass and other thermoplastic resin (F) 0 to
80 parts by mass [total of components (A), (B) and (F) 1
00 parts by mass].

The present invention is also a sheet-shaped molded article made of the above thermoplastic resin composition.

In the present invention, "(meth) acryl" is a general term for acryl and methacryl.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The graft copolymer (A) of the present invention
The (meth) acrylic acid ester-based rubbery polymer (G) constituting (1) is a polymer having a (meth) acrylic acid ester monomer unit.

Examples of the (meth) acrylic acid alkyl ester monomer to be used include methyl methacrylate, ethyl methacrylate, propyl methacrylate and methacrylic acid n.
-Butyl, 2-ethylhexyl methacrylate, methacrylic acid alkyl esters such as lauryl methacrylate, and acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. Yes, preferably n-butyl acrylate and / or acrylic acid-
It is 2-ethylhexyl.

In these (meth) acrylic acid alkyl ester monomers, it is preferable to use a (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 12 carbon atoms as an essential component.

The (meth) acrylic ester type rubber-like polymer (G) is one or more of the above-mentioned (meth) acrylic acid ester monomer units in 100% by weight of the rubber-like polymer. Is preferably contained in an amount of 50 mass% or more. From the excellent weather resistance of the resulting thermoplastic resin composition,
It is preferably 60% by mass, more preferably 70% by mass or more.

The (meth) acrylic acid ester type rubbery polymer (G) may contain other monomer units in addition to the above-mentioned (meth) acrylic acid alkyl ester monomer units. Other monomers that can be used include
For example, aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, 2-hydroxyethyl methacrylate and glycidyl methacrylate, N, N-dimethylaminoethyl methacrylate and the like. And other (meth) acrylic acid esters having a functional group of (1), diene compounds such as butadiene, chloroprene and isoprene, acrylamide and methacrylamide, maleic anhydride, N-substituted maleimide and the like. These may be used alone or in combination of two or more depending on the purpose.

In the present invention, the monomer units constituting the (meth) acrylic acid ester rubbery polymer (G) include
It can contain two or more different polyfunctional monomer units. The two or more polyfunctional monomers used are not particularly limited as long as the structures are not very similar,
It is preferable to use a cross-linking agent and a graft crossing agent together.

When two or more polyfunctional monomer units are used, the impact resistance and the matting property are well balanced, and as a result, it is not necessary to increase the ratio of the rubber-like polymer in the thermoplastic resin composition. As a result, the surface hardness tends to be improved.

Examples of cross-linking agents and graft crossing agents that can be used are allyl compounds such as allyl methacrylate, triallyl cyanurate and triallyl isocyanurate,
Examples of di (meth) acrylic acid ester compounds such as divinylbenzene, dimethacrylic acid ethylene glycol diester, dimethacrylic acid propylene glycol diester, dimethacrylic acid 1,3-butylene glycol diester, and dimethacrylic acid 1,4-butylene glycol diester. Therefore, two or more of these are used in combination.
Preferred is a combination of an allyl compound as a graft crossing agent and a di (meth) acrylic acid ester compound as a cross-linking agent, more preferably allyl methacrylate as a graft crossing agent and dimethacrylic acid 1, as a cross-linking agent.
In combination with 3-butylene glycol diester.

By emulsion-polymerizing a mixture of a monomer mixture containing a (meth) acrylic acid ester monomer as an essential component and two or more kinds of polyfunctional monomers, a small particle size can be obtained. A (meth) acrylic acid ester-based rubbery polymer (g) can be prepared.

The weight average particle size of the (meth) acrylic acid ester type rubbery polymer (g) having a small particle size is not particularly limited, but enlargement due to the acid group-containing copolymer latex (K) easily progresses. Therefore, preferably 30 to 250
nm, more preferably 40 to 200 nm, and particularly preferably 50 to 150 nm. When the weight average particle diameter is 250 nm or less, enlargement due to the acid group-containing copolymer latex (K) is likely to proceed, and the resulting matte resin composition has improved matte properties.

The acid group-containing copolymer latex (K) used as a thickening agent is a copolymer having an acid group-containing monomer unit and, for example, a (meth) acrylic acid alkyl ester monomer unit. It is a latex containing.

Examples of the acid group-containing monomer include acrylic acid, methacrylic acid, itaconic acid and crotonic acid, and the (meth) acrylic acid alkyl ester has an alkyl group having 1 to 12 carbon atoms (meta). ) Acrylic acid alkyl esters are preferred. As this (meth) acrylic acid alkyl ester, the same ones as those used in the production of the (meth) acrylic acid ester rubber-like polymer (G) can be used.

However, for the purpose of obtaining a thermoplastic resin composition excellent in impact resistance, matteness and moldability, which is the object of the present invention, the glass transition temperature (T
g) is preferably low, and it is preferable to use an acrylic acid ester monomer. At this time, it is more preferable to use an acrylic acid alkyl ester monomer having an alkyl group having a large number of carbon atoms.

The mass ratio of the (meth) acrylic acid alkyl ester in the acid group-containing copolymer controls the weight average particle diameter of the (meth) acrylic acid ester-based rubbery polymer (G) obtained by enlargement. Since it is easy and the resulting thermoplastic resin composition has excellent matting properties, it is preferably 0.1 to 30% by mass, more preferably 10 to 30% by mass in the copolymer.
It is 25 mass%. Further, the weight average particle size of the acid group-containing polymer in the acid group-containing polymer latex is such that the stability of the latex when enlarging the small particle size (meth) acrylate rubber polymer (g) is large. 50 to 250 nm is preferable because it is excellent and it is easy to control the weight average particle diameter of the (meth) acrylate rubber (G) obtained by enlarging and the matting property of the obtained thermoplastic resin composition is excellent. .

In the (meth) acrylic acid ester-based rubbery polymer (G) of the present invention, the (meth) acrylic acid ester-based rubber polymer (g) having a small particle diameter is the above-mentioned acid group-containing copolymer latex ( It has been enlarged by K).

In the enlargement treatment, the acid group-containing copolymer latex (K) is added to the small particle size (meth) acrylic acid ester type rubbery polymer (g) latex obtained by emulsion polymerization as described above. The method of increasing the size is described in JP-A-50-25655 and JP-A-5-55655.
The method described in JP-A No. 8-61102 and JP-A No. 59-149902 can be used.

Acid group-containing copolymer latex (K) used
The appropriate usage amount of the small particle size depends on the properties of the small particle size (meth) acrylate rubber polymer (g) and the composition and properties of the acid group-containing copolymer latex (K). (Meth) acrylic ester type rubbery polymer (g) 10
It is preferably 0.1 to 10 parts by mass (solid content), more preferably 0.3 to 5 parts by mass (solid content), relative to 0 parts by mass (solid content). If this amount is 0.1 part or more, the enlargement tends to proceed, the matte property of the thermoplastic resin composition obtained is improved, and further the impact resistance tends to be improved. If it is 10 parts by mass or less, the matting property of the obtained thermoplastic resin composition tends to be improved.

In the case of performing the enlargement treatment, JP-A-56-16
As proposed in Japanese Patent No. 6201, it is preferable to use a small amount of an inorganic electrolyte together in order to facilitate the progress of enlargement. Any inorganic electrolyte may be used, but a neutral or alkaline inorganic electrolyte such as sodium sulfate, sodium chloride, potassium chloride or potassium carbonate is preferred. Not limited to the method of using the inorganic electrolyte,
There is no problem even if it is included in advance before the polymerization of the rubbery polymer or added before the enlargement treatment.

Further, as proposed in Japanese Patent Application Laid-Open No. 50-25655, it is preferable to prepare the rubbery polymer latex (g) having a small particle size to be enlarged so that the pH thereof is 7 or more. , More preferably 8 or more, still more preferably 9 or more. Any method may be used to adjust the pH, but an example is a method of adding an alkaline substance such as sodium carbonate, potassium carbonate or sodium hydroxide.

The range of the weight average particle diameter of the enlarged (meth) acrylate rubber polymer (G) has an excellent balance between impact resistance and matteness of the resulting thermoplastic resin composition. Therefore, the upper limit is preferably 1000
nm, more preferably 800 nm, particularly preferably 60
0 nm, the lower limit is within a range not exceeding the particle size of the small particle size (meth) acrylic acid ester-based rubbery polymer (g) used, preferably 200 nm, more preferably 250 n.
m, particularly preferably 300 nm.

Further, in the enlargement treatment, the thermoplastic resin composition obtained has an excellent balance between impact resistance and matting property, so that it is enlarged in the (meth) acrylate rubber (G). It is preferable to enlarge the presence ratio of the small particle size (meth) acrylic acid ester rubber (g) which is not present to 15% by mass or less.

The graft copolymer (A) of the present invention is a (meth) acrylate rubber polymer (G) enlarged by the above-mentioned acid group-containing copolymer latex (K).
Can be obtained by graft polymerization of a vinyl monomer.

The vinyl monomer used in the graft polymerization is not particularly limited, but preferably at least one monomer component selected from aromatic alkenyl compounds, (meth) acrylic acid alkyl esters and vinyl cyanide compounds is used. To be

Among the monomer components, the aromatic alkenyl compound is, for example, styrene, α-methylstyrene, vinyltoluene, etc., and the (meth) acrylic acid alkyl ester is, for example, methyl methacrylate, ethyl methacrylate, methacrylic acid. Acid n-butyl, 2-ethylhexyl acrylate, methyl acrylate, ethyl acrylate,
Examples of the vinyl cyanide compound include n-butyl acrylate and the like, and examples thereof include acrylonitrile and methacrylonitrile. Of these, the use of a mixture of styrene and acrylonitrile is preferable because the resulting thermoplastic resin composition has excellent impact resistance.

The graft copolymer (A) is the enlarged (meth) acrylic acid ester type rubbery polymer (G) 10
It is preferable that 90 to 20 mass% of the monomer component is emulsion-grafted with respect to -80 mass%. When the emulsion graft polymerization is carried out in such a mass ratio, the thermoplastic resin composition finally obtained is excellent in impact resistance, fluidity and matteness. When the amount of the rubber-like polymer (G) is 10% by mass or more, the impact resistance of the finally obtained thermoplastic resin composition tends to be improved, and when it is 80% by mass or less, the impact resistance is improved. And the matting property tend to improve.

More preferably, the rubber-like polymer (G) in the graft copolymer (A) is 30 to 70% by mass,
The monomer component is 70 to 30 mass%. In such a case, the finally obtained thermoplastic resin composition is preferable because it exhibits impact resistance, moldability, and matting property at a high level in a well-balanced manner.

Emulsion polymerization for producing the (meth) acrylic acid ester type rubbery polymer (G) and the graft copolymer (A) can be carried out by a radical polymerization technique using an emulsifier. Further, in the monomer to be graft-polymerized,
Various chain transfer agents for controlling the graft ratio and the molecular weight of the graft component can be added.

As the radical polymerization initiator used in the graft polymerization, a peroxide, an azo type initiator or a redox type initiator in which an oxidizing agent and a reducing agent are combined is used. Of these, redox initiators are preferred, especially redox initiators that combine ferrous sulfate, sodium pyrophosphate, glucose, hydroperoxide, and ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, Rongalit, hydroperoxide. Agents are preferred.

The emulsifier used in the graft polymerization is not particularly limited, but since the stability of the latex during emulsion polymerization is excellent and the polymerization rate can be increased, sodium sarcosinate, potassium fatty acid, sodium fatty acid, dipotassium alkenyl succinate is used. Anionic emulsifiers selected from various carboxylic acid salts such as rosin acid soap, alkyl sulfates, sodium alkylbenzenesulfonate, sodium polyoxyethylene nonylphenyl ether sulfate, and the like are preferably used. These may be used properly according to the purpose, and needless to say, the emulsifier used in the preparation of the rubber-like polymer may be used as it is without additional addition during emulsion graft polymerization.

The graft copolymer (A) latex obtained by emulsion graft polymerization is recovered, for example, by a wet method in which it is coagulated in hot water in which a coagulant is dissolved to coagulate into a slurry state, or heated. By spraying the latex of the graft copolymer (A) in the atmosphere, the graft copolymer (A) can be recovered semi-directly by a method such as a spray drying method of recovering the graft copolymer (A).

As the coagulant used in the above-mentioned wet recovery method,
Inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid, and metal salts such as calcium chloride, calcium acetate and aluminum sulfate can be used. The coagulant is selected in combination with the emulsifier used in the polymerization. That is, when only carboxylic acid soap such as fatty acid soap or rosin acid soap is used, it can be recovered by using any coagulant, but stable emulsification is possible even in an acidic region such as sodium alkylbenzenesulfonate. When the emulsifier showing a force is contained, the above-mentioned inorganic acid is not sufficient and it is necessary to use a metal salt.

In order to make the graft copolymer (A) in a slurry state from the slurry graft copolymer (A) obtained by the above-mentioned wet recovery method, first, the remaining emulsifier residue is eluted in water and washed. After that, after undergoing a process such as a method of dehydrating this slurry by centrifugation or a press dehydrator and then drying with a gas stream dryer, a method of simultaneously performing dehydration and drying with a press dehydrator, an extruder, etc., the dried graft copolymer The polymer (A) can be obtained in the form of powder or particles. Further, at this time, it is also possible to directly send the product discharged from the press dehydrator or the extruder to the extruder or the molding machine for producing the thermoplastic resin composition to obtain a molded product.

The hydroxyl group-containing acrylic copolymer (B) constituting the thermoplastic resin composition of the present invention is particularly preferably one containing a hydroxyl group and further a (meth) acrylic acid ester unit. It is not limited to the configuration.

The monomer having a hydroxyl group is not particularly limited, but it is a compound having both a vinyl group capable of radical polymerization and a hydroxyl group, and examples thereof include (meth) acrylic acid hydroxyalkyl ester and hydroxyalkyl substituted. Aromatic alkenyl is mentioned, and (meth) acrylic acid hydroxyalkyl ester is preferably used.

Specific examples of the (meth) acrylic acid hydroxyalkyl ester include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate and 2-acrylic acid acrylic acid.
Hydroxyethyl, 4-hydroxybutyl acrylate,
Hydroxybenzyl methacrylate is mentioned. Specific examples of the hydroxyalkyl-substituted aromatic alkenyl include:
1-hydroxymethyl-4-vinylbenzene, 1- (2
-Hydroxyethyl) -4-vinylbenzene and the like, among which 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate is preferable.

Hydroxyl group-containing acrylic copolymer (B) 10
The proportion of the hydroxyl group-containing monomer in 0% by mass depends on the proportion of the hydroxyl group-containing acrylic copolymer (B) used in the thermoplastic resin composition of the present invention, but its matting effect is good. Therefore, the amount is preferably 0.5% by mass or more, more preferably 2% by mass or more, and particularly preferably 5% by mass or more. In addition, since the thermoplastic resin composition has good impact resistance and few fish eyes are generated, it is preferably 50% by mass or less, more preferably 45% by mass or less, and particularly preferably 40% by mass or less. Is good.

As the monomer constituting the (meth) acrylic acid ester unit constituting the hydroxyl group-containing acrylic copolymer (B), those mentioned above can be used. The upper limit of the (meth) acrylic acid ester unit in the hydroxyl group-containing acrylic copolymer (B) is preferably 99.5% by mass or less, more preferably 98% by mass or less, and particularly preferably 95% by mass or less. Is good. The lower limit of the (meth) acrylic acid ester unit is preferably 50% by mass or more, more preferably 55% by mass or more, and particularly preferably 60% by mass or more.

The hydroxyl group-containing acrylic copolymer (B) can contain other vinyl monomer units in addition to the hydroxyl group-containing monomer unit and the (meth) acrylic acid ester unit. , Examples of such other monomer constituting the vinyl monomer unit include aromatic alkenyl monomers, vinyl cyanide monomers, maleimide monomers,
Examples thereof include maleic anhydride, and of these, the aromatic alkenyl-based monomers and vinyl cyanide-based monomers described above can be used. Specific examples of the maleimide-based monomer include maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-propylmaleimide and N-cyclohexylmaleimide.

These other vinyl-based monomer units can be used depending on the purpose, but the upper limit of the amount used is 40% by mass.

Further, a crosslinking agent can be used in the hydroxyl group-containing acrylic copolymer (B), if necessary. As these cross-linking agents, the above-mentioned ones can be used, and the upper limit of their usable amount is 5% by mass, preferably 4% by mass, and more preferably 3% by mass, since the matte design of the surface is excellent.

The method for producing the hydroxyl group-containing acrylic copolymer (B) is not particularly limited, and known emulsion polymerization, suspension polymerization,
Emulsion-suspension polymerization, bulk polymerization, solution polymerization, bulk-suspension polymerization and the like can be used, but suspension polymerization is preferred from the viewpoint of industrial ease.

As the initiator used in the polymerization, known organic peroxides and azo compounds can be used. As the suspending / dispersing agent, known ones can be used, and examples thereof include organic colloidal polymeric substances, inorganic colloidal polymeric substances, inorganic fine particles, and combinations of these with a surfactant. At this time, a molecular weight or a molecular weight distribution may be adjusted by using a chain transfer agent such as mercaptan.

As a specific example of such suspension polymerization, it is possible to carry out aqueous suspension of a monomer or a mixture of monomers together with a polymerization initiator or a chain transfer agent in the presence of a suspension dispersant.
In addition to this, a part of the monomer or the monomer mixture may be charged in advance to start the polymerization, and then the monomer or the monomer mixture having a different composition may be supplied.

The lower limit of the amount of the hydroxyl group-containing acrylic polymer (B) used in 100 parts by mass of the thermoplastic resin composition of the present invention depends on the proportion of the hydroxyl group-containing monomer contained therein. The amount is preferably 2 parts by mass, more preferably 3 parts by mass, and particularly preferably 5 parts by mass because it has excellent matting properties. The upper limit of the amount used is preferably 50 parts by mass, because the thermoplastic resin composition is excellent in impact resistance.
It is more preferably 40 parts by mass, and particularly preferably 30 parts by mass.

If necessary, the thermoplastic resin composition of the present invention may be blended with other thermoplastic resin (F) within a range that does not significantly impair the desired performance of the present invention.

The other thermoplastic resin (F) is not particularly limited and includes, for example, polymethyl methacrylate, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-N-substituted maleimide terpolymer. , Styrene-maleic anhydride copolymer, styrene-maleic anhydride-N-substituted maleimide terpolymer, polycarbonate resin, polybutylene terephthalate (PB
T resin), polyethylene terephthalate (PET resin), polyvinyl chloride, polyethylene, polyolefins such as polypropylene, styrene-butadiene-styrene (SBS), styrene-butadiene (SBR), hydrogenated SBS, styrene-isoprene-styrene (SIS).
Styrene-based elastomers such as, various olefin-based elastomers, various polyester-based elastomers, polystyrene, methyl methacrylate-styrene copolymer (MS resin), acrylonitrile-styrene-methyl methacrylate copolymer, polyacetal resin, modified polyphenylene ether (modified PPE resin), ethylene-vinyl acetate copolymer, PPS resin, PES resin, PEEK resin, polyarylate, liquid crystal polyester resin, polyamide resin (nylon) and the like, and these may be used alone or in combination of two or more kinds. Can be used.

The upper limit of the amount of these other thermoplastic resins (F) that can be used is 80 parts by mass in 100 parts by mass of the thermoplastic resin composition.

It is preferable that the thermoplastic resin composition of the present invention further contains a phosphorus compound (P) for the purposes of both improving the matting property and the thermal coloring property.

As the phosphorus compound (P) which can be used in the present invention, phosphite compounds such as alkyl phosphite, alkyl aryl phosphite, aryl phosphite, nonyl phenyl phosphite, alkyl nonyl phenyl phosphite, and tris. Alkyl phosphates, tripolyoxyethylene alkyl ether phosphates, dialkyl phosphates and metal salts thereof, dipolyoxyethylene alkyl ether phosphates and metal salts thereof, alkyl phosphates and metal salts thereof,
Examples thereof include phosphate compounds such as polyoxyethylene alkyl ether phosphate and metal salts thereof, and phosphonate compounds such as dialkylalkylphosphonates, alkylalkylphosphonates and metal salts thereof.
Among them, a phosphite compound is preferable because of its excellent effect of improving the matting property, and a compound having no bulky substituent around the phosphite group is more preferable.

The upper limit of the amount of the phosphorus compound (P) used per 100 parts by mass of the thermoplastic resin composition of the present invention is 0 because the thermoplastic resin composition is excellent in mattness and the effect of improving thermal stability is 0. 0.1 to 3 parts by mass, preferably 0.1 to 2 parts by mass, and more preferably 0.1 to 1.5 parts by mass from the viewpoint of bleed-out and economics.

The thermoplastic resin composition of the present invention comprises a graft polymer (A), a hydroxyl group-containing acrylic polymer (B), and if necessary, other thermoplastic resin (F) and a phosphorus compound (P). , V-type blender, Henschel mixer or the like, and the mixture is melt-kneaded by using an extruder, a Banbury mixer, a pressure kneader, a kneader such as a roll, or the like.

The obtained thermoplastic resin composition is used as it is, or if necessary, additives such as dyes, pigments, stabilizers, reinforcing agents, fillers, flame retardants, foaming agents, lubricants and plasticizers are added. After that, it can be used as a raw material for manufacturing a molded product. This thermoplastic resin composition is made into a desired molded article by various molding methods such as an injection molding method, an extrusion molding method, a blow molding method, a compression molding method, a calender molding method and an inflation molding method.

It is also possible to use it by coating it with another resin or metal depending on the case. Other resins here are not particularly limited, but those described in the above other thermoplastic resins (F), ABS resins, thermoplastic rubber-modified resins such as high-impact polystyrene, and phenol resins and melamine resins can be used. A curable resin or the like can be widely used.

The thermoplastic resin composition of the present invention can be obtained as a molded product which has been subjected to primary processing by profile extrusion molding, sheet molding, or multilayer sheet molding with the above-mentioned other materials by the above-mentioned molding method. The molded product subjected to the primary processing as described above can be a material that can be used in a wide industrial field by thermoforming, vacuum forming, or the like depending on the application. In addition, such a sheet-shaped molded article has a surface glossiness (incident angle of 60 °) of 5
It is preferably 0% or less.

Examples of industrial applications of such a thermoplastic resin composition include vehicle parts, particularly various exterior parts used unpainted and interior parts around the dashboard, wall materials, window frames, rain gutters, various hoses. Building materials such as covers, sundries such as tableware and toys, household appliances such as vacuum cleaner housings, television housings, air conditioner housings, OA equipment housings, interior materials, ship materials, communication equipment housings, and the like.

[0070]

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The% and the number of parts in the following examples are based on mass unless otherwise specified.

[Production Example 1] Production of small particle size (meth) acrylic acid ester rubbery polymer (g-1) In a 10-liter stainless steel autoclave equipped with a stirrer and a temperature control jacket, deionized water (hereinafter Abbreviated as water) 400 parts Dipotassium alkenyl succinate (Latemul ASK manufactured by Kao Corporation) 1.0 part Sodium sulfate 0.3 parts n-Butyl acrylate 80 parts Acrylonitrile 3 parts Styrene 7 parts Triallyl cyanurate 0.8 parts 0.3 parts of dimethacrylic acid ethylene glycol diester was charged under stirring, and the inside of the reactor was replaced with nitrogen. Then, 10 parts of 1,3-butadiene was charged and the content was heated. At an internal temperature of 55 ° C., an aqueous solution containing 0.2 part of potassium persulfate and 5 parts of water was added to initiate polymerization. When the exothermic heat of polymerization was confirmed, the jacket temperature was set to 50 ° C., and the polymerization was continued until the exothermic heat of polymerization was not confirmed. After 3 hours from the initiation of polymerization, the mixture was cooled to obtain a small particle size acrylic acid ester rubbery polymer (g-1) latex having a solid content of 19.9%, a weight average particle size of 75 nm and a pH of 8.7. It was

[Production Example 2] Production of small particle size acrylate rubber polymer (g-2) In a 10 liter stainless steel autoclave equipped with a stirrer and a temperature control jacket, 400 parts of water dipotassium alkenyl succinate (Kao) Latemur ASK Co., Ltd. 1.0 part Sodium sulfate 0.3 part Sodium formaldehyde sulfoxylate dihydrate 0.3 part Separately, n-butyl acrylate 95 parts Acrylonitrile 5 parts Allyl methacrylate 0. 3 parts Dimethacrylic acid 1,3-butylene glycol diester 0.15 parts tert-Butyl hydroperoxide 0.2 parts A mixture prepared in advance was charged, and the inside of the reactor was heated under nitrogen with stirring. At an inner temperature of 50 ° C., an aqueous solution of ferrous sulfate heptahydrate 0.0005 parts ethylenediaminetetraacetic acid disodium 0.0015 parts water 5 parts was added to initiate polymerization. When the exothermic heat of polymerization was confirmed, the jacket temperature was set to 50 ° C., and the polymerization was continued until the exothermic heat of polymerization was not confirmed. After 2 hours from the start of polymerization, the mixture was cooled to obtain a small particle size acrylic acid ester rubbery polymer (g-2) latex having a solid content of 20.1%, a weight average particle size of 100 nm and a pH of 8.6. It was

[Production Example 3] Production of small particle size acrylic ester rubbery polymer (g-3) In a 10-liter stainless steel autoclave equipped with a stirrer and a temperature control jacket, 400 parts of water dipotassium alkenyl succinate (Kao) Latemur ASK Co., Ltd. 1.0 part Sodium sulfate 0.3 part Sodium formaldehyde sulfoxylate dihydrate 0.3 part Acrylamide 2 parts, separately, n-butyl acrylate 65 parts 2-Ethylhexyl acrylate 33 parts Allyl methacrylate 0.3 parts Dimethacrylic acid 1,3-butylene glycol diester 0.15 parts tert-Butyl hydroperoxide 0.2 parts A mixture prepared in advance was charged, and the inside of the reactor was replaced with nitrogen while stirring. The temperature was raised. At an inner temperature of 50 ° C., an aqueous solution of ferrous sulfate heptahydrate 0.0005 parts ethylenediaminetetraacetic acid disodium 0.0015 parts water 5 parts was added to initiate polymerization. When the exothermic heat of polymerization was confirmed, the jacket temperature was set to 50 ° C., and the polymerization was continued until the exothermic heat of polymerization was not confirmed. After 2 hours from the initiation of polymerization, the mixture was cooled to obtain a small particle size acrylic acid ester rubber polymer (g-3) latex having a solid content of 19.7%, a weight average particle size of 95 nm and a pH of 8.9. It was

[Production Example 4] Production of small particle size acrylic acid ester rubbery polymer (g-4) Polymerization was conducted in the same manner as in Production Example 1 except that ethylene glycol diester dimethacrylate was not used.
A small particle size acrylic acid ester rubbery polymer (g-4) latex having a solid content of 19.9%, a weight average particle size of 80 nm and a pH of 8.4 was obtained.

[Production Example 5] Production of small particle size acrylic acid ester rubbery polymer (g-5) Polymerization was conducted in the same manner as in Production Example 1 except that triallyl cyanurate was not used, and the solid content was 20. A small particle size acrylate rubber polymer (g-5) latex having a particle size of 0.0%, a weight average particle size of 75 nm, and a pH of 8.5 was obtained.

Production Example 6 Production of Small Particle Size Acrylate Ester Rubber Polymer (g-6) In Production Example 2, -n-butyl acrylate and acrylonitrile used were 95-n-butyl acrylate.
Parts, acrylonitrile 3 parts, and 2-hydroxyethyl methacrylate 2 parts were polymerized in the same manner except that the solid content was 19.9%, the weight average particle size was 86 nm, and the pH was 8.7. A small particle size acrylic acid ester-based rubbery polymer (g-6) latex was obtained.

[Production Example 7] Production of large particle size acrylic acid ester rubbery polymer (Z-1) In Production Example 1, the amount of dipotassium alkenyl succinate used was 0.2 parts, and further 0 after polymerization mass. Polymerization was carried out in the same manner except that 8 parts were additionally added, and the solid content was 1
An acrylic acid ester-based rubbery polymer (Z-1) latex having a large particle size of 9.4%, a weight average particle size of 370 nm, and a pH of 8.7 was obtained.

[Production Example 8] Preparation of acid group-containing copolymer latex (K-1) In a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirrer, water 200 parts potassium oleate 2 .2 parts Sodium dioctyl sulfosuccinate 2.5 parts Sodium formaldehyde sulfoxylate dihydrate 0.3 parts Ferrous sulfate heptahydrate 0.003 parts Ethylenediaminetetraacetic acid disodium 0.009 parts Charged under nitrogen flow The temperature was raised to 60 ° C. From the time when the temperature reached 60 ° C., a mixture of n-butyl acrylate 81.5 parts methacrylic acid 18.5 parts cumene hydroperoxide 0.5 parts was continuously added dropwise over 120 minutes. After the dropwise addition, the mixture was further aged for 2 hours at 60 ° C., and the acid group-containing copolymer latex (K-1) had a solid content of 33.0%, a polymerization conversion rate of 99%, and a weight average particle diameter of 145 nm. Got

[Production Example 9] Preparation of acid group-containing copolymer latex (K-2) In a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirrer, water 200 parts potassium oleate 2 1 part Sodium dioctyl sulfosuccinate 2.5 parts Sodium formaldehyde sulfoxylate dihydrate 0.3 parts Ferrous sulfate heptahydrate 0.003 parts Ethylenediaminetetraacetic acid disodium 0.009 parts Charged under nitrogen flow The temperature was raised to 70 ° C. From the time when the temperature reached 70 ° C., a mixture of n-butyl methacrylate 24 parts methacrylic acid 1 part tert-dodecyl mercaptan 0.1 part cumene hydroperoxide 0.03 part was continuously added dropwise over 75 minutes for polymerization. Let After holding for 30 minutes, n-butyl acrylate 25 parts n-butyl methacrylate 37 parts methacrylic acid 13 parts tert-dodecyl mercaptan 0.3 parts cumene hydroperoxide 0.08 parts were aged for 2 hours at 70 ° C. , Solids 33.1
%, The polymerization conversion rate is 99%, and the weight average particle size is 90 n.
m-group-containing copolymer latex (K-2) was obtained.

[Production Example 10] (Meth) acrylic acid ester rubbery polymer (G) Production Acrylic acid ester rubbery polymers (g-1) to (g-6) produced in Production Examples 1 to 6 Using the acid group-containing copolymer latexes (K-1) and (K-2) produced in Production Examples 8 and 9, the acrylic ester rubber-like polymer (g) was heated to an inner temperature of 65 ° C. and under stirring. Then, the predetermined amount shown in Table 1 was added all at once, and stirring was continued for 30 minutes while maintaining the temperature to enlarge the acrylate rubber polymer (G-1a).
-(G-1d), (G-2)-(G-6) latex was obtained. At this time, the pH of the acrylic ester rubber-like polymer (g) was adjusted to 9 to 10 with a 1% aqueous sodium hydroxide solution before the enlargement treatment.

[0081]

[Table 1] [Production Example 11] Production of graft copolymer (A-1) Acrylic ester-based rubbery polymer (G-1a) latex was placed in a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirrer. (As solid content) 50 parts Water (including water in acrylic ester-based rubbery polymer latex) Rongalit 0.15 parts Dipotassium alkenyl succinate 0.5 parts are added and the internal temperature is maintained under nitrogen stream while stirring. The temperature was raised to 75 ° C. Then, a mixed solution of 5 parts of acrylonitrile, 15 parts of styrene and 0.08 part of t-butyl hydroperoxide was added dropwise over 1 hour to carry out polymerization. After the dropping, the temperature of 75 ° C. was maintained for 1 hour, and then ferrous sulfate heptahydrate 0.001 part ethylenediaminetetraacetic acid disodium salt 0.003 part Rongalit 0.15 part ion-exchanged water 10 parts aqueous solution Then, a mixture of acrylonitrile 7.5 parts styrene 22.5 parts t-butyl hydroperoxide 0.2 parts was added dropwise over 1.5 hours, during which polymerization was performed so that the internal temperature did not exceed 80 ° C. I'm sorry. After completion of the dropping, the temperature of 80 ° C. was maintained for 30 minutes and then cooled to obtain a graft copolymer (A-1) latex.

Next, 150 parts of 1.2% sulfuric acid aqueous solution was added to 75 parts.
This graft copolymer (A
-1) 100 parts of latex was gradually dropped to coagulate, and the temperature was further raised to 90 ° C and kept for 5 minutes. Next, the precipitate is dehydrated, washed and dried to obtain a powdery graft copolymer (A having an acetone insoluble content of 70% and ηsp / C of 0.76 dl / g (A
-1) was obtained.

[Production Examples 12 to 21] The acrylic ester rubber-like polymer (G-1a) used in Production Example 1 of the graft copolymers (A-2) to (A-11) was replaced with (G- 1b) to (G-1d),
(G-2) to (G-6), (Z-1), and non-enlarged small particle acrylic acid ester rubber polymer (g
Polymerization was carried out in the same manner except that it was changed to -1a) to obtain graft copolymers (A-2) to (A-11). The production results are shown in Table 2.

[Production Example 22] Graft copolymer (A-1)
2) Production In a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirrer, acrylic ester type rubbery polymer (G-1a) latex (as solid content) 60 parts water (acrylic ester) (Including water in the rubbery polymer latex) Rongalit 0.15 part 0.5 part of sodium N-lauroyl sarcosinate was added, and the internal temperature was raised to 75 ° C under a nitrogen stream while stirring. Then, a mixed solution of 30 parts of methyl methacrylate, 3 parts of acrylonitrile, 3 parts of styrene, 7 parts of t-butyl hydroperoxide and 0.16 parts was added dropwise over 2 hours for polymerization. After completion of the dropping, the temperature of 75 ° C. was maintained for 1 hour and then cooled to obtain a graft copolymer (A-11) latex.

Next, 150 parts of 1.2% sulfuric acid aqueous solution was added to 75 parts.
This graft copolymer (A
-12) 100 parts of latex was gradually dropped to coagulate, and the temperature was further raised to 90 ° C. and kept for 5 minutes. Then, the precipitate is dehydrated, washed and dried to obtain a powdery graft copolymer (A having an acetone insoluble content of 80% and ηsp / C of 0.54 dl / g (A
-12) was obtained.

Various physical properties in the production examples were measured by the following methods. [Weight average particle size of polymer in latex] MATEC APPL
IED SCIENCES submicron particle size distribution analyzer CHDF
It was measured using -2000. [Intrinsic Viscosity of Acrylic Polymer Containing Hydroxyl Group] Intrinsic viscosity was measured by using chloroform as a solvent and solution viscosities with different concentrations at five points using an AVL-2C type fully automatic viscometer manufactured by Sun Electronics Industry. Sought by doing.

[0087]

[Table 2] [Production Example 23] Hydroxyl group-containing acrylic polymer (B-1)
In a reactor equipped with a reagent injection container, a condenser, a jacket heater and a stirrer, 250 parts of water, 20 parts of methyl acrylate, 60 parts of methyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate, 20 parts of t-dodecyl mercaptan. 5 parts Lauroyl peroxide 1 part Tricalcium phosphate 5 parts Phosphate ester type surfactant (Toho Kagaku Kogyo Co., Ltd. phosphanol GB-520) 0.02 parts was charged, and the inside of the reactor was sufficiently replaced with nitrogen, followed by stirring. Meanwhile, the internal temperature was raised to 75 ° C. to start the polymerization.

After 3 hours from the confirmation of the exothermic heat of polymerization, the internal temperature was raised to 90 ° C. and kept for 45 minutes to complete the polymerization, and the resulting slurry was dehydrated and dried to obtain an intrinsic viscosity of 0.1.
5 L / g, bead-shaped hydroxyl group-containing acrylic polymer (B
-1) was obtained.

[Production Example 24] Production of hydroxyl group-containing acrylic polymer (B-2) In Production Example 23, the monomer composition used was 10 parts by weight of methyl acrylate, 20 parts by weight of styrene and 40 parts by weight of methyl methacrylate.
Parts, 2-hydroxyethyl methacrylate 20 parts, except that the production was carried out in the same manner, the intrinsic viscosity 0.07L /
A hydroxyl group-containing acrylic polymer (B-2) of g was obtained.

[Production Example 25] Production of hydroxyl group-containing acrylic polymer (B-3) The same as in Production Example 23 except that 60 parts of methyl methacrylate was changed to 59 parts of methyl methacrylate and 1 part of allyl methacrylate. To produce a hydroxyl group-containing acrylic polymer (B-3). Since this was crosslinked, the intrinsic viscosity could not be measured.

[Production Example 26] Other thermoplastic resin (F
-1) Production of 7 parts of acrylonitrile, 23 parts of styrene and 70 parts of methyl methacrylate, and the reduced viscosity measured from an N, N-dimethylformamide solution at 25 ° C is 0.38 dl / g.
The acrylonitrile-styrene-methyl methacrylate terpolymer (F-1) was produced by known suspension polymerization.

[Production Example 27] Other thermoplastic resin (F
-2) Production of 99 parts of methyl methacrylate and 1 part of methyl acrylate, 25 parts from N, N-dimethylformamide solution
An acrylic resin (F-2) having a reduced viscosity measured at 0 ° C. of 0.25 dl / g was produced by known suspension polymerization.

[Production Example 28] Other thermoplastic resin (F
-3) Production of acrylonitrile-styrene copolymer (F-3) consisting of 29 parts of acrylonitrile and 71 parts of styrene and having a reduced viscosity of 0.60 dl / g measured at 25 ° C. from an N, N-dimethylformamide solution. It was produced by known suspension polymerization.

[Production Example 29] Other thermoplastic resin (F
-4) Preparation of 19 parts of acrylonitrile, 53 parts of styrene and 28 parts of N-phenylmaleimide and having a reduced viscosity of 0.6 measured from an N, N-dimethylformamide solution at 25 ° C.
An acrylonitrile-styrene-N-phenylmaleimide terpolymer (F-4) having a concentration of 5 dl / g was produced by a known continuous solution polymerization.

[Production Example 30] Other thermoplastic resin (F
Production of -5) 50 parts of polybutadiene rubber-like polymer latex (weight average particle size 280 nm, gel content 85%, solid content) was graft polymerized with a mixture of 15 parts acrylonitrile and 35 parts styrene by a known emulsion polymerization method. , Acrylonitrile-butadiene-styrene (ABS) polymer (F
-5) was produced.

[Production Example 31] Other thermoplastic resin (F
-6) Production of polybutadiene rubbery polymer (weight average particle diameter 380 n
m, gel content 85%, solid content), 10 parts of a rubber-like polymer (weight average particle diameter 300 nm, total 50 parts by mass) of 40 parts of an acrylic acid ester-based rubbery polymer, 15 parts of acrylonitrile and A mixture of 35 parts of styrene is graft-polymerized by a known emulsion polymerization method to obtain a butadiene-acrylic composite rubber-based graft copolymer (F-6).
Was manufactured.

[Production Example 32] Other thermoplastic resin (F
-7) Production of polydimethylsiloxane (weight average particle diameter 60 nm) 1
A known emulsion of a mixture of 15 parts of acrylonitrile and 35 parts of styrene in a rubber-like polymer (weight average particle diameter 120 nm, total 50 parts by mass) in which 5 parts of 35 parts of an acrylic ester rubber-like polymer is complexed. Graft polymerization was performed by a polymerization method to produce a polydimethylsiloxane-acrylic composite rubber-based graft copolymer (F-7).

[Examples 1 to 23 and Comparative Examples 1 to 5] Produced graft polymers (A-1) to (A-12) and hydroxyl group-containing acrylic polymers (B-1) to (B-3). And 0.4 parts of ethylene bis-stearyl amide with respect to 100 parts of the resin component, and other thermoplastic resins (F-1) to (F-7) as required, and Asahi Denka Kogyo Co., Ltd. as a phosphorus compound. ) "ADEKA STAB PEP-8F" (P-
1), "Adeka Stab 1500" (P-2), "Fosphanol LO529" (P- manufactured by Toho Chemical Industry Co., Ltd.)
3) was added according to the formulation shown in Table 1 and then mixed using a Henschel mixer, and the mixture was heated to a barrel temperature of 230 ° C. for degassing extruder (TEX-3 manufactured by Japan Steel Works Ltd.).
0) and kneaded to obtain pellets.

Table 3 shows the evaluation results of Izod impact strength, molding glossiness, appearance evaluation, and weather resistance measured using the obtained pellets.

The thermoplastic resin composition obtained was evaluated by the following methods. (1) Izod impact strength A method according to ASTM D256 was used, and a 1/4 "thick test piece with a notch was left in an atmosphere at 23 ° C for 12 hours or more, and then measured. Molding gloss Using a 25 mmφ single screw extruder manufactured by Thermoplastics Industry Co., Ltd., the resin is discharged in a sheet form from a T die with a width of 60 mm at a barrel temperature of 190 ° C. and 250 ° C. and a cooling roll temperature of 85 ° C., and a winding speed is set. A sheet having a width of 50 to 60 mm, whose thickness was adjusted to 200 to 250 μm by adjustment, was formed, and the obtained formed sheet was measured at an incident light of 60 °. [Gloss difference (%)] = (Glossiness at 250 ° C. molding) − (Glossiness at 190 ° C. molding) (1) (3) Molding appearance Molding obtained above To the seat Then, the matteness, the appearance of fish eyes and die lines, and the fineness of the surface were judged by visual inspection, and those that were recognized as good sheets without problems were evaluated as ○, and those with many problems that could not be put to practical use. ×,
The middle was evaluated as Δ. (4) A weatherproof 100 mm × 100 mm × 3 mm white colored plate was placed on a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) at a black panel temperature of 63 ° C. and a cycle condition of 60 minutes (rainfall: 12
Min) for 1,000 hours. In that case, the degree of color change (ΔE) measured by a color difference meter was evaluated.

[0101]

[Table 3] From the examples and comparative examples, the following facts were clarified. 1) The resin compositions of Examples 1 to 23 containing the graft polymer (A), the hydroxyl group-containing acrylic polymer (B), and optionally the other thermoplastic resin (F) and the phosphorus compound (P), The Izod impact strength, weather resistance, good matteness and appearance, and the temperature dependence of the matteness at the molding temperature were small and good. 2) The thermoplastic resin compositions of Comparative Examples 1 to 5 were inferior in any of the above items. 3) From Examples 11 to 12 and Comparative Examples 4 to 5, when the hydroxyl group-containing acrylic polymer (B) is not in the specific range, all the objects of the present invention cannot be achieved. 4) From the results of Examples 2 and 15 to 16, by adding a small amount of the phosphorus compound (P) to the thermoplastic resin composition of the present invention, it is possible to further suppress an increase in gloss during high temperature molding. Become.

[0102]

Industrial Applicability As described above, the thermoplastic resin composition of the present invention exerts particularly remarkable effects as follows, and its industrial utility value is extremely large. 1) The thermoplastic resin composition of the present invention is excellent in mechanical strength such as impact resistance, weather resistance, surface appearance such as fish eyes and rough skin, and excellent matting property in a wide molding temperature range. 2) Especially, the balance between impact resistance, matteness and weather resistance is
This is a very high level that cannot be obtained with conventionally known rubber-modified thermoplastic resin compositions, and its utility value as various industrial materials is extremely high. 3) The thermoplastic resin composition of the present invention exerts a great effect particularly when formed into a sheet-shaped molded product.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F071 AA12X AA22 AA22X AA33                       AA33X AA34X AA77X AC15                       AE05 AE22 AF23 AF32 AF45                       AF57 BA01 BB06 BC01                 4J002 AC08Y AC11Y BB03Y BB06Y                       BB12Y BC03Y BC05Y BC06Y                       BD04Y BF03Y BF05Y BG06Y                       BG07X BG10Y BH02Y BN12W                       BN14W BN16W CB00Y CF06Y                       CF07Y CG00Y CH07Y CH09Y                       CL00Y CN01Y EW046 EW066                       FD066 FD206 GN00

Claims (10)

[Claims] 1. A graft copolymer (G) in which a vinyl polymer is grafted to a (meth) acrylate rubber polymer (G) that has been enlarged by the acid group-containing copolymer latex (K). A) 10 to 98 parts by mass, hydroxyl group-containing acrylic copolymer (B) 2 to 50 parts by mass, and other thermoplastic resin (F) 0 to 80 parts by mass [component (A),
A total of 100 parts by weight of (B) and (F)]. 2. The (meth) acrylic acid ester rubber-like polymer (G) contains 50 (meth) acrylic acid alkyl ester monomer units having an alkyl group having 1 to 12 carbon atoms.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition contains at least mass%. 3. A compound in which two or more kinds of polyfunctional monomer units contained in the (meth) acrylate rubber polymer (G) are derived from one or more kinds of a graft crossing agent and a crosslinking agent, respectively. The thermoplastic resin composition according to claim 1 or 2. 4. A hydroxyl group-containing acrylic copolymer (B)
Is a copolymer containing a monomer unit containing a hydroxyl group and a (meth) acrylic acid ester unit, The thermoplastic resin composition according to claim 1. 5. A hydroxyl group-containing acrylic copolymer (B)
Is a copolymer containing a (meth) acrylic acid hydroxyalkyl ester unit as an essential component, The thermoplastic resin composition according to any one of claims 1 to 3. 6. A hydroxyl group-containing acrylic copolymer (B)
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is crosslinked. 7. The thermoplastic resin composition according to claim 1, which further comprises 0.1 to 3 parts by mass of the phosphorus compound (P). 8. A sheet-shaped molded article made of the thermoplastic resin composition according to claim 1. 9. A multilayer molded sheet-shaped molded article obtained by laminating the sheet-shaped molded article according to claim 8 and another thermoplastic resin composition. 10. Surface gloss (incident angle 60 °) is 50%
The sheet-shaped molded article according to claim 8 or 9, which is as follows.