JP2006016524A - Thermoplastic resin composition and molded product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in fluidity in molding, having a wide molding temperature range in which temperature range molded products having good mat externals are obtained, and obtaining molded products excellent in impact resistance and weatherability, and to provide molded products of the composition. <P>SOLUTION: As the thermoplastic resin composition, a composition comprising 1-99.9 pts. mass graft copolymer (A) obtained by graft-polymerizing a vinyl monomer to a (meth)acrylic ester rubber-like polymer (G) swelled by an acid group-containing copolymer latex (K), 0.1-50 pts. mass crosslinked hard polymer (B) and 0-80 pts. mass other thermoplastic resins (C) [total of the graft copolymer (A), the crosslinked hard polymer (B) and other thermoplastic resins (C) is 100 pts. mass] is used. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a thermoplastic resin composition that can be used as various industrial materials and molded articles thereof, and in particular, has a wide molding temperature range in which molded articles having excellent fluidity during molding and having a good matte appearance can be obtained. In addition, the present invention relates to a thermoplastic resin composition capable of obtaining a molded article having excellent impact resistance and weather resistance.

  Improving the impact resistance of resin materials not only expands the applications of resin materials, but also makes it possible to respond to the reduction in thickness and size of molded products. Various techniques have been proposed so far for improving the impact resistance of resin materials.

  Among these, a technique for increasing the impact resistance of a material by combining a rubbery polymer and a hard resin has already been industrialized. Examples of such materials include acrylonitrile-butadiene-styrene resin (ABS resin), high impact polystyrene resin (HIPS resin), acrylonitrile-styrene-acrylic ester resin (ASA resin), modified polyphenylene ether resin (modified PPE resin), And thermoplastic resin compositions such as MBS resin-reinforced polyvinyl chloride resin.

  Among thermoplastic resin compositions, components such as ASA resin using a component such as alkyl (meth) acrylate rubber which is a saturated rubber as a rubbery polymer, a composite rubber of alkyl (meth) acrylate rubber and polyorganosiloxane, etc. The SAS resin used and the AES resin using the ethylene-propylene rubber component are characterized by having good weather resistance.

  Recently, the demand for materials with significantly reduced gloss, so-called matte materials, is increasing, mainly in the fields of automotive interior parts such as dashboards and instrument panels, and resin-based building materials for housing. As such a matte material, the material which mix | blended the crosslinked hard polymer with the thermoplastic resin composition is proposed (for example, refer patent documents 1-9).

  The matte material described above is excellent in impact resistance and weather resistance. Recently, however, the requirements for impact resistance and weather resistance for materials have become stricter, and these matte materials cannot satisfy the requirements. Specifically, when such a cross-linked hard polymer is blended, the impact resistance is remarkably lowered, and its use is limited.

  Further, for the purpose of avoiding such a decrease in impact resistance, a matte thermoplastic resin composition containing a rubber-like polymer having a large particle size has been proposed (for example, see Patent Documents 10 to 14). . By including a rubbery polymer with a large particle size, the problem that impact resistance tends to decrease can be solved. There was a tendency for differences to occur and to tend to be spots.

Furthermore, a thermoplastic resin composition in which a polymer containing a reactive functional group is blended has been proposed as a material that is less dependent on molding conditions of the matte appearance and the occurrence of spots (for example, patent documents). 15-21).
However, when a polymer containing a reactive functional group is blended, the flowability of the resin material is remarkably lowered, and there are many problems that often hinder the molding process.

In view of the above, there has been a strong demand for a material that simultaneously satisfies all of the impact resistance, fluidity, weather resistance, and dependence of the matte appearance on the molding conditions.
JP 53-071146 A Japanese Patent Application Laid-Open No. 56-036355 JP 59-161459 A JP 63-086756 A JP-A 63-297449 Japanese Patent Laid-Open No. 08-073686 Japanese Patent Application Laid-Open No. 08-253641 Japanese Patent Laid-Open No. 08-199027 JP 2000-212293 A Japanese Patent Laid-Open No. 02-214712 Japanese translation of PCT publication No. 02-503322 Japanese National Patent Publication No. 11-508960 JP 09-194656 A JP 2000-198505 A Japanese Patent Laid-Open No. 60-018536 JP-A-61-236850 JP-A 63-156847 Japanese Unexamined Patent Publication No. 63-155681 Japanese Patent Laid-Open No. 01-056762 Japanese Patent Laid-Open No. 01-101355 Japanese Patent Laid-Open No. 10-219079

  The present invention has been made in view of the above circumstances, has a wide molding temperature range in which a molded product having excellent fluidity during molding and a good matte appearance can be obtained, and has impact resistance and weather resistance. It is an object of the present invention to provide a thermoplastic resin composition capable of obtaining a molded product excellent in resistance, and a molded product excellent in impact resistance and weather resistance and having a good matte appearance.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a heat containing a (meth) acrylate rubber-like polymer and a cross-linked hard polymer that have been enlarged by an acid group-containing copolymer latex. The present inventors have found that a plastic resin composition can solve the above problems, and have invented the following thermoplastic resin composition and molded article.

  That is, the thermoplastic resin composition of the present invention is obtained by adding a vinyl monomer to the (meth) acrylic ester rubber-like polymer (G) that has been enlarged by the acid group-containing copolymer latex (K). Graft-polymerized graft copolymer (A) 1 part by mass to 99.9 parts by mass, crosslinked hard polymer (B) 0.1 part by mass to 50 parts by mass, and other thermoplastic resins (C) 0 to 80 [The graft copolymer (A), the cross-linked hard polymer (B), and the other thermoplastic resin (C) in total 100 parts by mass]].

Here, it is desirable that the (meth) acrylic ester rubber-like polymer (G) has a structural unit derived from a graft crossing agent and a structural unit derived from a crosslinking agent.
Further, the structural unit derived from the graft crossing agent is a structural unit derived from an allyl compound, and the structural unit derived from the crosslinking agent is a structural unit derived from a di (meth) acrylate compound. desirable.
The mass average particle diameter of the (meth) acrylic acid ester rubbery polymer (G) is preferably 300 nm or more.

The crosslinked hard polymer (B) is preferably composed of a monovinyl monomer unit and a monomer unit having two or more vinyl groups.
The monomer unit having two or more vinyl groups is preferably a structural unit derived from an allyl compound or a structural unit derived from a dimethacrylate compound.
Moreover, it is desirable that the crosslinked hard polymer (B) does not contain a hydroxyl group.
The crosslinked hard polymer (B) preferably has a particulate shape and a mass average particle size of 1 μm to 300 μm.

  The other thermoplastic resins (C) include polymethyl methacrylate, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-N-substituted maleimide terpolymer, styrene-maleic anhydride-N. -Substituted maleimide terpolymer, polycarbonate resin, polybutylene terephthalate (PBT resin), polyethylene terephthalate (PET resin), polyvinyl chloride, polystyrene, methyl methacrylate-styrene copolymer (MS resin), acrylonitrile-styrene- It is desirable that it is at least one selected from the group consisting of a methyl methacrylate copolymer, a modified polyphenylene ether (modified PPE resin), and a polyamide.

Moreover, the molded article of the present invention is characterized by comprising the thermoplastic resin composition of the present invention.
Moreover, the sheet or the profile extrusion-molded product of the present invention is characterized by being formed by extruding the thermoplastic resin composition of the present invention.

  The thermoplastic resin composition of the present invention is a molded product having a wide molding temperature range that is excellent in fluidity during molding, capable of obtaining a molded product having a good matte appearance, and excellent in impact resistance and weather resistance. Obtainable. The molded product of the present invention is excellent in impact resistance and weather resistance, and has a good matte appearance.

Hereinafter, the present invention will be described in detail.
<Graft copolymer (A)>
The graft copolymer (A) in the present invention was obtained by enlarging a small particle size (meth) acrylate rubber-like polymer (g) with an acid group-containing copolymer latex (K) ( This is a product obtained by graft-polymerizing a vinyl monomer to a (meth) acrylic ester rubber-like polymer (G).

(Small particle size (meth) acrylic ester rubber polymer (g))
The small particle size (meth) acrylic acid ester rubbery polymer (g) is a polymer having a (meth) acrylic acid ester monomer unit.
Examples of the (meth) acrylic acid ester monomer include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate; acrylic acid Examples thereof include acrylic acid esters such as methyl, ethyl acrylate, propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. Among these, n-butyl acrylate and / or 2-ethylhexyl acrylate are preferable. As these (meth) acrylic acid ester monomers, it is preferable to use a (meth) acrylic acid ester monomer having an alkyl group having 1 to 12 carbon atoms as an essential component.

  The small particle diameter (meth) acrylic acid ester rubbery polymer (g) contains one or more (meth) acrylic acid ester monomer units in the rubbery polymer (100% by mass). It is preferable to have 50% by mass or more. Since the impact resistance of the obtained thermoplastic resin composition is excellent, it is preferably 60% by mass or more, more preferably 70% by mass or more.

  The small particle size (meth) acrylic acid ester rubbery polymer (g) may have other monomer units in addition to the above-mentioned (meth) acrylic acid ester monomer units. Examples of other monomers include aromatic alkenyl compounds such as styrene, α-methylstyrene, and vinyl toluene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; 2-hydroxyethyl methacrylate, glycidyl methacrylate, methacryl Other (meth) acrylic acid esters having a functional group such as acid N and N-dimethylaminoethyl; diene compounds such as butadiene, chloroprene and isoprene; acrylamide, methacrylamide, maleic anhydride, N-substituted maleimide and the like It is done. These can be used alone or in combination of two or more depending on the purpose.

  The small particle diameter (meth) acrylic acid ester rubbery polymer (g) preferably has a structural unit derived from a graft crossing agent and a structural unit derived from a crosslinking agent. When these units are contained, the balance between the impact resistance and the matte property of the resulting thermoplastic resin composition tends to be improved.

  Examples of the crosslinking agent and graft crossing agent include allyl compounds such as allyl methacrylate, triallyl cyanurate, triallyl isocyanurate; divinylbenzene; ethylene glycol diester dimethacrylate, propylene glycol diester dimethacrylate, and 1,3 dimethacrylate. -Di (meth) acrylic acid ester compounds such as butylene glycol diester and dimethacrylic acid 1,4-butylene glycol diester. Among them, a combination of an allyl compound as a graft crossing agent and a di (meth) acrylic acid ester compound as a cross-linking agent is preferable, and allyl methacrylate as a graft crossing agent and dimethacrylic acid as a cross-linking agent are more preferable. It is a combination with 1,3-butylene glycol diester.

  The structural unit derived from the graft crossing agent and the structural unit derived from the cross-linking agent are preferably 0.1 to 3 mass in the small particle size (meth) acrylate rubber polymer (g) (100 mass%). %, And more preferably 0.1 to 1% by mass.

  The small particle size (meth) acrylic acid ester rubbery polymer (g) comprises a monomer having a (meth) acrylic acid ester monomer as an essential component, and a crosslinking agent and a graft crossing agent as necessary. The mixed monomer mixture can be prepared by emulsion polymerization.

  The mass average particle diameter of the small particle diameter (meth) acrylic acid ester rubbery polymer (g) is not particularly limited, but is preferable because enlargement by the acid group-containing copolymer latex (K) is likely to proceed. Is 30 nm to 250 nm, more preferably 40 nm to 200 nm, still more preferably 50 nm to 150 nm. If it exceeds 250 nm, enlargement by the acid group-containing copolymer latex (K) is difficult to proceed, and the matte property of the resulting thermoplastic resin composition is deteriorated, which is not preferable.

(Acid group-containing copolymer latex (K))
The acid group-containing copolymer latex (K) used as a thickening agent is a latex containing a copolymer having an acid group-containing monomer unit and a (meth) acrylic acid ester monomer unit.
Examples of the acid group-containing monomer include acrylic acid, methacrylic acid, itaconic acid, and crotonic acid.
As a (meth) acrylic acid ester monomer, the thing similar to what was used for manufacture of a small particle diameter (meth) acrylic acid ester type rubber-like polymer (g) can be used, and carbon number is 1-. A (meth) acrylic acid ester monomer having 12 alkyl groups is preferred.

  The glass transition temperature (Tg) of the acid group-containing copolymer is preferably lower in order to obtain a thermoplastic resin composition excellent in moldability and a molded article excellent in impact resistance and matting property. . Therefore, the (meth) acrylic acid ester monomer is preferably an acrylic acid ester monomer. Moreover, it is more preferable to use an acrylate monomer having a large number of carbon atoms in the alkyl group.

  The mass ratio of the (meth) acrylic acid ester monomer unit in the acid group-containing copolymer is the mass average particle diameter of the (meth) acrylic acid ester rubbery polymer (G) obtained by the enlargement treatment. In the acid group-containing copolymer (100% by mass), it is preferably 0.1 to 30% by mass, more preferably 10 to 25% by mass because it is easy to control and the matte property of the obtained molded article is excellent. is there.

  The mass average particle size of the acid group-containing copolymer in the acid group-containing polymer latex (K) is the stability of the latex when the small particle size (meth) acrylate rubber polymer (g) is enlarged. 50 nm to 250 nm because of excellent properties and easy control of the mass average particle diameter of the (meth) acrylic acid ester rubber (G) obtained by the enlargement treatment, and the matteness of the resulting molded product is excellent. preferable.

((Meth) acrylic ester rubber polymer (G))
The (meth) acrylic acid ester-based rubbery polymer (G) has a small particle diameter (meth) acrylic acid ester-based rubber polymer (g) enlarged by an acid group-containing copolymer latex (K). Is. The enlargement treatment is performed by adding the acid group-containing copolymer latex (K) to the small particle size (meth) acrylate rubber-based polymer (g) latex obtained by emulsion polymerization as described above. As for the enlargement method, known methods such as JP-A-50-25655, JP-A-58-61102 and JP-A-59-149902 can be used.

  The proper use amount of the acid group-containing copolymer latex (K) includes the properties of the small particle size (meth) acrylic ester rubber polymer (g) and the acid group-containing copolymer latex (K). Although it depends on the composition and properties, it is 0.1 parts by mass to 10 parts by mass (solid content) with respect to 100 parts by mass (solid content) of the small particle size (meth) acrylic ester rubber polymer (g). . Preferably, it is 0.3 mass part-5 mass parts. When the amount of the acid group-containing copolymer latex (K) is less than 0.1 parts by mass, not only the enlargement does not proceed, but also the matte property of the obtained molded article deteriorates, There is a tendency for impact properties to decrease. Moreover, when it exceeds 10 mass parts, it exists in the tendency for the matte property of the molded article obtained to fall again.

  When the enlargement treatment is performed, as proposed in JP-A-56-166201, it is preferable to use a small amount of an inorganic electrolyte in terms of facilitating the enlargement. Any inorganic electrolyte may be used, but neutral or alkaline inorganic electrolytes such as sodium sulfate, sodium chloride, potassium chloride, and potassium carbonate are preferable. It is not limited to the method of using the inorganic electrolyte, and it can be included either before the polymerization of the small particle size (meth) acrylic ester rubber polymer (g) or before the enlargement treatment. There is no problem.

  Further, as proposed in Japanese Patent Application Laid-Open No. 50-25655, it is preferable to adjust the pH of the small particle diameter rubbery polymer latex (g) to be enlarged to 7 or more, more preferably Is 8 or more, more preferably 9 or more. Any method may be used for adjusting the pH, but a method of adding an alkaline substance such as sodium carbonate, potassium carbonate, sodium hydroxide or the like is exemplified.

The range of the mass average particle diameter of the enlarged (meth) acrylic acid ester rubbery polymer (G) is excellent in balance between impact resistance and matting property of the obtained molded product, so the upper limit is 1000 nm, preferably 800 nm, more preferably 600 nm, and the lower limit is 200 nm, preferably 250 nm, more preferably 300 nm as long as it does not fall below the particle size of the small particle size (meth) acrylate rubber polymer (g) used. It is.
In the enlargement treatment, the proportion of the small particle size (meth) acrylate rubber (g) that has not been enlarged in the (meth) acrylate rubber polymer (G) is 15% by mass. It is preferable to enlarge it so that it becomes less than the part.

(Vinyl monomer)
The vinyl monomer used for graft polymerization is not particularly limited, but is preferably at least one monomer selected from the group consisting of aromatic alkenyl compounds, (meth) acrylic acid ester monomers, and vinyl cyanide compounds. Is used.
Examples of the aromatic alkenyl compound include styrene, α-methylstyrene, vinyltoluene and the like.

Examples of the (meth) acrylic acid ester monomer include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, methyl acrylate, ethyl acrylate, and n-butyl acrylate. It is done.
Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.
Among these, it is preferable to use a mixture of styrene and acrylonitrile because the resulting molded article has excellent impact resistance.

(Production of graft copolymer (A))
The graft copolymer (A) is preferably obtained by emulsion graft polymerization of a vinyl monomer to an enlarged (meth) acrylic ester rubber-like polymer (G). More preferably, (meth) acrylic ester rubber polymer (G) 10 parts by weight to 80 parts by weight and graft part 90 parts by weight to 20 parts by weight of a vinyl monomer polymerized [(meth) acrylic ester The total amount of the rubber-based polymer (G) and the graft part is 100 parts by mass]. When emulsion graft polymerization is performed at such a mass ratio, the fluidity of the finally obtained thermoplastic resin composition, the impact resistance of the molded product, and the matte properties are excellent.

  When the amount of the (meth) acrylic ester rubber-like polymer (G) is less than 10 parts by mass, the impact resistance of the finally obtained molded product tends to be reduced. The impact resistance is lowered and the matte property tends to deteriorate. More preferably, in the graft copolymer (A), the (meth) acrylic ester rubber-like polymer (G) is 30 to 70 parts by mass, and the graft part is 70 to 30 parts by mass. In such a case, the thermoplastic resin composition finally obtained is preferable because the impact resistance, the moldability, and the matte property are expressed at a high level in a well-balanced manner.

  Emulsion polymerization in producing the (meth) acrylic ester rubber-like polymer (G) and the graft copolymer (A) can be performed by a radical polymerization technique using an emulsifier. Moreover, various chain transfer agents for controlling the graft ratio and the molecular weight of the graft component can be added to the monomer to be graft polymerized.

  The emulsifier used for the graft polymerization is not particularly limited, but it has excellent latex stability during emulsion polymerization and can increase the polymerization rate. An anionic emulsifier selected from various carboxylates such as acid soaps, alkyl sulfates, sodium alkylbenzenesulfonate, sodium polyoxyethylene nonylphenyl ether sulfate and the like is preferably used. These are properly used according to the purpose. Further, the emulsifier used for the preparation of the small particle (meth) acrylic acid ester-based rubbery polymer (g) may be used as it is, and may not be added at the time of emulsion graft polymerization.

  Although it does not specifically limit as a radical polymerization initiator used for graft polymerization, The redox initiator which combined the peroxide, the azo initiator, or the oxidizing agent and the reducing agent can be used. Of these, redox initiators are preferred, especially those that combine ferrous sulfate, sodium pyrophosphate, glucose, and hydroperoxide, and those that combine ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, Rongalite, and hydroperoxide. Redox initiators are preferred.

  The graft copolymer (A) latex obtained by emulsion graft polymerization is then charged into hot water in which a coagulant is dissolved, and coagulated and solidified. As the coagulant, 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. In other words, when only carboxylic acid soaps such as fatty acid soaps and rosin acid soaps are used, they can be collected using any coagulant, but stable emulsification is possible even in acidic regions such as sodium alkylbenzenesulfonate. When an emulsifier exhibiting power is contained, the above inorganic acid is insufficient, and a metal salt must be used.

  Next, the graft copolymer (A) solidified using a coagulant as described above is redispersed in water or warm water to form a slurry, and an emulsifier residue remaining in the graft copolymer (A) Elute in water and wash. After washing, the slurry is dehydrated with a dehydrator or the like, and the obtained solid is dried with an air dryer or the like, whereby the graft copolymer (A) is obtained in the form of powder or particles.

<Crosslinked hard polymer (B)>
The cross-linked hard polymer (B) is not particularly limited as long as it is a hard and cross-linked polymer, but preferably a monomer unit having a monovinyl monomer unit and two or more vinyl groups. It is comprised from.

  The monomer constituting the monovinyl monomer unit is not particularly limited. For example, aromatic alkenyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester monomers, and the like can be used. The same thing as what was used for manufacture of a polymer (A) can be used. It is preferable that both the aromatic alkenyl compound and the (meth) acrylic acid ester monomer are included as essential components because the surface of the molded article is less likely to be rough and has a matte appearance.

  The monomer having two or more vinyl groups is not particularly limited. For example, allyl compounds such as allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, propylene glycone diallyl ether; ethylene glycol dimethacrylate, 1, Dimethacrylate compounds such as 3-butylene dimethacrylate and 1,4-butylene dimethacrylate; divinylbenzene and the like can be used. Of these, allyl methacrylate and / or divinylbenzene are particularly preferred because the resulting molded article is excellent in balance between impact resistance and matte appearance.

  However, for the purpose of obtaining a thermoplastic resin composition excellent in fluidity, which is an object of the present invention, a monomer unit containing a hydroxyl group is not preferred. When the crosslinked hard polymer (B) has a hydroxyl group, the fluidity of the thermoplastic resin composition tends to decrease.

  The ratio of the monovinyl monomer unit to the monomer unit having two or more vinyl groups in the crosslinked hard polymer (B) is not particularly limited, but the impact resistance and matte appearance of the obtained molded product are not limited. Since the balance is excellent, it is preferable that the monomer unit containing two or more vinyl groups is 0 in a total of 100% by mass of the monovinyl monomer unit and the monomer having two or more vinyl groups. The range is from 5% by mass to 10% by mass, and more preferably from 1.5% by mass to 5% by mass.

The manufacturing method of a crosslinked hard polymer (B) is not specifically limited, It can manufacture by methods, such as well-known suspension polymerization, emulsion polymerization, block polymerization, and solution polymerization. In particular, suspension polymerization is preferable from the viewpoint of ease of production of the crosslinked hard polymer (B), particle diameter and ease of form control described below.
In producing the crosslinked hard polymer (B) including suspension polymerization, various known auxiliaries can be used. As the chain transfer agent, known ones such as mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan and t-dodecyl mercaptan, terpene compounds such as terpinolene, and α-methylstyrene dimer can be used.

Known polymerization initiators can be used, and examples thereof include organic peroxides such as benzoyl peroxide and lauroyl peroxide, and azo initiators such as azobisisobutyronitrile.
Known suspension stabilizers that can be used in suspension polymerization can be used, for example, organic polymer substances such as polyvinyl alcohol, polyacrylate, carboxymethylcellulose, gelatin, tragacanth; barium sulfate, magnesium carbonate, calcium phosphate Inorganic colloidal substances such as, and combinations of these with surfactants.

  The mass average particle diameter of the cross-linked hard polymer (B) is not particularly limited, but it is 1 μm to 300 μm for the purpose of imparting a good matte appearance to the molded product, particularly reducing the dependency of the molding temperature. It is preferable to control. More preferably, they are 5 micrometers-200 micrometers, More preferably, they are 10 micrometers-150 micrometers. When the mass average particle diameter of the crosslinked hard polymer (B) is less than 1 μm, a good matte appearance is difficult to develop, and when it exceeds 300 μm, the uneven size becomes very large and rough, and it is difficult to say matte. Become.

  The method for controlling the particle morphology of the crosslinked hard polymer (B) is not particularly limited. For example, a method of pulverizing and / or classifying a mass obtained by mass polymerization or solution polymerization, or an aqueous solution obtained by emulsion polymerization. A method for recovering the dispersion by coagulation or spray drying, a method for obtaining the desired particle size during polymerization by selecting the production conditions such as the amount and type of the dispersant during suspension polymerization, In particular, a method of selecting the production conditions such as the amount and type of the dispersant during suspension polymerization is preferable because the production method is simple.

<Other thermoplastic resin (C)>
Other thermoplastic resins (C) are not particularly limited, and examples thereof include 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 (PBT resin), polyethylene terephthalate (PET resin), polyvinyl chloride, polyethylene, polypropylene, etc. Styrene elastomers such as polyolefin, styrene-butadiene-styrene (SBS), styrene-butadiene (SBR), hydrogenated SBS, styrene-isoprene-styrene (SIS), various olefin elastomers, various polyester 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, Examples thereof include PES resin, PEEK resin, polyarylate, liquid crystal polyester resin, and polyamide resin (nylon).

  Preferably, polymethyl methacrylate, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-N-substituted maleimide terpolymer, styrene-maleic anhydride-N-substituted maleimide terpolymer, polycarbonate Resin, polybutylene terephthalate (PBT resin), polyethylene terephthalate (PET resin), polyvinyl chloride, polystyrene, methyl methacrylate-styrene copolymer (MS resin), acrylonitrile-styrene-methyl methacrylate copolymer, modified polyphenylene ether (Modified PPE resin) and polyamide resin, and these can be used alone or in combination of two or more according to the purpose. Another thermoplastic resin (C) can be used in the range of 0 to 80 parts by mass in 100 parts by mass of the thermoplastic resin composition.

<Thermoplastic resin composition>
The thermoplastic resin composition of the present invention comprises 1 to 99.9 parts by mass of the graft copolymer (A), 0.1 to 50 parts by mass of the crosslinked hard polymer (B), and other thermoplastics. Resin (C) 0 to 80 parts by mass [total 100 parts by mass of graft copolymer (A), cross-linked hard polymer (B), and other thermoplastic resin (C)].

When the graft copolymer (A) is less than 1 part by mass in a total of 100 parts by mass of the graft copolymer (A), the cross-linked hard polymer (B), and the other thermoplastic resin (C), impact resistance is reduced. In addition, it is impossible to obtain a molded product having excellent surface matte properties.
When the cross-linked hard polymer (B) is less than 0.1 parts by mass in a total of 100 parts by mass of the graft copolymer (A), the cross-linked hard polymer (B), and the other thermoplastic resin (C), it is wide. In the molding temperature range, a molded product having good matting properties cannot be obtained, and when the amount exceeds 50 parts by mass, the impact resistance of the obtained molded product becomes insufficient.
The other thermoplastic resin (C) is in the range of 0 to 80 parts by mass in a total of 100 parts by mass of the graft copolymer (A), the crosslinked hard polymer (B), and the other thermoplastic resin (C). Can be used within.

  The thermoplastic resin composition of the present invention is obtained by mixing the graft copolymer (A) and the crosslinked hard polymer (B), and if necessary, other thermoplastic resin (C) with a V-type blender or Henschel mixer, It is manufactured by melt-kneading the mixture. In the melt-kneading, an extruder or a kneader such as a Banbury mixer, a heating kneader, or a roll can be used.

  The obtained thermoplastic resin composition can be used as it is as a raw material for producing molded products. If necessary, this thermoplastic resin composition may be added to a colorant such as a pigment or dye, a heat stabilizer, a light stabilizer, a reinforcing agent, a filler, a flame retardant, a foaming agent, a lubricant, a plasticizer, or an antistatic agent. Agents, processing aids, etc. can be blended.

<Molded product>
The molded article of the present invention is obtained by molding the thermoplastic resin composition of the present invention by various molding methods such as an injection molding method, an extrusion molding method, a blow molding method, a compression molding method, a calendar molding method, and an inflation molding method. is there.
In addition, the thermoplastic resin composition of the present invention is suitably used particularly for a sheet or a profile extrusion-molded product because it can easily ensure extrusion molding and a uniform matte surface.

  In some cases, it may be used by coating with other resin or metal. Here, the other resin that can be coated is not particularly limited, but is modified with rubber described in the other thermoplastic resin (C) described above, ABS resin, high impact polystyrene resin (HIPS), or the like. Thermosetting resins, such as a thermoplastic resin, a phenol resin, and a melamine resin, are mentioned.

  The molded article of the present invention is used in various applications. For example, as industrial applications, vehicle parts, various exterior / interior parts used without painting, wall materials, building materials parts such as window frames, tableware, toys. It is suitable for household appliance parts such as vacuum cleaner housing, television housing, and air conditioner housing, interior members, marine members, communication device housings, notebook computer housings, PDA housings, liquid crystal projector housings, and other electrical equipment housings.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to the following examples, unless the summary is exceeded. In the following examples,% and parts are based on mass unless otherwise specified.

The average particle diameter of the graft copolymer in the production examples, the acetone insoluble content ratio, and the reduced viscosity of the acetone soluble content were measured by the following methods.
[Measurement of average particle diameter of rubbery polymer latex]
It measured using the submicron particle size distribution analyzer CHDF-2000 made from MATEC APPLIED SCIENCES.

[Acetone insoluble content ratio]
About 2.5 g (weighed) of the graft copolymer and 80 ml of acetone are placed in a flask equipped with a condenser and a heater, and heated and extracted at 55 ° C. for 3 hours with a heater. Acetone insolubles are separated by treating for 60 minutes under a condition of 14,000 rpm using a machine centrifuge, and the mass is measured after drying the precipitate after removing the supernatant. And calculated by the following formula.
Acetone insoluble content (mass%) = dry weight of precipitate after separation treatment / mass of graft copolymer before acetone extraction × 100

[Reduced viscosity of acetone-soluble matter (ηsp / C)]
Acetone-soluble components are precipitated and recovered by evaporating the acetone solvent in the supernatant obtained by extraction of the graft copolymer with an acetone solvent, followed by separation of insoluble acetone by centrifugation, and then allowing the acetone. The solvent viscosity of a solution obtained by dissolving 0.2 g of a soluble component in 100 cc of N, N-dimethylformamide was measured at 25 ° C. using an automatic viscometer (manufactured by Sun Electronics Co., Ltd.) and measured under the same conditions. The reduced viscosity of acetone-soluble matter was determined from the viscosity.

The average particle diameter of the crosslinked hard polymer in the production examples was measured by the following method.
[Measurement of average particle diameter of cross-linked hard polymer]
The obtained granular crosslinked hard polymer (B) was sieved with sieves of various mesh sizes, the mass distribution was measured, and the average particle diameter was calculated.

[Production Example 1]
Production of small particle diameter (meth) acrylic acid ester rubbery polymer (g-1):
In a 10 liter stainless steel autoclave equipped with a stirrer and a temperature control jacket, 400 parts of deionized water (hereinafter simply abbreviated as water), 1.0 part of dipotassium alkenyl succinate (Latemul ASK manufactured by Kao Corporation), sodium sulfate 0 .3 parts, 97 parts of n-butyl acrylate (BA), 3 parts of acrylonitrile (AN), 0.8 parts of triallyl cyanurate (TAC), 1,3-butylene glycol dimethacrylate (1,3BD) 3 parts were charged with stirring, and the contents in the reactor were heated after the atmosphere in the reactor was replaced with nitrogen.
At an internal temperature of 55 ° C., an aqueous solution consisting of 0.2 parts of potassium persulfate and 5 parts of water was added to initiate polymerization. When a polymerization exotherm was confirmed, the jacket temperature was set to 50 ° C., and the polymerization was continued until no polymerization exotherm was confirmed. The mixture was cooled 3 hours after the start of polymerization to obtain a small particle size acrylic ester rubbery polymer (g-1) latex having a solid content of 19.9%, a mass average particle size of 75 nm and a pH of 8.6. It was.

[Production Example 2]
Production of small particle size acrylic ester rubbery polymer (g-2):
In Production Example 1, polymerization was carried out in the same manner except that dimethacrylic acid 1,3-butylene glycol ester (1,3BD) was not used, the solid content was 19.9%, the mass average particle size was 80 nm, and pH A small particle size acrylic ester rubbery polymer (g-2) latex having a particle size of 8.4 was obtained.

[Production Example 3]
Production of small particle size acrylic ester rubbery polymer (g-3):
In Production Example 1, polymerization is carried out in the same manner except that triallyl cyanurate (TAC) is not used, the solid content is 20.0%, the mass average particle size is 75 nm, and the small particle size is pH 8.5. An acrylic ester rubbery polymer (g-3) latex was obtained.

[Production Example 4]
Preparation of acid group-containing copolymer latex (K):
In a reactor equipped with a reagent injection vessel, a condenser, a jacket heater and a stirrer, 2.5 parts of sodium, 0.3 parts of sodium formaldehyde sulfoxylate dihydrate, 200 parts of water, potassium oleate 2 parts, dioctylsulfosuccinic acid, 0.003 part of ferrous sulfate heptahydrate and 0.009 part of disodium ethylenediaminetetraacetate were charged under a nitrogen flow, and the temperature was raised to 60 ° C.
When the temperature reached 60 ° C., a mixture of 81.5 parts of n-butyl acrylate (BA), 18.5 parts of methacrylic acid (MAA) and 0.5 part of cumene hydroperoxide was continuously added over 120 minutes. It was dripped. After completion of the dropwise addition, the mixture was aged for 2 hours at 60 ° C. to obtain an acid group-containing copolymer latex (K) having a solid content of 33.0%, a polymerization conversion rate of 99%, and a mass average particle diameter of 145 nm. It was.

[Production Example 5]
Production of (meth) acrylic ester-based rubbery polymer (G):
Small particle size acrylic ester rubbery polymers (g-1) to (g-3) produced in Production Examples 1 to 3 and acid group-containing copolymer latex (K) produced in Production Example 4 And using an internal temperature of 65 ° C. and stirring, a predetermined amount of the acid group-containing copolymer latex (K) shown in Table 1 is added all at once to the acrylic ester rubber-like polymer (g). Stirring was continued for 30 minutes while maintaining the temperature to obtain enlarged acrylate rubber polymers (G-1a) to (G-1c), (G-2), and (G-3) latex. . At this time, the pH of the small particle size acrylic ester rubbery polymer (g) was adjusted between 9 and 10 with a 1% sodium hydroxide aqueous solution before the enlargement treatment.

[Production Example 6]
Production of large particle size acrylic ester rubbery polymer (Z-1) for comparison:
In the example described in Production Example 1, the polymerization was carried out in the same manner except that the amount of dipotassium alkenyl succinate used was 0.2 part and an additional 0.8 part was added after the polymerization, and the solid content was 19.4%. A large particle size acrylic ester rubbery polymer (Z-1) latex having a mass average particle size of 370 nm and a pH of 8.7 was obtained.

[Production Example 7]
Production of graft copolymer (A-1):
In a reactor equipped with a reagent injection container, a cooling tube, a jacket heater, and a stirrer, 50 parts of an acrylate rubber-based polymer (G-1a) latex (as solids), water (acrylate rubber) 170 parts (including water in the polymer latex), 0.15 part of Rongalite, and 0.5 part of dipotassium alkenyl succinate were added, and the internal temperature was raised to 75 ° C. under a nitrogen stream while stirring.
Subsequently, a mixed liquid of 5 parts of acrylonitrile (AN), 15 parts of styrene (St), and 0.08 part of t-butyl hydroperoxide was dropped over 1 hour for polymerization. After completion of dropping, the temperature is maintained at 75 ° C. for 1 hour, and then ferrous sulfate heptahydrate 0.001 part, ethylenediaminetetraacetic acid disodium salt 0.003 part, Rongalite 0.15 part, ion-exchanged water 10 parts Then, an aqueous solution consisting of 7.5 parts of acrylonitrile (AN), 22.5 parts of styrene (St) and 0.2 part of t-butyl hydroperoxide is added dropwise over 1.5 hours, Polymerization was performed so that the internal temperature did not exceed 80 ° C.
After completion of dropping, the temperature was maintained at 80 ° C. for 30 minutes and then cooled to obtain a graft copolymer (A-1) latex. Next, 150 parts of a 1.2% sulfuric acid aqueous solution was heated to 75 ° C., and 100 parts of the graft copolymer (A-1) latex was gradually dropped into the solution under stirring to solidify, and the temperature was further raised to 90 ° C. Hold for 5 minutes. Next, the precipitate was dehydrated, washed and dried to obtain a powdery graft copolymer (A-1) having an acetone insoluble content of 72% and an ηsp / C of 0.74 dl / g.

[Production Examples 8 to 11]
Production of graft copolymers (A-2) to (A-5):
The same as in Production Example 7, except that the acrylate rubber polymer (G-1a) used is changed to (G-1b), (G-1c), (G-2), (G-3). Polymerization was carried out to obtain graft copolymers (A-2) to (A-5). The production results are shown in Table 2.

[Production Example 12] Production of graft copolymer (A-6):
In a reactor equipped with a reagent injection container, a cooling tube, a jacket heater, and a stirrer, 60 parts of an acrylic ester rubbery polymer (G-1b) latex (as solids), water (acrylic ester rubber) 170 parts (including water in the polymer latex), 0.15 part of Rongalite, and 0.5 part of sodium N-lauroyl sarcosinate were added, and the internal temperature was raised to 75 ° C. under a nitrogen stream while stirring.
Subsequently, a mixed solution of 30 parts of methyl methacrylate (MMA), 3 parts of acrylonitrile (AN), 7 parts of styrene (St) and 0.16 part of t-butyl hydroperoxide was dropped over 2 hours for polymerization. After completion of the dropwise addition, the state at a temperature of 75 ° C. was maintained for 1 hour and then cooled to obtain a graft copolymer (A-6) latex. Next, 150 parts of a 1.2% sulfuric acid aqueous solution was heated to 75 ° C., and 100 parts of the graft copolymer (A-6) latex was gradually dropped into the solution under stirring to solidify it. Warmed and held for 5 minutes. Next, the precipitate was dehydrated, washed and dried to obtain a powdery graft copolymer (A-6) having an acetone insoluble content of 79% and an ηsp / C of 0.54 dl / g.

[Production Example 13]
Production of graft copolymer (A-7):
In Production Example 7, the acrylic acid ester rubbery polymer (G-1a) used is a large particle size acrylic acid ester rubbery polymer (Z-1) that is not enlarged by the acid group-containing copolymer (K). The polymerization was carried out in the same manner except for changing to) to obtain a graft copolymer (A-7) having an acetone insoluble content of 69% and an ηsp / C of 0.77 dl / g.

[Production Example 14]
Production of cross-linked hard polymer (B-1):
In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen gas inlet, etc., 19 parts of methyl methacrylate (MMA), 60 parts of styrene (St), 20 parts of ethyl acrylate (EA), 1 part of allyl methacrylate (AMA) ), 0.1 part of n-octyl mercaptan, 0.5 part of lauroyl peroxide, 0.5 part of polyvinyl alcohol and 200 parts of ion-exchanged water were charged, and the inside of the container was sufficiently replaced with nitrogen gas.
While stirring in a nitrogen stream, the contents were heated to 75 ° C. to initiate polymerization. After 3 hours, the temperature was raised to 85 ° C. and held for another 3 hours, and finally the temperature was raised to 95 ° C. and held for 1 hour to complete the polymerization. The obtained slurry was dehydrated and dried to obtain a bead-like crosslinked hard polymer (B-1). The mass average particle diameter was 150 μm.

[Production Examples 15 to 20]
Production of crosslinked hard polymers (B-2) to (B-7):
As shown in Table 3, a crosslinked hard polymer (B-2) was prepared in the same manner as in Production Example 14 except that the kind and amount of the monovinyl monomer and the monomer having two or more vinyl groups were changed. To (B-7) were obtained.

[Production Example 21]
Production of cross-linked hard polymer (B-8):
In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen gas inlet, etc., 95 parts of methyl methacrylate (MMA), 5 parts of ethylene glycol dimethacrylate (EGMA), 0.3 part of n-dodecyl mercaptan, t-butyl per 0.2 parts of oxy-2-ethylhexanoate and 150 parts of a 2% calcium triphosphate aqueous solution were charged into a container substituted with nitrogen gas.
The contents were heated to 70 ° C. under high-speed stirring to initiate polymerization, and after 5 hours, held at 100 ° C. for 1 hour to complete the polymerization. The content was dehydrated, filtered and dried to obtain a white powdery cross-linked hard polymer (B-8). The mass average particle diameter was 5 μm.

[Production Example 22]
Production of cross-linked hard polymer (B-9):
Polymerization was carried out in the same manner as in Production Example 14 except that the type and amount of the monomer were changed as shown in Table 3, to obtain a crosslinked hard polymer (B-9). Mass average particle diameter The particle diameter was 15 μm.

[Production Example 23]
Production of hard polymer (b-10):
Polymerization was carried out in the same manner as in Production Example 14 except that the type and amount of the monomer were changed as shown in Table 3, to obtain a non-crosslinked hard polymer (b-10). The mass average particle diameter was 170 μm.

[Production Example 24]
Production of other thermoplastic resin (C-1):
Known suspension polymerization of acrylic resin (C-1) consisting of 99 parts of methyl methacrylate and 1 part of methyl acrylate and having a reduced viscosity of 0.25 dl / g measured at 25 ° C. from an N, N-dimethylformamide solution Manufactured by.

[Production Example 25]
Production of other thermoplastic resin (C-2):
Acrylonitrile-styrene-methyl methacrylate ternary copolymer consisting of 7 parts of acrylonitrile, 23 parts of styrene, 70 parts of methyl methacrylate and having a reduced viscosity of 0.38 dl / g measured from an N, N-dimethylformamide solution at 25 ° C. The union (C-2) was produced by a known suspension polymerization.

[Production Example 26]
Production of other thermoplastic resin (C-3):
Known suspension polymerization of acrylonitrile-styrene copolymer (C-3) comprising 29 parts of acrylonitrile and 71 parts of styrene and having a reduced viscosity of 0.60 dl / g measured from an N, N-dimethylformamide solution at 25 ° C. Manufactured by.

[Example 1 to Example 21, Comparative Example 1 to Comparative Example 5]
Production of thermoplastic resin composition:
Graft copolymers (A-1) to (A-7) produced in Production Examples, cross-linked hard polymers (B-1) to (B-9), hard polymers (b-10), other thermoplastics Resins (C-1) to (C-3) were blended in the proportions shown in Tables 4 and 5, and 0.4 parts of ethylene bisstearylamide, ADK STAB LA-63P (Asahi Denka Kogyo Co., Ltd.) 0 .2 parts, Adekastab LA-36 (Asahi Denka Kogyo Co., Ltd.) 0.2 parts, and titanium oxide ("CR60-2", Ishihara Sangyo Co., Ltd.) 3 parts as a colorant, Henschel mixer The mixture was shaped with a degassing twin screw extruder ("PCM-30" manufactured by Ikekai Tekko Co., Ltd.) heated to a barrel temperature of 230 ° C to produce pellets.
The obtained pellets were discharged in a sheet form from a die having a width of 60 mm at a barrel temperature of 190 ° C. and 250 ° C. and a cooling roll temperature of 85 ° C. using a 25 mmφ single screw extruder manufactured by Thermo Plastics Industry Co., Ltd. By adjusting the thickness, a sheet having a width of 50 mm to 60 mm, whose thickness was adjusted to 200 μm to 250 μm, was extruded.

The thermoplastic resin compositions obtained in the examples and comparative examples were evaluated by the following evaluation tests. The results of evaluation are shown in Table 4 and Table 5.
(I) Charpy impact strength:
The measurement was carried out by a method in accordance with ISO 179, using a notched specimen and leaving the specimen for 12 hours or more in an atmosphere at 23 ° C.
(Ii) Melt volume rate (fluidity):
Measurement was performed under the conditions of a barrel temperature of 220 ° C. and a load of 98 N by a method based on ISO 1133.

(iii) Molding gloss and its temperature dependence:
The glossiness was measured as a reflectance of incident light of 60 °.
The temperature dependence of the molded sheet under the barrel temperature conditions of 190 ° C. and 250 ° C. was determined by the following equation (1).
[Gloss difference (%)] = (Glossiness at 250 ° C. molding) − (Glossiness at 190 ° C. molding) Formula (1)

(Iv) Molding appearance:
Judgment of matteness, appearance of fish eyes and die lines, and fineness of the surface are judged by visual judgment. ○ is recognized as a good sheet without problems. The middle was evaluated as Δ.
(V) Weather resistance (accelerated exposure test):
The white colored sheet was treated with a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) for 1,000 hours at a black panel temperature of 63 ° C. and a cycle condition of 60 minutes (rainfall: 12 minutes). The difference in color between the exposed test piece and the unexposed test piece measured with a color difference meter was evaluated by the degree of color change ΔE.

From the examples and comparative examples, the following became clear.
(1) The thermoplastic resin compositions of Examples 1 to 21 have both high Charpy impact strength and melt volume rate, good mattness at molding temperatures of 190 ° C. and 250 ° C., and light resistance by a sunshine weather meter. In the test, the discoloration was small. Such a resin composition has high industrial value.
(2) In particular, the thermoplastic resin compositions of Examples 1 to 3, Example 10, Example 12, Example 13, Example 19, and Example 21 show good material properties in all items. In particular, the gloss value is extremely low, and such resin compositions have extremely high industrial value.
(3) Since the thermoplastic resin composition of Comparative Example 1 does not contain the graft copolymer (A), the fluidity and weather resistance were good, but the Charpy impact strength was remarkably low, and such a resin composition The product has low industrial utility value.
(4) Since the thermoplastic resin composition of Comparative Example 2 does not contain the crosslinked hard polymer (B), the Charpy impact strength, fluidity, weather resistance, and matteness at a molding temperature of 190 ° C. are relatively good. Further, the matte property at a molding temperature of 250 ° C. is insufficient, and thus the resin composition whose matte appearance changes depending on the molding temperature has a low industrial utility value.
(5) The thermoplastic resin composition of Comparative Example 3 is a graft copolymer (a-) containing a (meth) acrylic acid ester-based rubbery polymer (G) to which the acid group-containing copolymer latex (K) is not applied. 7) is used, no matte properties are obtained at any molding temperature of 190 ° C. and 250 ° C. Such a resin composition has low industrial utility value.
(6) Since the thermoplastic resin composition of Comparative Example 4 contains a large amount of the crosslinked hard polymer (B), the matte property is good, but the Charpy impact strength and fluidity are low. Such a resin composition has low industrial utility value.
(7) Since the thermoplastic resin composition of Comparative Example 5 uses a non-crosslinked hard polymer (b-10), the glossiness at a molding temperature of 250 ° C. is high, and such a resin composition is industrial. The practical use value is low.

The thermoplastic resin composition of the present invention is a molded product having a wide molding temperature range that is excellent in fluidity during molding, capable of obtaining a molded product having a good matte appearance, and excellent in impact resistance and weather resistance. Obtainable. These balances are at a very high level that cannot be obtained with conventional thermoplastic resin compositions, and the utility value as various industrial materials is extremely high. The thermoplastic resin composition of the present invention is used for vehicle parts, particularly various exterior / interior parts used without painting, wall materials, building material parts such as window frames, tableware, toys, vacuum cleaner housings, television housings, air conditioner housings. It is suitably used for molded products such as household electrical appliance parts such as interior parts, marine members, communication device housings, notebook computer housings, PDA housings, liquid crystal projector housings, etc., particularly sheets or profile extrusion molded products.

Claims (11)

1 mass of graft copolymer (A) obtained by graft-polymerizing vinyl monomer to (meth) acrylic ester rubber-like polymer (G) that has been enlarged by acid group-containing copolymer latex (K) Parts to 99.9 parts by mass;
0.1 to 50 parts by mass of a crosslinked hard polymer (B),
Containing 0 to 80 parts by mass of other thermoplastic resin (C) [total 100 parts by mass of graft copolymer (A), crosslinked hard polymer (B), and other thermoplastic resin (C)] A thermoplastic resin composition characterized by the above.   The thermoplastic resin composition according to claim 1, wherein the (meth) acrylic ester rubber-like polymer (G) has a structural unit derived from a graft crossing agent and a structural unit derived from a crosslinking agent. object.   The structural unit derived from the graft crossing agent is a structural unit derived from an allyl compound, and the structural unit derived from the crosslinking agent is a structural unit derived from a di (meth) acrylate compound. The thermoplastic resin composition according to claim 2.   The thermoplastic resin composition according to any one of claims 1 to 3, wherein the (meth) acrylic acid ester-based rubbery polymer (G) has a mass average particle diameter of 300 nm or more.   The cross-linked hard polymer (B) is composed of a monovinyl monomer unit and a monomer unit having two or more vinyl groups. The thermoplastic resin composition according to claim 1.   6. The thermoplastic resin composition according to claim 5, wherein the monomer unit having two or more vinyl groups is a structural unit derived from an allyl compound or a structural unit derived from a dimethacrylate compound. .   The thermoplastic resin composition according to any one of claims 1 to 6, wherein the crosslinked hard polymer (B) contains no hydroxyl group.   The thermoplastic resin composition according to any one of claims 1 to 7, wherein the crosslinked hard polymer (B) has a particulate shape and a mass average particle diameter of 1 µm to 300 µm. object.   The other thermoplastic resin (C) is polymethyl methacrylate, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-N-substituted maleimide terpolymer, styrene-maleic anhydride-N-substituted. Maleimide terpolymer, polycarbonate resin, polybutylene terephthalate (PBT resin), polyethylene terephthalate (PET resin), polyvinyl chloride, polystyrene, methyl methacrylate-styrene copolymer (MS resin), acrylonitrile-styrene-methacrylic acid The thermoplastic resin composition according to any one of claims 1 to 8, wherein the thermoplastic resin composition is at least one selected from the group consisting of a methyl copolymer, a modified polyphenylene ether (modified PPE resin), and a polyamide.   A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 9.   A sheet or a profile extrusion-molded product obtained by extruding the thermoplastic resin composition according to any one of claims 1 to 9.