JP2002327124A - Thermoplastic resin composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molded product hardly having rough surface and filler speck, hardly causing the reduction of an impact resistance, and having excellent appearance, without causing scam and bleeding out at the time of molding even if a filler is compounded therewith. SOLUTION: This thermoplastic resin composition is obtained by compounding (A) 100 pts.wt. thermoplastic resin, (B) 0.1-400 pts.wt. acrylic high-molecular weight polymer, (C) a mixed powder including a polytetrafluoroethylene, and (D) 1-2,000 pts.wt. filler, regulated so that the content of the tetrafluoroethylene component in the powder (C) including the polytetrafluoroethylene may be 0.01-400 pts.wt. based on 100 pts.wt. thermoplastic resin (A).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermoplastic resin composition to which various fillers are added, a method for producing the same, and a molded article.

[0002]

2. Description of the Related Art Thermoplastic resins are widely used in various fields such as soft or hard films, sheets, flooring materials and irregularly shaped articles. These are molded by applying various methods such as extrusion, calendar, blow, injection molding, etc., depending on the target product.In this case, in order to exhibit various properties such as strength according to the product, Various fillers are added. As the filler, for example, impact strength modifiers, fillers, flame retardants, pigments and the like, wood powder for the purpose of increasing the amount,
Examples include paper and fiber. Recently, reuse of waste paper, recycled wood flour, and the like as a filler has been studied.

[0003] However, if a large amount of the filler is added in order to greatly exert the effect of the filler, a so-called eye dust or resin composition in which the deteriorated resin and the filler in the resin adhere to the lip of the die during molding. Plate-out, in which the filler in the material migrates to the metal surface in contact with the resin, may cause roughening of the surface of the molded product, filler damage (filler speck), or a decrease in impact strength. is there. In particular, the amount of filler added is 10 parts by mass with respect to 100 parts by mass of the thermoplastic resin.
When the amount is more than the mass part, these problems become remarkable. In order to solve such a problem, a polyvinyl chloride resin composition is disclosed in JP-B-6-62826 and JP-B-262826.
Japanese Patent Application Laid-Open No. 9-208798 and the like for ABS resin compositions and Japanese Patent Application Laid-Open No. 10-87928 and the like for styrene-based resin compositions, widely examine processing aids to be added to thermoplastic resins. Thus, the releasability of the calender roll of the resin and the deterioration of the retention have been improved to some extent.

[0004]

However, molding of a thermoplastic resin and / or a recycled thermoplastic resin, in particular, contains various fillers such as rubber, recycled wood flour, waste paper, flame retardants, and pigments. In the case where the thermoplastic resin composition is formed by extrusion molding, calendar molding, blow molding, or the like, eye tanning and plate out are not sufficiently suppressed. If such eye frays or plate-outs occur, the appearance of the molded body may deteriorate or the subsequent molding may become impossible.Therefore, the molding operation is interrupted at regular intervals and the die lip is cleaned. Must be performed, which greatly reduces productivity. There is a method of adding an external acrylic lubricant or a lubricant such as a metal soap or a wax to a thermoplastic resin in advance to suppress eyelashes and plate-out, but the effect of these additions is not always sufficient.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the polytetrafluoroethylene-containing mixed powder and the acrylic high molecular weight polymer have been converted into a thermoplastic resin. It has been found that when added, even if a filler is blended, no eye mold or plate-out occurs during molding. When such a thermoplastic resin is used, the surface of the molded body becomes rough, and the filler is damaged (filler spec.
The present inventors have found that a molded article excellent in appearance, which does not cause k) and does not lower impact strength, can be obtained, and has reached the present invention. That is, the thermoplastic resin composition of the present invention comprises 0.1 to 400 parts by mass of the acrylic high molecular weight polymer (B) and 100 parts by mass of the thermoplastic resin (A) and 100 parts by mass of the polytetrafluoroethylene-containing mixed powder. Body (C) and filler (D) 1-20
The polytetrafluoroethylene-containing mixed powder (C) contains 100 parts by mass of the thermoplastic resin (A) in which the polytetrafluoroethylene component in the polytetrafluoroethylene-containing mixed powder (C) is 100 parts by mass. 0.0 for
It is characterized by being blended in an amount of 1 to 400 parts by mass.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the present invention, various thermoplastic resins can be used as the thermoplastic resin (A). For example, polypropylene (P
P), high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LL)
Styrene resins such as DPE), polyvinyl chloride resin (PVC), polystyrene (PS), high impact polystyrene (HIPS), styrene / acrylonitrile copolymer resin (SAN), and rubber-reinforced styrene / acrylonitrile copolymer resin (ABS, ASA, SAS), methacrylic resin, polycarbonate (PC), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polybutylene naphthalate (PBN), polyethylene naphthalate (PEN), polycyclohexane terephthalate (PCT) , Polyphenylene ether resin (PPE) and its modified products, polyamide resin (PA) such as polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polylactic acid, polycaprolactone, Vinyl alcohol, modified starch, a biodegradable resin such as polyhydroxybutyric acid, poly-1
-Butene, polyisobutylene, random copolymer or block copolymer in any ratio of propylene and ethylene and / or 1-butene, ethylene in which the diene component is 50% by mass or less in any ratio of ethylene and propylene Propylene-diene terpolymer,
Cyclic polyolefins such as polymethylpentene, copolymers of cyclopentadiene with ethylene and / or propylene, up to 50% by weight of ethylene or propylene with eg vinyl acetate, alkyl methacrylates,
Acrylic esters, aromatic alkyl esters, random copolymers with vinyl compounds such as aromatic vinyl,
Examples include a block copolymer or a graft polymer. Above all, PP, HDPE, LDPE, LLDP
E, PVC, PS, HIPS, AS, ABS, ASA,
SAS, methacrylic resin, PC, PBT, PET, PB
N, PEN, PCT, at least one selected from ethylene-propylene random or block copolymer,
This is preferable in that it has high versatility and is inexpensive. Further, among these, at least one selected from polyethylene resins, polypropylene resins, and styrene resins is preferable.

Further, a recycled resin material can be used alone or in combination with a non-recycled resin material for the thermoplastic resin (A). Examples of the recycled resin material include bumpers, door trims, instrument panel interior materials, and outer plates. Resin parts such as automobile resin parts, recycled PET bottles, housings of home electric appliances such as televisions, personal computers, and printers can be used. In particular, polyolefin automobile bumpers are preferable from the viewpoint of recyclability.

[0008] The thermoplastic resin (A) may be an alkyl (meth) acrylate or a maleic anhydride, acrylic acid, glycidyl methacrylate or the like which has been conventionally added for improving the compatibility between the filler and the thermoplastic resin. A modified polyolefin resin (E) modified with an organic acid or the like can be used in combination. Examples of the alkyl (meth) acrylate-based modified polyolefin resin include ethylene such as ethylene-methyl methacrylate, ethylene-ethyl acrylate, ethylene-methyl acrylate, ethylene-butyl methacrylate, ethylene-hexyl acrylate, ethylene-lauryl methacrylate, and ethylene-stearyl acrylate. Acrylic ester or various methacrylic esters, preferably 99 to 60% by mass
Of ethylene and 1 to 40% by mass of methyl methacrylate, and a blend of one or more of these. As the organic acid-modified polyolefin, maleic anhydride,
Polyolefin modified with a modifying compound such as dimethyl maleate, diethyl maleate, acrylic acid, methacrylic acid, tetrahydrophthalic acid, glycidyl methacrylate, hydroxyethyl methacrylate, and the like. The amount (denaturation amount) is 0.1 to 60% by mass. These modified polyolefin resins can be used alone or in combination of two or more, and are contained in the thermoplastic resin (A) in an amount of 0.1 to 100.
% By mass, preferably 0.2 to 30% by mass.

[0009] The acrylic high molecular weight polymer (B) used in the present invention is blended with the thermoplastic resin composition in order to enhance the lubricity of the thermoplastic resin composition. -1) is obtained by polymerization. The acrylic monomer (b-1) has an alkyl group having 1 to 18 carbon atoms.
It is preferable to include the alkyl methacrylate and / or the alkyl acrylate. Examples of such alkyl methacrylate or alkyl acrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, methyl acrylate, Examples include ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, and the like. On the other hand, alkyl methacrylates and / or alkyl acrylates in which the alkyl group has 19 or more carbon atoms tend to be less likely to undergo a copolymerization reaction.
Moreover, even if the acrylic monomer (b-1) contains a vinyl monomer having 1 to 18 carbon atoms in the alkyl group and copolymerizable with an alkyl methacrylate and / or an alkyl acrylate. Good. Examples of such a vinyl monomer include styrene, α-methylstyrene, acrylonitrile, vinyl acetate, and the like.

Alkyl methacrylate and / or alkyl acrylate in the acrylic monomer (b-1);
Preferred mixing ratios of these with a copolymerizable vinyl monomer are as follows: alkyl methacrylate is 40 to 95% by mass, alkyl acrylate is 5 to 60% by mass, and vinyl monomer is 0 to 30% by mass. is there. When the acrylic monomer (b-1) is used in such a mixing ratio, the lubricity of the thermoplastic resin composition is further increased, and the occurrence of die build-up and plate-out during molding can be effectively suppressed.

The acrylic high molecular weight polymer (B) preferably has a reduced viscosity (η sp / C) of 15 or less, more preferably 3 or less. Reduced viscosity (η
When (sp / C) exceeds 15, the appearance of the molded article tends to deteriorate. Here, the reduced viscosity (η sp / C)
The term means a value measured at 25 ° C. for a solution obtained by dissolving 0.1 g of the polymer in 100 ml of chloroform.

The most suitable method for producing the acrylic high molecular weight polymer (B) is an emulsion polymerization method, which can be polymerized in one step or multiple steps. Preferably, the polymerization is carried out in three or three stages. Obtaining the acrylic high molecular weight polymer (B) as a powder by treating the acrylic high molecular weight polymer (B) latex obtained by the emulsion polymerization method with a rapid coagulation method using an acid or a salt. Can be. The obtained acrylic high molecular weight polymer (B) exerts a sufficient effect even in a powder state for use in a thermoplastic resin composition. However, the thermoplastic resin (A), which is a matrix resin, is often in the form of bead particles or pellets. Therefore, in order to suppress classification during mixing with the matrix resin, an acrylic high molecular weight polymer (B) is used. Is preferably set as a granular powder. Further, it is more preferable to form pellet-like particles.

Means for forming a granular powder include a solvent method in which a solvent is added during coagulation with an acid or a salt and acid precipitation is carried out to form granules, and an acid or a salt is used to coagulate under a slow condition using an acid or a salt. Examples thereof include a slow solidification method in which a latex is precipitated and granulated, and a spray dry method in which latex is sprayed in a high-temperature air stream and dried to obtain a granular powder. Examples of the means for forming pellet-like particles include an extrusion granulation method using an extruder, a roll pellet method for cutting a roll sheet to obtain cube-shaped pellets, and a means for pelletizing with a pellet-shaped briquetting roll having a dent. And the like. In this case, in order to improve the dispersibility at the time of the subsequent molding, it is preferable to compress as loosely as possible into a pellet. Pelletization may be performed by a granulation method using a transfer agent. As a transfer agent, liquid paraffin commonly used, DOP
(Dioctyl phthalate) and the like can be used. The amount of the transfer agent used is preferably 50% by mass or less. As for the pellet-shaped particles, in order to further improve the dispersibility in the resin composition at the time of molding, those previously formed into pellets by dilution with a thermoplastic resin may be used. In this case, the content of the thermoplastic resin in the pellet is preferably 70% by mass or less, more preferably 3% by mass.
0 to 60% by mass. If it exceeds 70% by mass, the amount of the acrylic high molecular weight polymer (B) in the pellets is small, and the productivity per acrylic high molecular weight polymer (B) is undesirably reduced. The type of the thermoplastic resin used for this dilution does not have to be the same type as the matrix resin as long as it is dispersed in the resin composition at the time of molding. It is preferable that

The mixing ratio of the acrylic high molecular weight polymer (B) is 0.1 to 100 parts by mass of the thermoplastic resin (A).
４００400 parts by mass. If the amount of the acrylic high molecular weight polymer (B) is less than 0.1 part by mass, the lubricity of the thermoplastic resin composition is not sufficiently improved. Worsens. More preferably, the mixing ratio of the acrylic high molecular weight polymer (B) is 0.5 to 360 with respect to 100 parts by mass of the thermoplastic resin (A).
Parts by weight. In addition, acrylic high molecular weight polymer (B)
Is diluted with a thermoplastic resin in advance and molded into pellets or the like, the amount of the thermoplastic resin used for the dilution is calculated as a part of the thermoplastic resin (A).

The polytetrafluoroethylene-containing mixed powder (C) used in the present invention comprises polytetrafluoroethylene particles, preferably polytetrafluoroethylene particles having a particle diameter of 10 μm or less, and an organic polymer. In the present invention, in the polytetrafluoroethylene-containing mixed powder (C), one polytetrafluoroethylene is contained.
No aggregates exceeding 0 μm were formed. Generally used polytetrafluoroethylene fine powder is a step of recovering a powder from the state of a particle dispersion liquid, and usually comprises 1
It is difficult to uniformly disperse the particles in the thermoplastic resin because the aggregates are formed to have a size of 00 μm or more. On the other hand, the polytetrafluoroethylene-containing mixed powder (C) used in the present invention is a mixed powder with an organic polymer, and polytetrafluoroethylene alone does not form a domain having a particle diameter exceeding 10 μm. Therefore, the dispersibility in a thermoplastic resin, particularly a styrene resin, is extremely excellent. Therefore, in the thermoplastic resin composition of the present invention, particularly in the styrene resin composition, polytetrafluoroethylene is efficiently fiberized in the resin, and various moldability is excellent, and also the surface property is excellent. . The content ratio of polytetrafluoroethylene in the polytetrafluoroethylene-containing mixed powder (C) used in the present invention is 0.1 to 90.
What is mass% is preferable. More preferably, 20 to 6
0% by mass.

The polytetrafluoroethylene-containing mixed powder (C) is prepared by mixing an aqueous dispersion of polytetrafluoroethylene particles having a particle diameter of 0.05 to 1.0 μm with an aqueous dispersion of organic polymer particles. And coagulation or powderization by spray drying, particle size 0.05-1.0μ
m, a method of polymerizing the monomer (c-1) constituting the organic polymer in the presence of the aqueous polytetrafluoroethylene particle dispersion, followed by coagulation or spray-drying to obtain a powder.
Alternatively, in a dispersion obtained by mixing an aqueous dispersion of polytetrafluoroethylene particles having an average particle diameter of 0.05 to 1.0 μm and an aqueous dispersion of organic polymer particles, a monomer having an ethylenically unsaturated bond (c- After 2) is emulsion-polymerized, it can be obtained by a method of pulverizing by coagulation or spray drying. In the method of powdering by coagulation, latex is put into hot water in which metal salts such as calcium chloride and magnesium sulfate are dissolved.

The particle size of the polytetrafluoroethylene-containing mixed powder (C) is 0.05 to 1.0 μm.
The aqueous dispersion of polytetrafluoroethylene particles of m can be obtained by polymerizing a tetrafluoroethylene monomer by emulsion polymerization using a fluorinated surfactant. In the case of emulsion polymerization, a fluorinated olefin such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, or perfluoroalkylvinyl ether, or a Fluorine-containing alkyl (meth) acrylates such as fluoroalkyl (meth) acrylate can be used. The use amount of these copolymer components is 10% by mass based on tetrafluoroethylene.
The following is preferred. Commercially available raw materials for the aqueous dispersion of polytetrafluoroethylene particles include Fluon AD-1 and AD-936 manufactured by Asahi ICI Fluoropolymer Co., Ltd., and Polyflon D-1 and D-2 manufactured by Daikin Industries, and DuPont Mitsui Fluorochemical Co., Ltd. Teflon (registered trademark) 30J and the like can be cited as typical examples.

The organic polymer constituting the polytetrafluoroethylene-containing mixed powder (C) is not particularly limited. However, from the viewpoint of dispersibility when blended with a thermoplastic resin, each organic polymer may be mixed with each other. It is preferable that the affinity is high. Monomer (c-) for producing an organic polymer
Specific examples of 1) include styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, t-butylstyrene, o-ethylstyrene, p-chlorostyrene, o-chlorostyrene, and 2,4-dichloro. styrene,
p-methoxystyrene, o-methoxystyrene, 2,4
-Aromatic vinyl monomers such as dimethylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate,
Ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, (Meth) acrylate monomers such as cyclohexyl acrylate and cyclohexyl methacrylate; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; α, β-unsaturated carboxylic acids such as maleic anhydride; Maleimide monomers such as phenylmaleimide, N-methylmaleimide and N-cyclohexylmaleimide; glycidyl group-containing monomers such as glycidyl methacrylate; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether Vinyl monomers such as vinyl acetate and vinyl butyrate; olefin monomers such as ethylene, propylene and isobutylene; and diene monomers such as butadiene, isoprene and dimethylbutadiene. be able to.

These can be used alone or as a mixture of two or more. For example, when a styrene resin, a polypropylene resin, a polyethylene resin, or the like is used as the thermoplastic resin (A) as the matrix resin, From the viewpoint of affinity, it is preferable to use an aromatic vinyl monomer, a (meth) acrylate monomer, or a vinyl cyanide monomer as the monomer (c-1). Further, as particularly preferred, 1 selected from the group consisting of styrene, butyl acrylate, and acrylonitrile
Monomer containing at least 10% by mass of at least one kind of monomer (c-
1) can be mentioned.

The monomer (c-2) having an ethylenically unsaturated bond used in the production of the polytetrafluoroethylene-containing mixed powder (C) includes aromatic vinyl monomers, (meth) Acrylic ester monomers, vinyl cyanide monomers and the like can be mentioned. The polytetrafluoroethylene-containing mixed powder (C) is a thermoplastic resin (A) 10
The polytetrafluoroethylene component is blended so as to be 0.01 to 400 parts by mass with respect to 0 parts by mass. More preferably, with respect to 100 parts by mass of the thermoplastic resin (A),
The polytetrafluoroethylene component is in the range of 0.1 to 200 parts by mass. If the polytetrafluoroethylene component is less than 0.01 parts by mass, eyelashes and plate-out occur when the thermoplastic resin composition is molded, and the appearance tends to be poor. Further, roughening of the surface of the molded body occurs, and the impact strength is reduced. If the polytetrafluoroethylene component exceeds 400 parts by mass, the rubber elasticity of the thermoplastic resin composition at the time of melting may be too high to deteriorate the surface appearance.

Among the fillers (D) used in the present invention, those intended to improve the physical properties and increase the amount of the filler include:
Metal powders, oxides, hydroxides, silicic acid or silicates, carbonates, silicon carbide, vegetable fibers, animal fibers, synthetic fibers, and the like, specific examples of which include aluminum powder, copper Powder, iron powder, alumina, natural wood, paper, calcium carbonate, talc, glass fiber, magnesium carbonate, mica, kaolin, calcium sulfate, barium sulfate, aluminum hydroxide, magnesium hydroxide, silica, clay, zeolite, acetate powder, Silk powder, aramid fiber,
Azodicarbonamide, graphite, and reclaimed filler materials. These can be used alone or in combination of two or more. Recycled filler materials used for the filler (D) include rice husk, bran, rice bran,
Agricultural wastes such as corn shavings, sweet potatoes, defatted soybeans, walnut shells, coconut coconut shells, coconut shells, bagasse, distilled spirits such as shochu, beer malt cake, wine grape cake,
Sake lees, brewed lees such as soy sauce lees, tea dregs, coffee dregs, various types of dregs from beverage factories such as citrus squeeze, food processing wastes such as okara and chlorella, shells such as oyster shells, shrimp and crab shells, etc. Examples include marine waste, sawdust, waste wood, bark, logging bamboo, woody waste such as waste wood generated from demolition of wooden houses, and waste such as waste pulp and paper chips from the waste paper and paper industry. Can be These can be used alone or in combination of two or more.

Examples of the flame retardant used in the filler (D) include antimony oxide, titanium phosphate, vinyl bromide, chlorinated paraffin, decabromodiphenyl, decabromophenol oxide, TBA epoxy oligomer, TBA epoxy oligomer,
BA polycarbonate oligomer, TPP, phosphate ester, hexabromobenzene, aluminum hydroxide, magnesium hydroxide and the like can be mentioned, and these can be used alone or in combination of two or more. Examples of the pigment used for the filler (D) include titanium white, titanium yellow, red iron, cobalt blue, and carbon black. These can be used alone or in combination of two or more. .

In the present invention, a foaming agent can be used as the filler (D), and typical examples thereof include an inorganic foaming agent, a volatile foaming agent, and a decomposition type foaming agent. Examples of the inorganic blowing agent include carbon dioxide, air, and nitrogen. Examples of the volatile blowing agent include aliphatic hydrocarbons such as propane, n-butane, isobutane, pentane, and hexane, trichlorofluoromethane, dichlorofluoromethane, and dichlorotetrafluoroethane. And halogenated hydrocarbons such as methyl chloride, ethyl chloride and methylene chloride. As the decomposition type foaming agent, azodicarbonamide, dinitrosopentamethylenetetramine, azobisisobutyronitrilyl, sodium bicarbonate and the like can be used. These foaming agents can be appropriately mixed and used. When using a foaming agent,
A bubble regulator may be further added to the melt-kneaded product of the thermoplastic resin composition. Examples of the cell regulator include inorganic powders such as talc and silica, acidic salts of polycarboxylic acids, reaction mixtures of polycarboxylic acids with sodium carbonate or sodium bicarbonate, and citric acid.

These fillers (D) are blended in an amount of 1 to 2,000 parts by mass based on 100 parts by mass of the thermoplastic resin (A). If the amount of the filler (D) is less than 1 part by mass, the effect of improving the moldability tends to decrease, and if it exceeds 2000 parts by mass, the appearance tends to deteriorate.

Various additives can be added to the thermoplastic resin composition of the present invention as needed. For example, as a stabilizer, pentaerythrityl-tetrakis 3- (3,
5-di-t-butyl-4-hydroxyphenyl) propionate}, triethylene glycol-bis {3- (3
-T-butyl-5-methyl-4-hydroxyphenyl)
Phenolic stabilizers such as propionate II, tris (monononylphenyl) phosphite, tris (2,
Examples thereof include phosphorus-based stabilizers such as 4-di-t-butylphenyl) phosphite and sulfur-based stabilizers such as dilauroyldipropionate. These may be used alone or in combination of two or more. it can. In addition, as long as the object of the present invention is not impaired, 2,6-di-butyl-
Phenolic antioxidants such as 4-methylphenol, 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), tris (mixed, mono and dinyphenyl) phosphite, diphenyl isodecyl phosphite Phosphite-based antioxidants, such as dilauryl thiodipropionate, dimyristyl thiodipropionate diasterial thiodipropionate, 2-hydroxy-4-octoxybenzophenone, 2- (2 Benzotriazole-based ultraviolet absorbers such as -hydroxy-5-methylphenyl) benzotriazole, light stabilizers such as bis (2,2,6,6) -tetramethyl-4-piperidinyl), hydroxylalkylamine, sulfonate Antistatic agents such as ethylene bisstearyl urea Various additives such as lubricants such as amides and metal soaps can be appropriately blended to further adjust physical properties and characteristics.

The above-mentioned essential components and optional components optionally added are added in predetermined amounts, that is, 0.1 to 400 parts by mass of the acrylic high molecular weight polymer (B) per 100 parts by mass of the thermoplastic resin (A). The polytetrafluoroethylene-containing mixed powder (C) is mixed with the polytetrafluoroethylene component in the polytetrafluoroethylene-containing mixed powder (C) in an amount of 0.01 to 100 parts by mass of the thermoplastic resin (A). ４００400 parts by mass,
A thermoplastic resin composition can be prepared by mixing 1 to 2000 parts by mass of the filler (D) and kneading the mixture with a usual kneading machine such as a roll, a Banbury mixer, a single screw extruder, or a twin screw extruder. In this case, particularly, a master pellet containing a part of the thermoplastic resin (A), the acrylic high molecular weight polymer (B) and the polytetrafluoroethylene-containing mixed powder (C) is manufactured in advance, and then the remaining master pellets are prepared. By mixing the thermoplastic resin and the filler (D) into the master pellet, a thermoplastic resin composition having more excellent dispersibility of each component can be obtained. The obtained thermoplastic resin composition is appropriately formed into pellets.

The thermoplastic resin composition of the present invention can be applied to various molding methods, and examples thereof include injection molding, calender molding, blow molding, extrusion molding, thermoforming, foam molding, and melt spinning. Examples of the molded article include an injection molded article, a sheet, a film, a hollow molded article, a pipe, a square rod, a deformed article, a thermoformed article, a foam, and a fiber. The extruded product obtained can suppress tar and plate-out, and has no surface roughness on the surface of the molded product, no filler speck, etc., does not decrease impact strength, and has excellent appearance of the molded product. Extrusion molding can use general extrusion production equipment, and examples thereof include a single screw extruder, a parallel twin screw extruder, and a conical twin screw extruder. As the die provided at the tip of the extruder, a commonly used die can be used without any limitation. Thus, the thermoplastic resin (A) 1
Acrylic high molecular weight polymer (B) based on 00 parts by mass
0.1 to 400 parts by mass and the polytetrafluoroethylene-containing mixed powder (C) are mixed with the polytetrafluoroethylene component in the polytetrafluoroethylene-containing mixed powder (C) by 100 parts by mass of the thermoplastic resin (A). 0.0 per part
Even if the filler (D) is blended, the thermoplastic resin composition is blended so as to be 1 to 400 parts by mass and the filler (D) is blended with 1 to 2000 parts by mass. Occasionally, no eye repelling or plate-out occurs, no roughening of the surface of the molded body, no flaws (filler speck),
In addition, a molded article excellent in the appearance of the molded article, in which the impact strength does not decrease, can be obtained, and the moldability can be improved.

[0028]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition, "part" in an example shows a mass part. [Reference Example 1: Acrylic high molecular weight polymer (B-1)] In a reactor equipped with a stirrer and a reflux condenser, ion-exchanged water 28 was added.
0 parts, 1.5 parts of potassium alkenyl succinate, 2 parts of ammonium persulfate, 25 parts of methyl methacrylate, and 0.05 part of n-octyl mercaptan were charged. After the atmosphere in the vessel was replaced with nitrogen, the temperature was raised to 65 ° C. with stirring. And heated and stirred for 2 hours. Subsequently, 25 parts of n-butyl methacrylate, n
A mixture of -butyl acrylate (25 parts) and n-octyl mercaptan (0.5 parts) was added dropwise over 1 hour, and after the addition was completed, the mixture was further stirred for 2 hours. Thereafter, to this reaction system, a mixture of 25 parts of methyl methacrylate and 0.03 part of n-octyl mercaptan was added over 30 minutes, and the mixture was further stirred for 2 hours to terminate the polymerization.
P-3). The reduced viscosity (η sp / C) of this acrylic high molecular weight polymer was 0.8.

Next, 600 parts of ion-exchanged water and 3 parts of sulfuric acid were charged into a reactor equipped with a stirrer, heated to 50 ° C., and the above-prepared P-3 was charged over 5 minutes with stirring.
After charging, the temperature was raised to 95 ° C., and the temperature was maintained for 5 minutes, followed by filtration, washing and drying to obtain an acrylic high molecular weight polymer (B-1).

Reference Example 2: Acrylic high molecular weight polymer (B-2) In a reactor equipped with a stirrer and a reflux condenser, 280 parts of ion-exchanged water, 1.5 parts of potassium alkenyl succinate, and 2 parts of ammonium persulfate were used. , 92 parts of methyl methacrylate, 8 parts of n-butyl acrylate, and 0.03 part of n-octyl mercaptan, and after the atmosphere in the vessel was replaced with nitrogen, the temperature was increased to 65 ° C. with stirring, and the mixture was heated with stirring for 4 hours. The polymerization is terminated, and the copolymer particle dispersion (hereinafter referred to as P-
4). The reduced viscosity (η sp / C) of this acrylic high molecular weight polymer was 8.0.

Next, 600 parts of ion-exchanged water and 3 parts of sulfuric acid were charged into a reactor equipped with a stirrer, heated to 50 ° C., and the above-prepared P-4 was added thereto with stirring for 5 minutes.
After charging, the temperature was raised to 95 ° C., and the temperature was maintained for 5 minutes, followed by filtration, washing and drying to obtain an acrylic high molecular weight polymer (B-2).

Reference Example 3: Mixed powder containing polytetrafluoroethylene (C-1) In a separable flask equipped with a stirrer, a condenser, a thermocouple, and a nitrogen inlet, 190 parts of distilled water and dodecylbenzenesulfonic acid were added. Sodium 1.
5 parts, 100 parts of styrene and 0.5 part of cumene hydroperoxide were charged and heated to 40 ° C. under a nitrogen stream. Subsequently, 0.001 part of iron sulfate, 0.003 part of disodium ethylenediaminetetraacetate, 0.24 part of Rongalit salt,
A mixed solution of 10 parts of distilled water was added to perform radical polymerization. After the end of the heat generation, the temperature in the system was maintained at 40 ° C. for 1 hour to complete the polymerization, and the styrene polymer particle dispersion (hereinafter referred to as P-
1). Styrene polymer particle dispersion (P-
The solid concentration of 1) was 33.3% by mass, the particle size distribution showed a single peak, and the weight average particle size was 96 nm. On the other hand, as a polytetrafluoroethylene-based particle dispersion, “Fluon AD93” manufactured by Asahi ICI Fluoropolymer Co., Ltd.
6 "was used. The solid content of “Fluon AD936” was 63.0% by mass, and polytetrafluoroethylene 1
It contains 5 parts of polyoxyethylene alkylphenyl ether with respect to 00 parts. "Fluon AD93
The particle size distribution of "6" showed a single peak, and the weight average particle size was 290 nm. 833 copies of “Fluon AD9
36 ”, 1167 parts of distilled water was added, and the solid content concentration was 2
A 6.2% by mass polytetrafluoroethylene particle dispersion (F-1) was obtained. The polytetrafluoroethylene particle dispersion (F-1) contains 25% by mass of polytetrafluoroethylene particles and 1.2% by mass of polyoxyethylene nonylphenyl ether. 160 parts of F-1
(40 parts of polytetrafluoroethylene) and 181.8 parts of P-1 (60 parts of polystyrene) were charged into a separable flask equipped with a stirrer, a condenser, a thermocouple, and a nitrogen inlet, and then heated at room temperature under a nitrogen stream. Stir for 1 hour. Thereafter, the inside of the system was heated to 80 ° C. and kept for 1 hour. No solids were separated during the series of operations, and a uniform particle dispersion was obtained. The solid content concentration of the particle dispersion is 29.3% by mass, the particle size distribution is relatively broad, and the weight average particle size is 168 n.
m. 341.8 parts of this particle dispersion liquid is put into 700 parts of 85 ° C. hot water containing 5 parts of calcium chloride, the solid content is separated, filtered and dried to obtain a mixed powder containing polytetrafluoroethylene (C-1). 98 parts were obtained. After the polytetrafluoroethylene-containing mixed powder (C-1) was shaped into strips at 250 ° C. by a press molding machine, ultrathin sections were observed with a microtome without staining using a transmission electron microscope. Although polytetrafluoroethylene was observed as a dark part, no aggregate exceeding 10 μm was observed.

Reference Example 4: Mixed powder containing polytetrafluoroethylene (C-2) Dodecyl methacrylate 75
Azobisdimethylvaleronitrile (0.1 part) was dissolved in a mixed solution of 1 part and 25 parts of methyl methacrylate. 2.0 parts of sodium dosylbenzenesulfonate and 3 parts of distilled water
Add 00 parts of the mixed solution, and mix
After stirring for 4 minutes at rpm, the homogenizer was
Passing twice at a pressure of g / cm ² gave a stable dodecyl methacrylate / methyl methacrylate pre-dispersion. This was charged into a separable flask equipped with a stirrer, a condenser, a thermocouple, and a nitrogen inlet, and the internal temperature was raised to 80 under a nitrogen stream.
The mixture was stirred at a temperature of 3 ° C. for 3 hours for radical polymerization to obtain a dodecyl methacrylate / methyl methacrylate copolymer particle dispersion (hereinafter referred to as P-2). The solid concentration of P-2 was 25.1% by mass, the particle size distribution showed a single peak, and the weight average particle size was 198 nm. 160 parts (40 parts of polytetrafluoroethylene) of F-1 and 159.4 parts of P-2 (40 parts of dodecyl methacrylate / methyl methacrylate copolymer) used in Reference Example 1 were mixed with a stirrer, a condenser, and a thermoelectric device. The mixture was charged into a separable flask equipped with a nitrogen inlet and a dropping funnel, and stirred at room temperature for 1 hour under a nitrogen stream. Thereafter, the temperature of the system was raised to 80 ° C., and a mixed solution of 0.005 part of iron sulfate, 0.003 part of disodium ethylenediaminetetraacetate, 0.24 part of Rongalite salt and 10 parts of distilled water was added, and then methyl methacrylate was added. A mixture of 20 parts and 0.1 part of tertiary butyl peroxide was added dropwise over 30 minutes.
For 1 hour to complete the radical polymerization. No solid content was separated through a series of operations, and a uniform particle dispersion was obtained. The solid content concentration of the particle dispersion is 28.5% by mass,
The particle size distribution is relatively broad and the weight average particle size is 248.
nm. 349.7 parts of this particle dispersion liquid is put into 600 parts of 75 ° C. hot water containing 5 parts of calcium chloride, the solid content is separated, filtered and dried to obtain a mixed powder containing polytetrafluoroethylene (C-2). 97 parts were obtained. The dried polytetrafluoroethylene-containing mixed powder (C-2) was mixed with 2
After shaping into a strip shape at 20 ° C. by a press molding machine, ultrathin sections were observed with a microtome under a transmission electron microscope without staining. Although polytetrafluoroethylene was observed as a dark part, no aggregate exceeding 10 μm was observed.

[Reference Example 5: Master batch (M-1) of mixed powder containing polytetrafluoroethylene] Linear homopolypropylene pellets ("EA" manufactured by Nippon Polychem Co., Ltd.)
7 ", MFR: 1.2 g / 10 min.) 75 parts of the polytetrafluoroethylene-containing mixed powder (C-2) obtained in Reference Example 4 were blended in 25 parts, and hand blended.
Twin screw extruder (“ZSK30” manufactured by Werner & Pfleiderer)
Using a barrel temperature of 200 ° C. and a screw rotation speed of 20
The mixture was melt-kneaded at 0 rpm and shaped into pellets to obtain a master batch (hereinafter, referred to as M-1) of a polytetrafluoroethylene-containing mixed powder.

In each of the above Reference Examples, the measurement of the solid content concentration and the like was carried out by the following methods. (1) Solid concentration: determined by drying the particle dispersion at 170 ° C. for 30 minutes. (2) Particle size distribution, weight-average particle size: A sample obtained by diluting a particle dispersion with water was subjected to a dynamic light scattering method (“ELS800” manufactured by Otsuka Electronics Co., Ltd., temperature 25 ° C., scattering angle 90).
Degree). (3) Reduced viscosity (η sp / C): For a solution obtained by dissolving 0.1 g of the polymer in 100 ml of chloroform,
It was determined by measuring at 25 ° C.

[Examples 1-26, Comparative Examples 1-21] Mixed powders containing the following polypropylene, acrylic high molecular weight polymers (B-1 and 2) obtained in the above reference example, and polytetrafluoroethylene (C-1 to 2) or the ratio (parts) of the master pellet (M-1) and the filler shown in Tables 1 and 2
And extrusion-molded under the following molding machine and conditions to produce a molded article of the thermoplastic resin composition. The molded product was evaluated as described below with respect to the occurrence of die build-up, appearance in the molded product, and occurrence of plate-out, and the results are shown in Table 1.
-4 are shown. In Tables 1 to 4, CD-123 indicates a commercially available powdered polytetrafluoroethylene ("Fluon CD123" manufactured by Asahi ICI Fluoropolymers Co., Ltd., molecular weight: 12,000,000) which has not been treated with an organic polymer.

Polypropylene: “Novatec PP” manufactured by Nippon Polychem “BC06C”: MFR; 60 g / 10 min “BC03C”: MFR; 30 g / 10 min “FY-6C”: MFR; 2.4 g / 10 min Extruder : IKG screw diameter: φ50mm single screw extruder, rotation speed 50rpm
m Die shape: width 80mm, thickness 3mm

[Generation of Eye Dye] The time until the occurrence of eye die was measured. [Appearance of molded article] The appearance of the sheet was visually judged according to the following criteria. ：: good ×: rough skin or swelling [plate out] Using a two-roll mill, the roll surface during molding was visually observed. ：: No plate out △: Roll surface was slightly dirty ×: Roll surface was very dirty

[0039]

[Table 1]

[0040]

[Table 2]

[0041]

[Table 3]

[0042]

[Table 4]

[Examples 27 to 52, Comparative Examples 22 to 42]
The following polyethylene is filled with the acrylic high molecular weight polymer (B-1 or 2) obtained in the above reference example and the mixed powder (C-1 or 2) or the master pellet (M-1) containing tetrafluoroethylene. The materials were blended at the ratios shown in Tables 3 and 4, and a thermoplastic resin molded body was produced using the molding machine and conditions described above in the same manner as in Example 1 above. The molded article was evaluated with respect to the occurrence of die cast, appearance in the molded article, and occurrence of plate-out, and the results are shown in Tables 5 to 8. In Tables 5 to 8, CD-123 is a commercially available powdered polytetrafluoroethylene not treated with an organic polymer ("Fluon CD12" manufactured by Asahi ICI Fluoropolymers Co., Ltd.).
3 "Molecular weight: 12,000,000).

Polyethylene: “Novatech” “HD HY540” (HDPE) manufactured by Nippon Polychem Co., Ltd .: MFR; 1.0 g
/ 10 min "LD LJ801N" (LDPE): MFR; 30 g
/ 10 min “UE 320” (LLDPE): MFR; 0.7 g /
10 minutes

[0045]

[Table 5]

[0046]

[Table 6]

[0047]

[Table 7]

[0048]

[Table 8]

Examples 53 to 75, Comparative Examples 43 to 60
Acrylic high molecular weight polymer (B-1 to 2) obtained in the above reference example and tetrafluoroethylene-containing mixed powder (C-1 to 2) or master pellet (M-1) are added to the following thermoplastic resin. And a filler were blended at the ratios shown in Tables 5 and 6, and a thermoplastic resin molded body was produced in the same manner as in Example 1 using the above-described molding machine and conditions. The molded body was evaluated with respect to the occurrence of die cast, appearance in the molded body, and occurrence of plate-out, and the results are shown in Tables 9 to 12.
In Tables 9 to 12, CD-123 is a commercially available powdered polytetrafluoroethylene not treated with an organic polymer ("Fluon CD12" manufactured by Asahi ICI Fluoropolymers Co., Ltd.).
3 "Molecular weight: 12,000,000).

Thermoplastic resin: Metallocene polyethylene: “Kernel” “KS 240” (PE): NFR: 2.2 g / 10 min. Polyvinyl chloride: “Shin-Etsu PVC compound” “EX 282E” manufactured by Shin-Etsu Polymer Co., Ltd. (PVC) Polystyrene: A & M Styrene “SC001” (PS): MFR: 3.7 g / 10 min Impact Polystyrene: Nippon Polystyrene “H450K” (HIPS) Poly-1-butene: Mitsui Petrochemical "BURON""P5040B":MFR; 0.4 g / 10 min Copolymer of acrylonitrile and styrene: "Styrac" manufactured by Asahi Kasei Kogyo Co., Ltd. "AS783" (AS): MFR; 9.0 g / 10 min Acrylonitrile reinforced with rubber And styrene copolymer (ABS, ASA, SAS): Mitsubishi Rayon Co., Ltd. "Diapet ABS""SW-3" (ABS): MFR; 0.4 g / 10 minutes Methacrylic resin: "Acripet" manufactured by Mitsubishi Rayon Co., Ltd. "VH" (MMA): MFR; 0.4 g / 10 minutes Polycarbonate: "NOVAREX""7030A" (PC) manufactured by Mitsubishi Engineering-Plastics Co., Ltd .: MFR; 3.5 g / 10 minutes Polyethylene terephthalate: "Dianite" manufactured by Mitsubishi Rayon "PA-200" (PET) Polybutylene terephthalate: Mitsubishi Rayon "Tuffpet""N-1000" (PBT) Polymethylpentene, cyclic polyolefin such as a copolymer of cyclopentadiene and ethylene and / or propylene: "MX001" (PMP): MFR; 26 g / by Mitsui Petrochemicals 10 minutes Ethylene vinegar bipolymer: Nippon Polyke "Novatec EV
A "LV260": MFR: 8.5 g / 10 min 2,6-dimethyl-1,4-phenylene ether Reduced viscosity (ηsp / c) = 0.59 dl / g (PPE) Polycaproamide: manufactured by Toray Industries, Ltd. "CM1017" (PA6) Polyhexamethylene adipamide: "CM3001N" (PA66) manufactured by Toray Industries, Ltd. Polylactic acid resin: "Lacti 9400" (biodegradable resin) manufactured by Shimadzu Corporation Recycled PP: Mainly polypropylene A car bumper was crushed and pelletized.

[0051]

[Table 9]

[0052]

[Table 10]

[0053]

[Table 11]

[0054]

[Table 12]

Examples 76 to 81 and Comparative Examples 61 to 66
Polypropylene "Novatech PPFY manufactured by Nippon Polychem Co., Ltd.
-6C ", the following modified olefin resin, the acrylic high molecular weight polymer (B-1) obtained in the above Reference Example, and the polytetrafluoroethylene-containing mixed powder (C-2) and the filler (D) are shown in Table. The mixture was blended at the ratio (parts) shown in 13 and extruded under the same molding machine and conditions as in Example 1 to produce a molded article of the thermoplastic resin composition. About the molded body,
Occurrence of eye spots and maleic anhydride-modified PP in the molded product: “Umex 1 manufactured by Sanyo Chemical Co., Ltd.
010 "Acrylate-modified polyethylene:" Aclift WD201 manufactured by Sumitomo Chemical Co., Ltd. "

[0056]

[Table 13]

The appearance and occurrence of plate-out were evaluated in the same manner as in Example 1. Table 13 shows the results.

[0058]

As described above, according to the thermoplastic resin composition of the present invention, even when a filler is added to various thermoplastic resins such as polyethylene resin, polypropylene resin, styrene resin, etc. It is possible to prevent eye stains and plate out that occur. Therefore, it is possible to produce a molded article having improved appearance, excellent continuous productivity, and excellent appearance.

Continued on the front page (72) Inventor Hideo Aoki 3816 Noborito, Tama-ku, Kawasaki City, Kanagawa Prefecture Mitsubishi Rayon Co., Ltd.Tokyo Technology and Information Center Tokyo Technology and Information Center (72) Inventor Masaro Mohri 3816 Noto, Noto, Tama-ku, Kawasaki City, Kanagawa Prefecture Mitsubishi Rayon Co., Ltd. Tokyo Technology and Information Center F-term (reference) 4J002 AA01W BB02W BB11W BB15W BB17W BC03W BC06W BD03W BD15Y BE00W BG04XBG06 BG06X BN14W BN15W BP02W BP03W CF03W CF06W CF07W CG00W CH07W CL01W CL03W FD016 FD030 FD096 FD136 FD326

Claims (12)

[Claims] 1. An acrylic high-molecular-weight polymer (B) of 0.1 to 400 parts by mass, a polytetrafluoroethylene-containing mixed powder (C), and a filler, based on 100 parts by mass of a thermoplastic resin (A). A thermoplastic resin composition containing 1 to 2000 parts by mass of a material (D), wherein the polytetrafluoroethylene-containing mixed powder (C) is a polytetrafluoroethylene-containing mixed powder (C). A thermoplastic resin composition comprising a fluoroethylene component in an amount of 0.01 to 400 parts by mass per 100 parts by mass of the thermoplastic resin (A). 2. The thermoplastic resin (A) according to claim 1,
0.1-100% by mass of modified polyolefin resin (E)
A thermoplastic resin composition comprising: 3. The acrylic high molecular weight polymer (B) is composed of an acrylic monomer (b-1) containing alkyl methacrylate and / or alkyl acrylate having an alkyl group having 1 to 18 carbon atoms. 3. The thermoplastic resin composition according to claim 1, wherein a reduced viscosity (η sp / C) at 25 ° C. (η sp / C) of a solution obtained by dissolving 0.1 g in 100 ml of chloroform is 15 or less. . 4. The thermoplastic resin composition according to claim 3, wherein the reduced viscosity (η sp / C) of the acrylic high molecular weight polymer (B) is 3 or less. 5. The acrylic monomer (b-1) further includes a vinyl monomer having an alkyl group of 1 to 18 carbon atoms and copolymerizable with an alkyl methacrylate and / or an alkyl acrylate. The thermoplastic resin composition according to claim 3, wherein the thermoplastic resin composition is used. 6. The polytetrafluoroethylene-containing mixed powder (C) comprises polytetrafluoroethylene particles having a particle diameter of 10 μm or less and an organic polymer. A thermoplastic resin composition according to any one of the above. 7. The polytetrafluoroethylene-containing mixed powder (C) is obtained by mixing an aqueous dispersion of polytetrafluoroethylene particles having a particle diameter of 0.05 to 1.0 μm and an aqueous dispersion of organic polymer particles. The thermoplastic resin composition according to any one of claims 1 to 6, wherein the thermoplastic resin composition is manufactured by pulverization by solidification or spray drying. 8. The polytetrafluoroethylene-containing mixed powder (C) is a monomer constituting an organic polymer in the presence of an aqueous dispersion of polytetrafluoroethylene particles having a particle diameter of 0.05 to 1.0 μm. The thermoplastic resin composition according to any one of claims 1 to 6, which is produced by polymerizing (c-1) and pulverizing by coagulation or spray drying. 9. The polytetrafluoroethylene-containing mixed powder (C) is obtained by mixing an aqueous dispersion of polytetrafluoroethylene particles having an average particle diameter of 0.05 to 1.0 μm with an aqueous dispersion of organic polymer particles. 7. The composition according to claim 1, wherein the monomer (c-2) having an ethylenically unsaturated bond is emulsion-polymerized in a liquid, and then powdered by coagulation or spray drying. The thermoplastic resin composition according to any one of the above. 10. A molded article comprising the thermoplastic resin composition according to claim 1. 11. An acrylic high molecular weight polymer (B) of 0.1 to 400 with respect to 100 parts by mass of the thermoplastic resin (A).
Parts by mass, a polytetrafluoroethylene-containing mixed powder (C), and 1 to 2000 parts by mass of a filler (D) are blended, and a polytetrafluoroethylene-containing mixed powder (C)
Is mixed such that the polytetrafluoroethylene component in the polytetrafluoroethylene-containing mixed powder (C) is 0.01 to 400 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A). This is a method for producing a thermoplastic resin composition, and produces a master pellet containing a thermoplastic resin (A), an acrylic high molecular weight polymer (B), and a mixed powder (C) containing polytetrafluoroethylene. And then
A method for producing a thermoplastic resin composition, comprising mixing the remaining thermoplastic resin (A) and filler (D) into the master pellet. 12. An acrylic high molecular weight polymer (B) 0.1 to 400 parts by mass per 100 parts by mass of the thermoplastic resin (A).
1 part by mass, a polytetrafluoroethylene-containing mixed powder (C), and 1 to 2000 parts by mass of a filler (D). The powder (C) is prepared such that the polytetrafluoroethylene component in the polytetrafluoroethylene-containing mixed powder (C) is 0.01 to 400 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A). A method for improving the moldability of a thermoplastic resin composition, characterized by being blended with a thermoplastic resin composition.