JP2005036118A - Modifier for thermoplastic resin and thermoplastic resin composition and molded product using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modifier for a thermoplastic resin which shows high handleability and dispersibility of polytetrafluoroethylene and imparts an excellent flame retardance and appearance of a molded product when added to the thermoplastic resin, and a thermoplastic resin composition using the same. <P>SOLUTION: The modifier for the thermoplastic resin is produced by adding 0.01-10 pts.mass inorganic additive and/or organic rigid polymer to 100 pts.mass polymer containing polytetrafluoroethylene. Here, the polymer comprises polytetrafluoroethylene and an alkyl (meth)acrylate polymer produced by copolymerizing a monomer component containing 50-90 mass% alkyl methacrylate having a 1-4C alkyl group and 50-10 mass% alkyl acrylate having a 1-4C alkyl group. The thermoplastic resin composition is produced by compounding the modifier with the thermoplastic resin. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a thermoplastic resin modifier and a thermoplastic resin composition obtained by adding this to a thermoplastic resin.

  Conventional thermoplastic resin molded products used in homes, offices, factories, etc., for example, housing materials for OA equipment such as computers and printers, home appliances such as televisions and audio equipment, many thermoplastic resins are flammable. Therefore, there is a strong demand for incombustibility to reduce fire damage. Usually, a technique for improving the flame retardancy of a resin molded product by adding and blending a flame retardant to the thermoplastic resin used in these applications is common. However, although many flame retardants have the effect of making the resin difficult to burn, the effect of suppressing the dripping (dropping) of the flame drops of the thermoplastic resin once is poor.

  In recent years, housing materials for home appliances such as OA equipment such as computers and printers, televisions, and audio equipment are required to have higher flame resistance as the equipment becomes lighter, thinner, or more complicated in shape. It is coming. In order to have high flame retardancy, it is important not only to shorten the combustion time but also to not drip the flame droplets during combustion.

  It is known that polytetrafluoroethylene is effective in preventing drip when a thermoplastic resin burns. Since polytetrafluoroethylene is highly crystalline and has a low intermolecular force, it has the property of forming fibers with a slight stress. Because of its properties, when polytetrafluoroethylene powder or aqueous dispersion is mixed with a thermoplastic resin, the polytetrafluoroethylene is fibrillated by the shearing force at the time of mixing, and the fiberized polytetrafluoroethylene is contained in the thermoplastic resin. scatter. The fiberized polytetrafluoroethylene remains in a fiberized state even in the final molded product, and exhibits a drip prevention action during combustion.

  Polytetrafluoroethylene for preventing drip is a powder obtained by coagulating and drying latex obtained by emulsion polymerization of tetrafluoroethylene, or an aqueous dispersion concentrated and stabilized after adding a dispersion stabilizer to the latex. Used (see Patent Document 1 and Patent Document 2).

  Further, it is known that not only the anti-drip agent but also the molding processability and mechanical properties are improved when blended with a thermoplastic resin. For example, polytetrafluoroethylene is also used as an additive for thermoplastic resins (see Patent Document 3).

  However, since polytetrafluoroethylene has almost no affinity for the thermoplastic resin, it is difficult to uniformly disperse the polytetrafluoroethylene in the thermoplastic resin while making it into fibers. If molding is performed using a thermoplastic resin composition in which the dispersion of polytetrafluoroethylene is non-uniform, polytetrafluoroethylene aggregates are observed on the surface of the molded product, resulting in an unfavorable product in appearance. In addition, poor dispersion of polytetrafluoroethylene hinders uniform expression of flame retardancy, and may cause deterioration in mechanical properties such as impact resistance.

  For example, the technique of Patent Document 1 has a problem in that the storage stability and the handling and workability during mixing are deteriorated because the powder of polytetrafluoroethylene has the property of easily fiberizing at room temperature. . Further, since no improvement has been made with respect to the dispersibility of polytetrafluoroethylene in the thermoplastic resin, the appearance of the molded product may be deteriorated due to poor dispersibility of polytetrafluoroethylene.

  For example, the technique of Patent Document 2 discloses that the dispersibility in a thermoplastic resin can be improved because the polytetrafluoroethylene particles in the aqueous dispersion are smaller than the particle diameter of the powdered polytetrafluoroethylene. Yes. However, in the same way as powder, the polytetrafluoroethylene in the aqueous dispersion is easily fiberized with a low shearing force. In addition, if the aqueous dispersion is stored for a long period of time, the polytetrafluoroethylene will settle. In order to occur, it is necessary to carry out stirring at regular intervals. Further, when polytetrafluoroethylene aggregates are produced by precipitation, there is a risk of poor appearance in molded articles of the resin composition using the same. Therefore, the aqueous dispersion of polytetrafluoroethylene also has a problem in terms of handleability and storage stability like the powder. In addition, after mixing with thermoplastic resin powder or pellets, an unnecessary water and emulsifier removal step is required, which is not an economical technique.

  Thus, in the production of a thermoplastic resin composition containing polytetrafluoroethylene, the handleability of polytetrafluoroethylene powder or aqueous dispersion, the suppression of fiberization during the handling of polytetrafluoroethylene, and the thermoplastic resin composition There has been no technology that can achieve both improvement in dispersibility in the product and appearance of the molded product.

  Technology for coating polytetrafluoroethylene by polymerizing vinyl monomers and other monomers in an aqueous dispersion of polytetrafluoroethylene particles as a technology to improve the handling and dispersibility of polytetrafluoroethylene Alternatively, a technique of mixing an aqueous dispersion of polytetrafluoroethylene and an aqueous dispersion of a polymer of a vinyl monomer or another monomer is disclosed (Patent Document 4, Patent Document 5, and Patent Document 6). Patent Document 7, Patent Document 8, Patent Document 9, Patent Document 10, Patent Document 11, and Patent Document 12).

  For example, in Patent Literature 4 and Patent Literature 5, polytetrafluoroethylene-containing mixed powder obtained by polymerizing an organic monomer in the presence of a polytetrafluoroethylene dispersion is dispersible in a thermoplastic resin. And a technology that is excellent in handleability is disclosed. However, when the polymerization is carried out in the presence of a polytetrafluoroethylene dispersion, the range of the particle size of the organic polymer necessary for completely or partially encapsulating the polytetrafluoroethylene with the organic polymer is limited. Although it should exist, there is no description regarding the particle size of the organic polymer in this technology. The polymer of the organic monomer used in this technique is an acrylonitrile / styrene copolymer, and the glass transition temperature (Tg) of the acrylonitrile / styrene copolymer is as high as 100 ° C. or higher. In the powder recovery method, polytetrafluoroethylene is agglomerated with each other, and it is difficult to recover a powder having excellent handleability and dispersibility. Further, the content of polytetrafluoroethylene cannot be increased. Therefore, according to this technique, as the content of polytetrafluoroethylene increases, the polymers containing polytetrafluoroethylene tend to agglomerate with each other. There is a fear that it is not possible.

  For example, in Patent Document 6, a mixed powder of polytetrafluoroethylene obtained by polymerizing a vinyl monomer in a dispersion obtained by mixing an organic polymer particle dispersion and a polytetrafluoroethylene particle dispersion is: A technique for improving the dispersibility of polytetrafluoroethylene is disclosed. However, in the polytetrafluoroethylene-containing mixed powder of the art, dodecyl methacrylate having a low glass transition temperature (Tg) accounts for half of the mixed powder. Therefore, when the powder obtained by this technique is stored for a long period of time in a place where the temperature is high or a load is applied, the handling property may be remarkably lowered due to the fusion of the powders. Further, when this powder is added to a thermoplastic resin, the appearance of the molded product may be deteriorated due to the undispersed polytetrafluoroethylene mixed powder due to a decrease in dispersibility.

For example, in Patent Literature 7, Patent Literature 8, Patent Literature 9, Patent Literature 10, Patent Literature 11, and Patent Literature 12, polytetrafluoroethylene is obtained from a mixture of an organic polymer particle dispersion and a polytetrafluoroethylene particle dispersion. A technique for obtaining a mixed powder is disclosed. However, the polytetrafluoroethylene-containing mixed powder disclosed in the art is composed of an aqueous dispersion of polytetrafluoroethylene and an aqueous dispersion of acrylonitrile / styrene copolymer or acrylonitrile / styrene copolymer containing polybutadiene rubber. It is obtained by co-precipitation of solid content from the mixture, but when the former is used, the rubbery elastic body is present on the surface of the dried powder, resulting in poor fluidity and improved handling. Is inappropriate. In addition, when the latter is used, the glass transition temperature (Tg) of the acrylonitrile / styrene copolymer is as high as 100 ° C. or higher, so that the coating of polytetrafluoroethylene is insufficient, and the resulting powder has fluidity and handling. It becomes inferior. In addition, the content of polytetrafluoroethylene cannot be increased.
Japanese Examined Patent Publication No. 59-36657 (2nd page, lines 22-25) JP 2000-129141 A (page 3, right 24th line-page 4, left 39th line) Japanese Patent No. 2958175 (2nd page, right 39th line-3rd page, 8th line) JP-A-9-95583 (2nd page, 25th line to 44th right) Japanese Patent Application Laid-Open No. 11-49912 (second page, left line 32-right line 36) JP 2000-297220 A (6th page, 25th line on the left-7th page, 23rd line on the left) JP-A-61-55145 (2nd page, lines 25-32 on the right) Japanese Patent Laid-Open No. 61-127759 (page 2, right 34th-38th lines) JP 61-261352 A (page 6) Japanese Patent Publication No. 1-60181 (page 6, left 3rd line-26th line) Japanese Patent Publication No. 5-8749 (page 2, left line 8-line 31) Japanese Patent No. 3162426 (7th page, right 1st line-8th page, 21st line on the left) The Polymer Society of Japan "Polymer Data Handbook" Baifukan, January 30, 1986, first edition, pages 690-699 J. et al. BRANDRUP, E.I. H. IMMERGUT "Polymer Handbook 3rd Edition" A WILEY-INTERSCIENCE PUBLICATION, 1989, VI / 209

  The present invention has been made to solve the above-described problems of the prior arts, and has high handleability and high dispersibility of polytetrafluoroethylene. It aims at providing the modifier for thermoplastic resins which is excellent, and a thermoplastic resin composition using the same.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that polytetrafluoroethylene (a-1-1), methyl methacrylate, and an alkyl group having 1 to 4 carbon atoms excluding methyl methacrylate. (Meth) acrylic acid alkyl ester polymer (a-1-2) having a glass transition temperature (Tg) of 40 to 85 ° C. obtained by copolymerizing a monomer component containing (meth) acrylic acid alkyl ester having A polytetrafluoroethylene-containing thermoplastic resin modifier obtained by adding an inorganic additive and / or an organic hard polymer to 100 parts by mass of the polytetrafluoroethylene-containing polymer (a-1) is provided. The inventors have found that an excellent effect is achieved and have completed the present invention.

  That is, the present invention includes polytetrafluoroethylene (a-1-1), methyl methacrylate, and (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms excluding methyl methacrylate. Polytetrafluoroethylene-containing polymer (a-1) comprising a (meth) acrylic acid alkyl ester polymer (a-1-2) having a glass transition temperature (Tg) of 40 to 85 ° C. obtained by copolymerizing monomer components ) Modifier for thermoplastic resin (A) obtained by adding 0.01 to 10 parts by mass of inorganic additive (a-2) and / or organic hard polymer (a-3) to 100 parts by mass It is.

  Polytetrafluoroethylene (a-1-1) is coated with a (meth) acrylic acid alkyl ester polymer (a-1-2) and fiberized polytetrafluoroethylene is a polytetrafluoroethylene-containing polymer. In addition to the fact that it is not substantially present on the particle surface of (a-1), it contains polytetrafluoroethylene by the addition of inorganic additive (a-2) and / or organic hard polymer (a-3) Since the contact between the polymers (a-1) is hindered, the thermoplastic resin modifier (A) has good powder free-flowability, and is excellent in handleability and storage stability. ).

  Furthermore, this invention is the said thermoplastic resin so that content of polytetrafluoroethylene (a-1-1) may be 0.001-20 mass parts with respect to 100 mass parts of thermoplastic resins (B). It is a thermoplastic resin composition to which a modifying agent (A) is added, and further includes at least one of a flame retardant (C) and a filler (D).

  In the present invention, “(meth) acryl” means acrylic and / or methacrylic.

  When the thermoplastic modifier of the present invention is used, the handling property and the dispersibility of polytetrafluoroethylene are high, and when added to a thermoplastic resin, the modifier for a thermoplastic resin is excellent in flame retardancy and molded article appearance. , And a thermoplastic resin composition using the same.

  The polytetrafluoroethylene (a-1-1) used in the present invention is obtained by polymerizing a monomer containing tetrafluoroethylene as a main component. It may be copolymerized with other monomers as long as the desired properties of polytetrafluoroethylene are not impaired. Examples of copolymer components include fluorine-containing olefins such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, and perfluoroalkyl vinyl ether; fluorine-containing (meth) acrylates such as (meth) acrylic acid perfluoroalkyl esters Ester; etc. are mentioned. The amount of the copolymer component is preferably 10% by mass or less in 100% by mass of the total amount of tetrafluoroethylene and the copolymer component.

  The solid content of the aqueous dispersion in which the polytetrafluoroethylene (a-1-1) particles used in the present invention are dispersed is preferably 20 to 60% by mass, and the average particle diameter of the polytetrafluoroethylene (a-1-1) particles Is preferably in the range of 0.05 to 1.0 μm.

  The aqueous dispersion of polytetrafluoroethylene (a-1-1) particles can be obtained, for example, by emulsion polymerization of a monomer component mainly composed of tetrafluoroethylene. Moreover, as a commercial item (brand name) of the aqueous dispersion of polytetrafluoroethylene (a-1-1) particles, Asahi Glass Fluoropolymers Co., Ltd. full-on AD-1, AD-936, AD-911, AD-938; Polyflon D-1, D-2, D-2CE, D-3E, D-30E manufactured by Daikin Industries, Ltd .; Teflon 30J manufactured by Mitsui DuPont Fluorochemical Co., Ltd .; Dyneon Co., Ltd. Examples include Dinion TF5032, TF5035, TF5235, and the like.

  The (meth) acrylic acid alkyl ester polymer (a-1-2) used in the present invention includes methyl methacrylate and (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms excluding methyl methacrylate. It is a copolymer having a glass transition temperature (Tg) of 40 to 85 ° C. obtained by copolymerization of a monomer component containing.

  The monomer component can be polymerized by radical polymerization, ionic polymerization or the like. Radical polymerization is preferred, and emulsion polymerization using an emulsifier is particularly preferred. In the present invention, since the (meth) acrylic acid alkyl ester polymer (a-1-2) as described above is used, it is various in comparison with a conventional polytetrafluoroethylene-containing thermoplastic resin modifier. The dispersibility of polytetrafluoroethylene (a-1-1) in the thermoplastic resin and thermoplastic elastomer becomes better. Further, the (meth) acrylic acid alkyl ester polymer (a-1-2) has no fear of generation of toxic gas at the time of combustion as compared with the conventional acrylonitrile-styrene polymer, and the single polymer remaining at the end of the polymerization. There is much less mass, and the burden on the environment is low.

  Specific examples of (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms excluding methyl methacrylate used in combination with methyl methacrylate in (meth) acrylic acid alkyl ester polymer (a-1-2) Examples include ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, and the like. The alkyl group may be linear or branched. These can be used alone or in combination of two or more. As the (meth) acrylic acid alkyl ester polymer (a-1-2), a polymer obtained by copolymerizing a monomer component containing 50 to 90% by mass, more preferably 70 to 90% by mass of methyl methacrylate, This is preferable in that a powder having good handleability can be obtained.

  The monomer component to be the (meth) acrylic acid alkyl ester polymer (a-1-2) can also contain other copolymerizable monomers. Other monomers include vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; vinyl carboxylate monomers such as vinyl acetate and vinyl butyrate; olefin monomers such as ethylene, propylene and isobutylene. Diene monomers such as butadiene, isoprene and dimethylbutadiene; However, these monomers have a glass transition temperature (Tg) of the (meth) acrylic acid alkyl ester-based polymer (a-1-2) of 40 to 85 ° C., and the thermoplastic resin modifier of the present invention. It is necessary to use it in an amount that does not impair the handleability of (A), the dispersibility in the thermoplastic resin, and the like, and it is preferably used at 30% by mass or less. Moreover, although it is also possible to use the (meth) acrylic-acid alkylester which has a C5 or more alkyl group, with the increase in carbon number of an alkyl group, a (meth) acrylic-acid alkylester type polymer (a-1 -2) tends to decrease the glass transition temperature (Tg), and may greatly impair the storage stability of the resulting thermoplastic resin modifier (A).

  As a polymerization initiator used for superposition | polymerization of a (meth) acrylic-acid alkylester type | system | group polymer (a-1-2), the single type of a water-soluble initiator or an oil-soluble initiator, or a redox type thing is mentioned, for example. Specific examples of the water-soluble initiator include inorganic initiators such as persulfate. Specific examples of the oil-soluble initiator include organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide and lauroyl peroxide; azo compounds and the like. Specific examples of redox initiators include those in which the above-mentioned inorganic initiators are combined with sulfites, bisulfites, thiosulfates, etc., and the above-mentioned organic peroxides and azo compounds are combined with thorium formaldehyde sulfoxylate, etc. And the like. However, it is not limited to these specific examples.

  The molecular weight of the (meth) acrylic acid alkyl ester polymer (a-1-2) can be adjusted by a polymerization condition such as a chain transfer agent such as n-octyl mercaptan or t-dodecyl mercaptan, an initiator amount, and a polymerization temperature. it can. However, it is not limited to these specific examples.

  The dispersion liquid in which the (meth) acrylic acid alkyl ester polymer (a-1-2) particles are dispersed is obtained by emulsion polymerization or miniemulsion polymerization. The emulsifier that can be used for these polymerizations is not particularly limited, and various conventionally known emulsifiers can be used. For example, anionic surfactants such as fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfonate salt, alkyl phosphate ester salt, dialkyl sulfosuccinate salt; polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, glycerin Nonionic surfactants such as fatty acid esters; cationic surfactants such as alkylamine salts can be used. These emulsifiers can be used alone or in combination.

  When the pH of the polymerization system is on the alkali side depending on the type of emulsifier used, an appropriate pH adjuster can be used to prevent hydrolysis of the (meth) acrylic acid alkyl ester. Examples of the pH regulator include boric acid-potassium chloride-potassium hydroxide, potassium dihydrogen phosphate-disodium hydrogen phosphate, boric acid-potassium chloride-potassium carbonate, citric acid-potassium hydrogen citrate, diphosphate phosphate. Examples include potassium hydrogen-boric acid, disodium hydrogen phosphate-citric acid, and the like.

  The weight average molecular weight (Mw) of the (meth) acrylic acid alkyl ester polymer (a-1-2) is preferably 20,000 to 5,000,000, and more preferably 20,000 to 4,000,000. This Mw is a value measured by gel permeation chromatography. If the weight average molecular weight (Mw) is less than 20,000, the mechanical properties of the thermoplastic resin may be lowered. If it is greater than 5,000,000, the polytetrafluoroethylene-containing polymer (a-1) in the thermoplastic resin There is a possibility that the dispersibility of the structure (described later) is lowered.

  The polytetrafluoroethylene-containing polymer (a-1) constituting the thermoplastic resin modifier (A) of the present invention includes the above-mentioned polytetrafluoroethylene (a-1-1) and alkyl (meth) acrylate. The polytetrafluoroethylene (a-1-1) is coated with a (meth) acrylic acid alkyl ester polymer (a-1-2). In addition, it is important that the fiberized polytetrafluoroethylene has a structure that does not substantially exist on the particle surface of the polytetrafluoroethylene-containing polymer (a-1). About the ratio of both, it is preferable that polytetrafluoroethylene (a-1-1) is 0.01-70 mass parts on the basis of both 100 mass parts in total, and 40-70 mass parts is especially preferable. The addition efficiency of the modifier is improved at 0.01 parts by mass or more, and the dispersibility and workability are not impaired at 70 parts by mass or less.

  In the present invention, the inorganic additive (a-2) is preferably used as an additive for the purpose of improving the handleability and storage stability (cohesiveness) of the polytetrafluoroethylene-containing polymer (a-1). I can do things. Specific examples of the inorganic additive (a-2) in the present invention include calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, aluminum hydroxide, magnesium hydroxide, talc, mica, kaolin, silica, clay, zeolite, Mention may be made of fibers, powders or beads of wollastonite, glass and graphite. These inorganic additives can be used alone or in combination of two or more. Of these, calcium carbonate, talc, mica, kaolin, silica, clay, and wollastonite can be preferably used.

  The inorganic additive (a-2) is preferably added in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the polytetrafluoroethylene-containing polymer (a-1). If the amount is less than 0.01 part by mass, the effect of improving the powder handleability of the polytetrafluoroethylene-containing polymer (a-1) cannot be obtained. . Especially preferably, it is 0.1-5 mass parts.

  For example, in the state of a slurry in which solid content is coagulated from a mixed aqueous dispersion of polytetrafluoroethylene (a-1-1) particles and (meth) acrylic acid alkyl ester polymer (a-1-2) particles. Since the inorganic additive cannot adhere to the surface of the polytetrafluoroethylene-containing polymer (a-1) even if the inorganic additive (a-2) is added, the resulting thermoplastic resin modifier (A) This is not preferable because the powder handleability cannot be improved.

  Such a thermoplastic resin modifier (A) of the present invention is obtained by, for example, (meth) acrylic acid by emulsion polymerization in an aqueous dispersion in which polytetrafluoroethylene (a-1-1) particles are dispersed. An inorganic additive (a- 2) is obtained by the method [first production method].

  Further, for example, an aqueous dispersion in which (meth) acrylic acid alkyl ester polymer (a-1-2) particles are formed by emulsion polymerization and an aqueous dispersion in which polytetrafluoroethylene (a-1-1) particles are dispersed. A method of blending an inorganic additive (a-2) with a polytetrafluoroethylene-containing polymer (a-1) obtained by mixing a liquid with a liquid and solidifying or spray-drying the solid content of the resulting mixed aqueous dispersion [second Manufacturing method].

  In the present invention, an organic hard polymer (a-3) is preferably used as an additive for the purpose of improving the handleability and storage stability (cohesiveness) of the polytetrafluoroethylene-containing polymer (a-1). I can do it. The organic hard polymer (a-3) in the present invention is a hard thermoplastic polymer having a glass transition temperature (Tg) of 50 to 98 ° C. obtained by emulsion polymerization of one or more vinyl monomers. Can be used. As a vinyl-type monomer, 1 or more types chosen from the (meth) acrylic-acid alkylester which has a C1-C4 alkyl group, and an aromatic alkenyl compound are preferable.

  Specific examples of the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and the like. The alkyl group may be linear or branched.

  Specific examples of the aromatic alkenyl compound include styrene, α-substituted styrene, nucleus-substituted styrene and derivatives thereof such as α-methylstyrene, chlorostyrene and vinyltoluene.

  Moreover, the other monomer copolymerizable with these can also be used. Other monomers include vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; vinyl carboxylate monomers such as vinyl acetate and vinyl butyrate; olefin monomers such as ethylene, propylene and isobutylene. Diene monomers such as butadiene, isoprene and dimethylbutadiene; However, these monomers need to be used in such an amount that the glass transition temperature (Tg) of the obtained organic hard polymer (a-3) does not deviate from the range of 50 to 98 ° C.

  Specific examples of the organic hard polymer (a-3) in the present invention include copolymers of methyl methacrylate and (meth) acrylic acid alkyl esters other than methyl methacrylate, and other than methyl methacrylate and methyl methacrylate. Examples thereof include a copolymer of (meth) acrylic acid alkyl ester and an aromatic alkenyl compound. Further, these copolymers may be used in a batch or multistage polymerization format.

  Examples of the polymerization initiator include a water-soluble initiator or an oil-soluble initiator alone or a redox type. Specific examples of the water-soluble initiator include inorganic initiators such as persulfate. Specific examples of the oil-soluble initiator include organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide and lauroyl peroxide; azo compounds and the like. Specific examples of redox initiators include those in which the above-mentioned inorganic initiators are combined with sulfites, bisulfites, thiosulfates, etc., and the above-mentioned organic peroxides and azo compounds are combined with thorium formaldehyde sulfoxylate, etc. And the like. However, it is not limited to these specific examples.

  The dispersion liquid of organic hard polymer (a-3) particles is obtained by emulsion polymerization or miniemulsion polymerization. The emulsifier that can be used for these polymerizations is not particularly limited, and various conventionally known emulsifiers can be used. For example, anionic surfactants such as fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfonate salt, alkyl phosphate ester salt, dialkyl sulfosuccinate salt; polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, glycerin Nonionic surfactants such as fatty acid esters; cationic surfactants such as alkylamine salts can be used. These emulsifiers can be used alone or in combination.

  When the pH of the polymerization system is on the alkali side depending on the type of emulsifier used, an appropriate pH adjuster can be used to prevent hydrolysis of the (meth) acrylic acid alkyl ester. Examples of the pH regulator include boric acid-potassium chloride-potassium hydroxide, potassium dihydrogen phosphate-disodium hydrogen phosphate, boric acid-potassium chloride-potassium carbonate, citric acid-potassium hydrogen citrate, diphosphate phosphate. Examples include potassium hydrogen-boric acid, disodium hydrogen phosphate-citric acid, and the like.

  However, it is important that the glass transition temperature (Tg) of the organic hard polymer (a-3) in the present invention is in the range of 50 to 98 ° C. When the glass transition temperature is lower than 50 ° C., the effect of reinforcing the storage stability of the polytetrafluoroethylene-containing polymer (a-1) cannot be obtained, and the effect of suppressing the aggregation of the powder is increased when stored for a long time. There is a risk of lowering.

  When the glass transition temperature is higher than 98 ° C., it is necessary to increase the agglomeration temperature at the time of agglomeration of solids from the aqueous dispersion due to coagulation. There is a possibility that it will be generated in a large amount and the molding appearance may be deteriorated due to poor dispersion in the thermoplastic resin. In addition, it is necessary to set the inlet temperature of the spray drying device high when the solid content is recovered from the aqueous dispersion by spray drying, and there is a risk of particle breakage during spray drying. When the particle breakage occurs, at the same time as polytetrafluoroethylene (a-1-1) is exposed, modifier particles are taken into the network of fiberized polytetrafluoroethylene (a-1-1), There is a risk that the storage stability, handleability and fluidity of the powder will be greatly reduced.

  The organic hard polymer (a-3) in the present invention is preferably added in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the polytetrafluoroethylene-containing polymer (a-1). If the amount is less than 0.01 parts by mass, the effect of improving the powder handleability of the polytetrafluoroethylene-containing polymer (a-1) cannot be obtained, and if it exceeds 10 parts by mass, the mechanical properties of the thermoplastic resin composition may be reduced. is there. Moreover, since a flammable component increases, when it adds to the thermoplastic resin composition by which high flame retardance is requested | required, there exists a possibility that a flame retardance may be reduced significantly. Especially preferably, it is 0.5-5 mass parts.

  The organic hard polymer (a-3) is a mixed aqueous dispersion of polytetrafluoroethylene (a-1-1) particles and (meth) acrylic acid alkyl ester-based polymer (a-1-2) particles, Spray drying after mixing the aqueous dispersion in which the organic hard polymer (a-3) particles are dispersed, or spraying simultaneously with the aqueous dispersion in which the organic hard polymer (a-3) particles are dispersed. It is preferable to add by drying. Alternatively, an organic system is formed into a slurry obtained by coagulating solid components from a mixed aqueous dispersion of polytetrafluoroethylene (a-1-1) particles and (meth) acrylic acid alkyl ester polymer (a-1-2) particles. It is preferable to add an aqueous dispersion in which the hard polymer (a-3) particles are dispersed. For example, even if the powder of the organic hard polymer (a-3) is added to the powder of the polytetrafluoroethylene-containing polymer (a-1), the polytetrafluoro by the organic hard polymer (a-3) is used. Since the ethylene-containing polymer cannot be coated, it is not preferable because the powder handling property of the resulting thermoplastic resin modifier (A) cannot be improved.

  Such a thermoplastic resin modifier (A) of the present invention is obtained by, for example, (meth) acrylic acid by emulsion polymerization in an aqueous dispersion in which polytetrafluoroethylene (a-1-1) particles are dispersed. An organic hard polymer (a-1) is slurried in a slurry of polytetrafluoroethylene-containing polymer (a-1) in which alkyl ester polymer (a-1-2) particles are formed and the solid content of the resulting mixed aqueous dispersion is coagulated. a-3) Obtained by a method [third production method] of adding an aqueous dispersion in which particles are dispersed.

  Further, for example, an aqueous dispersion in which (meth) acrylic acid alkyl ester polymer (a-1-2) particles are formed by emulsion polymerization and an aqueous dispersion in which polytetrafluoroethylene (a-1-1) particles are dispersed. An aqueous dispersion in which organic hard polymer (a-3) particles are dispersed in a slurry of a polytetrafluoroethylene-containing polymer (a-1) in which the solid content of the resulting mixed aqueous dispersion is coagulated. It is obtained by the method [fourth production method] by adding a liquid.

  Further, for example, the (meth) acrylic acid alkyl ester polymer (a-1-2) particles are formed by emulsion polymerization in an aqueous dispersion in which the polytetrafluoroethylene (a-1-1) particles are dispersed. The obtained mixed aqueous dispersion and the aqueous dispersion in which the organic hard polymer (a-3) particles are dispersed are mixed and then spray-dried [fifth manufacturing method].

  Further, for example, the (meth) acrylic acid alkyl ester polymer (a-1-2) particles are formed by emulsion polymerization in an aqueous dispersion in which the polytetrafluoroethylene (a-1-1) particles are dispersed. The obtained mixed aqueous dispersion and the aqueous dispersion in which the organic hard polymer (a-3) particles are dispersed are simultaneously spray-dried [sixth manufacturing method].

  Further, for example, an aqueous dispersion in which the (meth) acrylic acid alkyl ester polymer (a-1-2) particles are formed by emulsion polymerization and the polytetrafluoroethylene (a-1-1) particles are dispersed. It is obtained by mixing the aqueous dispersion, mixing the resulting mixed aqueous dispersion and the aqueous dispersion in which the organic hard polymer (a-3) particles are dispersed, and then spray drying the mixture (seventh manufacturing method). .

  Further, for example, an aqueous dispersion in which the (meth) acrylic acid alkyl ester polymer (a-1-2) particles are formed by emulsion polymerization and the polytetrafluoroethylene (a-1-1) particles are dispersed. The aqueous dispersion is mixed, and the resulting mixed aqueous dispersion and the aqueous dispersion in which the organic hard polymer (a-3) particles are dispersed are simultaneously spray-dried [eighth production method].

  In the present invention, as an additive for the purpose of improving the handleability and storage stability (cohesiveness) of the polytetrafluoroethylene-containing polymer (a-1), the above inorganic additive (a-2) and organic A hard polymer (a-3) can also be used in combination. In this case, it is preferable that 0.01-10 mass parts is added as a sum total with respect to 100 mass parts of polytetrafluoroethylene containing polymers (a-1). If the amount is less than 0.01 part by mass, the effect of improving the powder handleability of the polytetrafluoroethylene-containing polymer (a-1) cannot be obtained. . Moreover, since a flammable component increases, when it adds to the thermoplastic resin composition by which high flame retardance is requested | required, there exists a possibility that a flame retardance may be reduced significantly. Especially preferably, it is 0.1-5 mass parts.

  The inorganic additive (a-2) is preferably added to the powder of the polytetrafluoroethylene-containing polymer (a-1). For example, in the state of a slurry in which solid content is coagulated from a mixed aqueous dispersion of polytetrafluoroethylene (a-1-1) particles and (meth) acrylic acid alkyl ester polymer (a-1-2) particles. Since the inorganic additive cannot adhere to the surface of the polytetrafluoroethylene-containing polymer (a-1) even if the inorganic additive (a-2) is added, the resulting thermoplastic resin modifier (A) This is not preferable because the powder handleability cannot be improved.

  The organic hard polymer (a-3) is a mixed aqueous dispersion of polytetrafluoroethylene (a-1-1) particles and (meth) acrylic acid alkyl ester-based polymer (a-1-2) particles, Spray drying after mixing the aqueous dispersion in which the organic hard polymer (a-3) particles are dispersed, or spraying simultaneously with the aqueous dispersion in which the organic hard polymer (a-3) particles are dispersed. It is preferable to add by drying. Alternatively, an organic system is formed into a slurry obtained by coagulating solid components from a mixed aqueous dispersion of polytetrafluoroethylene (a-1-1) particles and (meth) acrylic acid alkyl ester polymer (a-1-2) particles. It is preferable to add an aqueous dispersion in which the hard polymer (a-3) particles are dispersed. For example, even if the powder of the organic hard polymer (a-3) is added to the powder of the polytetrafluoroethylene-containing polymer (a-1), the polytetrafluoro by the organic hard polymer (a-3) is used. Since the ethylene-containing polymer cannot be coated, it is not preferable because the powder handling property of the resulting thermoplastic resin modifier (A) cannot be improved.

  Such a modifier for thermoplastic resins (A) of the present invention is obtained by, for example, the (meta) by emulsion polymerization in an aqueous dispersion in which the polytetrafluoroethylene (a-1-1) particles are dispersed. In the slurry of the polytetrafluoroethylene-containing polymer (a-1) in which the acrylic acid alkyl ester-based polymer (a-1-2) particles are formed and the solid content of the resulting mixed aqueous dispersion is coagulated, the organic hard A method in which an aqueous dispersion in which particles of polymer (a-3) are dispersed is mixed, and the inorganic additive (a-2) is blended with the resulting polytetrafluoroethylene-containing polymer (a-1 ′) [No. 9 It can be obtained by the following process.

  Further, for example, an aqueous dispersion in which the (meth) acrylic acid alkyl ester polymer (a-1-2) particles are formed by emulsion polymerization and the polytetrafluoroethylene (a-1-1) particles are dispersed. An aqueous dispersion of the organic hard polymer (a-3) particles in a slurry of a polytetrafluoroethylene-containing polymer (a-1) obtained by mixing an aqueous dispersion and coagulating the solid content of the obtained mixed aqueous dispersion It is obtained by a method [tenth production method] of mixing the dispersion and blending the inorganic additive (a-2) into the resulting polytetrafluoroethylene-containing polymer (a-1 ′).

  Further, for example, the (meth) acrylic acid alkyl ester polymer (a-1-2) particles are formed by emulsion polymerization in an aqueous dispersion in which the polytetrafluoroethylene (a-1-1) particles are dispersed. The resulting mixed aqueous dispersion and the aqueous dispersion in which the organic hard polymer (a-3) particles are dispersed are mixed and then spray-dried, and the resulting polytetrafluoroethylene-containing polymer (a-1 ′) is inorganic. It is obtained by the method [11th manufacturing method] which mixes system additive (a-2).

  Further, for example, the (meth) acrylic acid alkyl ester polymer (a-1-2) particles are formed by emulsion polymerization in an aqueous dispersion in which the polytetrafluoroethylene (a-1-1) particles are dispersed. The resulting mixed aqueous dispersion and the aqueous dispersion in which the organic hard polymer (a-3) particles are dispersed are spray-dried simultaneously, and the resulting polytetrafluoroethylene-containing polymer (a-1 ′) is added with an inorganic system. It is obtained by the method [Twelfth production method] of blending agent (a-2).

  Further, for example, an aqueous dispersion in which the (meth) acrylic acid alkyl ester polymer (a-1-2) particles are formed by emulsion polymerization and the polytetrafluoroethylene (a-1-1) particles are dispersed. An aqueous dispersion is mixed, and the resulting mixed aqueous dispersion is mixed with an aqueous dispersion in which organic hard polymer (a-3) particles are dispersed, followed by spray drying, and the resulting polytetrafluoroethylene-containing polymer ( a-1 ′) and the inorganic additive (a-2) is added by the method [Thirteenth Production Method].

  Further, for example, an aqueous dispersion in which the (meth) acrylic acid alkyl ester polymer (a-1-2) particles are formed by emulsion polymerization and the polytetrafluoroethylene (a-1-1) particles are dispersed. An aqueous dispersion is mixed, and the resulting mixed aqueous dispersion and the aqueous dispersion in which the organic hard polymer (a-3) particles are dispersed are simultaneously spray-dried, and the resulting polytetrafluoroethylene-containing polymer (a- It is obtained by a method [fourteenth manufacturing method] in which the inorganic additive (a-2) is blended with 1 ′).

  The solidification of the mixed aqueous dispersion in [First production method] to [14th production method] is performed, for example, by putting it in hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved. This can be done by coagulation. Spray drying can be performed, for example, by spraying the mixed aqueous dispersion as it is.

  When solid content in the mixed aqueous dispersion is coagulated or spray-dried to obtain a polytetrafluoroethylene-containing polymer (a-1), the average particle of (meth) acrylic acid alkyl ester polymer (a-1-2) particles The diameter is preferably 0.05 to 1.0 μm, more preferably 0.05 to 0.15 μm, still more preferably 0.05 to 0.1 μm.

  The thermoplastic resin composition of the present invention has a polytetrafluoroethylene (a-1-1) content of 0.001 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin (B). It is the composition which added the modifier (A) for thermoplastic resins of this invention. When the modifier for thermoplastic resin (A) of the present invention is used in an amount within this range, the polytetrafluoroethylene (a-1-1) component is uniformly dispersed in the form of fine fibrils in the thermoplastic resin (B). In addition, mechanical properties and flame retardancy are improved. Preferably, it is 0.1-10 mass parts.

  Examples of the thermoplastic resin (B) include conventionally known various thermoplastic resins. The “thermoplastic resin” as used in the present invention is meant to include thermoplastic elastomers. Specific examples include polystyrene (PS), high impact polystyrene (HIPS), (meth) acrylic acid ester / styrene copolymer (MS), acrylonitrile / styrene copolymer (SAN), styrene / maleic anhydride copolymer. Styrene resin (St resin) such as coalescence (SMA), ABS, ASA, AES, acrylic resin (Ac resin) such as polymethyl methacrylate (PMMA), polycarbonate resin (PC resin), polyamide Resin (PA resin), polyester resin (PEs resin) such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polyphenylene ether resin (PPE resin), modified polyphenylene ether resin, polyoxymethylene resin Resin (POM resin), Polysulfo Resin (PSO resin), polyarylate resin (PAr resin), polyphenylene sulfide resin (PPS resin), engineering polyurethane such as thermoplastic polyurethane resin (PU resin), PC such as PC / ABS Resin / St resin alloy, PA resin such as PA / ABS / St resin alloy, PA resin such as PA / PP / polyolefin resin alloy, PC resin such as PC / PBT / PEs resin alloy, Alloys of polyolefin resins such as PP / PE, polymer alloys such as PPE / HIPS, PPE / PBT, PPE resin alloys such as PPE / PA, polyethylene, low density polyethylene, ultra low density polyethylene, polypropylene, polybutene, poly Poly-α-olefins such as -4-methylpentene, ethylene propylene Copolymers of α-olefins such as len rubber, ethylene butene copolymer, ethylene butene terpolymer, ethylene vinyl acetate copolymer, ethylene / ethyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / Polyolefin resins such as copolymers of α-olefin and various monomers such as ethylene / acrylic acid copolymer, ethylene / acrylic acid copolymer, ethylene / glycidyl methacrylate copolymer, polylactic acid, polycaprolactone, fat Aliphatic polyester resins based on aliphatic glycols and aliphatic dicarboxylic acids or their derivatives, biodegradable cellulose esters, polypeptides, polyvinyl alcohol, starch, carrageenan, chitin / chitosan, natural linear polyester resins, etc. Biodegradable resin, styrene elastomer And thermoplastic elastomers such as urethane elastomers, polyester elastomers, polyamide elastomers, fluorine elastomers, 1,2-polybutadiene, trans 1,4-polyisoprene, and acrylic elastomers. The thermoplastic resin is not limited to these, and a general thermoplastic resin can be used. These may be used alone or in combination of two or more.

  It is preferable that the thermoplastic resin composition of the present invention further contains a flame retardant (C). A well-known thing can be used as a flame retardant (C), What is necessary is just to select the quantity which can achieve a desired flame retardance for a thermoplastic resin composition suitably. At this time, a drip is prevented and a highly flame-retardant thermoplastic resin composition is obtained.

  Examples of the flame retardant (C) include tricresyl phosphate, triallyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tri (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (2,3-dibromopropyl) Phosphate esters such as phosphate, condensed phosphate esters such as phenylenebis (phenylglycidyl phosphate), red phosphorus, phosphorus compounds such as ammonium polyphosphate / pentaerythritol complex, phosphate type polyols, halogen-containing polyols, phosphorus-containing polyols, etc. Polyols, aromatic halogen compounds such as hexabromobenzene and decabromodiphenyl oxide, halogenated epoxy resins such as brominated bisphenol epoxy resins, halogenated Metals such as polycarbonate resin, brominated polystyrene resin, brominated bisphenol cyanurate resin, brominated polyphenylene oxide, decabromodiphenyl oxide bisphenol condensate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium aluminate, hydrotalcite Antimony compounds such as hydroxide, antimony trioxide and antimony pentoxide, triazine compounds such as melamine, cyanuric acid and melamine cyanurate, other kaolin clay, dosonite, zinc carbonate calcium borate, molybdenum compound, ferrocene, tin compound And inorganic complex salts. In particular, phosphoric acid esters such as tricresyl phosphate, triallyl phosphate, triphenyl phosphate and cresyl diphenyl phosphate which do not contain halogen, and condensed phosphate esters such as phenylenebis (phenylglycidyl phosphate) are preferably used.

  Moreover, an alkali metal salt or an alkaline earth metal salt can also be used as the flame retardant (C) in the thermoplastic resin composition of the present invention. Examples thereof include alkali metal salts or alkaline earth metal salts of organic sulfonic acids, alkali metal salts or alkaline earth metal salts of sulfate esters, and alkali metal salts or alkaline earth metal salts of organic sulfonamides.

  Specifically, alkali metal salts or alkaline earths of alkanesulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, methylbutanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, octanesulfonic acid, etc. Metal salts, and alkali metal salts or alkaline earth metal salts of fluorinated alkanesulfonic acids in which part of the hydrogen of the alkyl group is substituted with fluorine atoms, perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropane Alkali metal salts of perfluoroalkanesulfonic acids such as sulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, perfluorohexanesulfonic acid, perfluoroheptanesulfonic acid, perfluorooctanesulfonic acid, etc. Is an alkali metal salt or alkaline earth of sulfonic acid of monomeric or polymeric aromatic sulfide such as alkaline earth metal salt, diphenyl sulfide-4,4′-disulfonic acid, diphenyl sulfide-4,4′-disulfonic acid, etc. Metal salts, alkali metal salts or alkaline earth metal salts of aromatic carboxylic acids and esters such as 5-sulfoisophthalic acid, 5-sulfoisophthalic acid, polyethylene terephthalic acid polysulfonic acid, 1-methoxynaphthalene-4-sulfone Acid, 4-dodecylphenyl ether disulfonic acid, poly (2,6-dimethylphenylene oxide) polysulfonic acid, poly (1,3-dimethylphenylene oxide) polysulfonic acid, poly (1,4-dimethylphenylene oxide) polysulfonic acid, poly (2, -Alkali metal salts or alkaline earth metal salts of sulfonic acids of monomeric or polymeric aromatic ethers such as dimethylphenylene oxide) polysulfonic acid and poly (2-fluoro-6-butylphenylene oxide) polysulfonic acid, benzene sulfonate Alkali metal salts or alkaline earth metal salts of aromatic sulfonates such as sulfonic acids, benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, p-benzenedisulfonic acid, naphthalene-2,6-disulfonic acid, biphenyl- Monomer or polymer aromatic sulfonic acid alkali metal salt or alkaline earth metal salt such as 3,3′-disulfonic acid, diphenylsulfone-3-sulfonic acid, diphenylsulfone-3-sulfonic acid, diphenylsulfone-3 , 3 ' -Alkali metal salt or alkaline earth metal salt of monomeric or polymeric aromatic sulfonesulfonic acid such as disulfonic acid, diphenylsulfone-3,4'-disulfonic acid, α, α, α-trifluoroacetophenone-4- Alkali metal salts or alkaline earth metal salts of aromatic ketones such as sulfonic acid and benzophenone-3,3′-disulfonic acid, thiophenone-2,5-disulfonic acid, thiophenone-2,5-disulfonic acid, thiophenone Alkali metal salts of heterocyclic sulfonic acids such as sodium 2,5-disulfonic acid and sodium benzothiophene sulfonate, alkaline earth metal salts, alkali sulfonates of aromatic sulfoxides such as diphenyl sulfoxide-4-sulfonic acid Metal salt or alkaline earth metal salt, naphthalene Condensates of alkali metal or alkaline earth metal salts of aromatic sulfonic acids such as acid and anthracene sulfonic acid by methylene type bonds, methyl sulfate ester, ethyl sulfate ester, lauryl sulfate ester, hexadecyl sulfate ester, polyoxyethylene alkyl Monovalent and / or polyhydric alcohols such as phenyl ether sulfate, pentaerythritol mono-, di-, tri-, tetra-sulfate, lauric acid monoglyceride sulfate, palmitic acid monoglyceride sulfate, stearic acid monoglyceride sulfate Alkali metal salt or alkaline earth metal salt of sulfate, saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonimide, N- (N′-benzylaminocarbonyl) sulfani Imide, N- (phenyl carboxyl) sulfanyl alkali metal salts or alkaline earth aromatic sulfonamides such as Louis bromide metal salts and the like. In particular, an alkali metal salt or alkaline earth metal salt of perfluoroalkanesulfonic acid, an alkali metal salt or alkaline earth metal salt of aromatic sulfonic acid, an alkali metal salt or alkaline earth metal salt of aromatic sulfonamide is preferably used. It is done.

  With respect to the thermoplastic resin composition of the present invention, the above-mentioned compounds mentioned as the flame retardant (C) can be used alone or in combination of two or more as required.

  The thermoplastic resin composition of the present invention preferably further contains a filler (D).

  Examples of the filler (D) include powders made of metals, oxides, hydroxides, silicic acid or silicates, carbonates, silicon carbide, vegetable fibers, animal fibers, synthetic fibers, and the like. Typical examples include aluminum powder, copper powder, iron powder, alumina, natural wood, paper, calcium carbonate, talc, magnesium carbonate, mica, kaolin, calcium sulfate, barium sulfate, aluminum hydroxide, magnesium hydroxide, silica , Clay, zeolite, talc, wollastonite, acetate powder, silk powder, aramid fiber, glass fiber, carbon fiber, metal fiber, carbon black, graphite, glass beads and the like.

  Furthermore, a regenerated filler material can also be used as the filler (D). Recycled filler materials include rice husk, bran, rice bran, corn waste, coconut husk, defatted soybeans, walnut husk, coconut coconut shell, susoco, bagasse, etc. Boiled rice cakes such as koji, wine grape koji, sake koji, soy sauce koji, various koji from tea plants, coffee koji, citrus squeezed koji, food processing waste such as okara and chlorella, shells such as oyster shells, shrimp Marine waste such as wood shells, wood shells, wood waste such as sawdust, waste wood, bark, felling bamboo, wood cutting at sawmills, and demolition of wooden houses, waste paper and paper Examples include waste pulp and paper waste generated from the industry. These can be used alone or in admixture of two or more.

  The shape and size of the filler (D) are not particularly limited, but if the particles are large, if the particles are too long, if the fibers are too long, the dispersibility of the filler (D) decreases, and the product Since the appearance deteriorates, it is preferable to use a pulverized one, preferably 10 mesh pass or less, more preferably 100 mesh pass or less. Moreover, 10,000 mesh pass or more is preferable at the point of handling of a pulverized product. The moisture content of the filler (D) is not particularly limited, but the filler (D) often contains a large amount of water, and the moisture content of 20% by mass or less is obtained from the handling property as a powder. It is preferable to dry by heating and stirring. Furthermore, even if the moisture content is 20% by mass or less, if abnormal foaming or the like occurs in the molded product, it is preferable to further dry it with an oven or a heating and stirring treatment, and the moisture content is dried to 1% or less. It is particularly preferred to do this.

  In addition, in order to improve the dispersibility in the thermoplastic resin (B), polybasic acid anhydrides such as maleic anhydride, organic peroxides such as dicumyl peroxide, acid-modified modified polyolefins, polyester waxes Further, a filler (D) surface-treated with fine particles such as fatty acid metal salts such as zinc stearate and metal oxides such as titanium oxide and calcium oxide can also be used.

  These fillers (D) can be used alone or in admixture of two or more. Usually, it mix | blends in 0-2000 mass parts with respect to 100 mass parts of thermoplastic resins (B). When a filler (D) exceeds 2000 mass parts, there exists a possibility that an external appearance may deteriorate.

  If necessary, a foaming agent can be added to the thermoplastic resin composition of the present invention. Examples of the foaming agent include inorganic foaming agents, volatile foaming agents, and decomposable foaming agents. Carbon dioxide, air, nitrogen, etc. as inorganic blowing agents, volatile blowing agents, aliphatic hydrocarbons such as propane, n-butane, isobutane, pentane, hexane, trichlorofluoromethane, dichlorofluoromethane, dichlorotetrafluoroethane , Halogenated hydrocarbons such as methyl chloride, ethyl chloride, and methylene chloride. As the decomposable foaming agent, azodicarbonamide, dinitrosopentamethylenetetramine, azobisisobutyronitrile, sodium bicarbonate, or the like can be used. These foaming agents can be mixed and used as appropriate. Moreover, when using a foaming agent, you may add a bubble regulator in the melt-kneaded material of a thermoplastic resin composition further. Examples of the air conditioner include inorganic powders such as talc and silica, acidic salts of polyvalent carboxylic acids, reaction mixtures of polyvalent carboxylic acids with sodium carbonate or sodium bicarbonate, citric acid, and the like.

  If necessary, a plasticizer can be added to the thermoplastic resin composition of the present invention. Examples of the plasticizer include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dinormal octyl phthalate, 2-ethylhexyl phthalate, diisooctyl phthalate, dicapryl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl phthalate. Phthalates such as diundecyl phthalate, dilauryl phthalate, ditridecyl phthalate, dibenzyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, octyl decyl phthalate, butyl octyl phthalate, octyl benzyl phthalate, normal hexyl normal decyl phthalate, normal octyl normal decyl phthalate Acid ester plasticizer; tricresyl phosphate; Phosphate ester plasticizers such as -2-ethylhexyl phosphate, triphenyl phosphate, 2-ethylhexyl diphenyl phosphate, cresyl diphenyl phosphate; di-2-ethylhexyl adipate, diisodecyl adipate, normal octyl-normal decyl adipate, normal heptyl- Adipate plasticizers such as normal nonyl adipate, diisooctyl adipate, diisonormal octyl adipate, dinormal octyl adipate, didecyl adipate; dibutyl sebacate, di-2-ethylhexyl sebacate, diisooctyl sebacate, Sebacic acid ester plasticizers such as butylbenzyl sebacate; di-2-ethylhexyl azelate, dihexyl azelate, diisooctyl azelate Azelaic acid ester plasticizers; citrate plasticizers such as triethyl citrate, triethyl acetyl citrate, tributyl citrate, tributyl acetyl citrate, tri-2-ethylhexyl citrate; methyl phthalyl ethyl glycolate, Glycolic acid ester plasticizers such as ethyl phthalyl ethyl glycolate and butyl phthalyl butyl glycolate; tributyl trimellitate, tri-normal hexyl trimellitate, tri-2-ethylhexyl trimellitate, tri-normal octyl trimellitate Trimellitic acid ester plasticizers such as tate, tri-isoctyl trimellitate, tri-isodecyl trimellitate; phthalic acid isomers such as di-2-ethylhexyl isophthalate and di-2-ethylhexyl terephthalate Steril plasticizer; Risilolinic acid ester plasticizer such as methyl acetyl ricinolate and butyl acetyl ricinolate; Polyester plasticizer such as polypropylene adipate, polypropylene sebacate and their modified polyesters; Epoxidized soybean oil, Epoxy butyl stearate And epoxy plasticizers such as epoxy (2-ethylhexyl) stearate, epoxidized linseed oil, and 2-ethylhexyl epoxy torate. These may be used alone or in combination of two or more as required.

  If necessary, a stabilizer can be added to the thermoplastic resin composition of the present invention. Examples of stabilizers include lead-based stabilizers such as tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite and lead silicate; metals such as potassium, magnesium, barium, zinc, cadmium and lead And metal soap stabilizers derived from 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, and behenic acid Organotin stabilizers derived from alkyl groups, ester groups and fatty acid salts, maleates, and sulfides; Ba—Zn, Ca—Zn, Ba—Ca, Ca—Mg—Sn, Ca -Zn-Sn-based, Pb-Sn-based, Pb-Ba-Ca-based complex metal soap stabilizers; metals such as barium and zinc; 2-ethylhexanoic acid, isodecanoic acid, tria Two types of normal fatty acids such as branched fatty acids such as killed acetic acid, unsaturated fatty acids such as oleic acid, ricinoleic acid and linoleic acid, alicyclic acids such as naphthenic acid, and aromatic acids such as carboxylic acid, benzoic acid, salicylic acid and substituted derivatives thereof Metal salt stabilizers derived from the above organic acids; these stabilizers are dissolved in an organic solvent such as petroleum hydrocarbons, alcohols, glycerin derivatives, and further phosphites, epoxy compounds, and coloring inhibitors. , Metal stabilizers such as metal salt liquid stabilizers, which are blended with stabilizers such as transparency improvers, light stabilizers, antioxidants, and lubricants; epoxy resins, epoxidized soybean oil, epoxidized vegetable oils, Epoxy compounds such as epoxidized fatty acid alkyl esters, phosphorus is substituted with alkyl groups, aryl groups, cycloalkyl groups, alkoxyl groups, etc., and propylene glycol Dihydric alcohols such as bisphenols, organic phosphites with aromatic compounds such as hydroquinone and bisphenol A, hindered phenols such as bisphenol dimerized with BHT, sulfur and methylene groups, salicylic acid esters, benzophenone, benzo UV absorbers such as triazole, hindered amine or nickel complex salt light stabilizers, UV screening agents such as carbon black and rutile type titanium oxide, polyhydric alcohols such as trimerolpropane, pentaerythritol, sorbitol, mannitol, β-aminocrotonate, Nitrogen-containing compounds such as 2-phenylindole, diphenylthiourea, dicyandiamide, sulfur-containing compounds such as dialkylthiodipropionate, acetoacetate, dehydroacetic acid, β-diketone Keto compounds of the organosilicon compound, non-metallic stabilizers such as boric acid esters. These can be used alone or in combination of two or more.

  If necessary, an impact modifier may be added to the thermoplastic resin composition of the present invention. Examples of the impact modifier include polybutadiene, polyisoprene, polychloroprene, fluororubber, styrene-butadiene copolymer rubber, methyl methacrylate-butadiene-styrene copolymer, and butadiene rubber-containing methyl methacrylate-styrene. Graft copolymer, acrylonitrile-styrene-butadiene copolymer rubber, butadiene rubber-containing acrylonitrile-styrene graft copolymer, styrene-butadiene-styrene block copolymer rubber, styrene-isoprene-styrene copolymer rubber, Styrene-ethylene-butylene-styrene copolymer rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber (EPDM), silicone-containing acrylic rubber-containing methyl methacrylate graft copolymer Silicone-containing acrylic rubber-containing methyl methacrylate-styrene graft copolymer, Silicone-containing acrylic rubber-containing acrylonitrile-styrene graft copolymer, Silicone / acrylic composite rubber-containing methyl methacrylate graft copolymer, Silicone / acrylic composite Rubber-containing methyl methacrylate-styrene graft copolymer, Silicone / acrylic composite rubber-containing acrylonitrile-styrene graft copolymer, Silicone rubber-containing methyl methacrylate graft copolymer, Silicone rubber-containing methyl methacrylate-styrene system Examples include graft copolymers, silicone rubber-containing acrylonitrile-styrene graft copolymers, and the like. As the diene of the ethylene-propylene-diene copolymer rubber (EPDM), 1,4-hexanediene, dicyclopentadiene, methylene norbornene, ethylidene norbornene, propenyl norbornene and the like are used. These impact modifiers can be used alone or in combination of two or more.

  If necessary, a lubricant can be added to the thermoplastic resin composition of the present invention. Examples of the lubricant include pure hydrocarbons such as liquid paraffin, natural paraffin, micro wax, synthetic paraffin, and low molecular weight polyethylene; halogenated hydrocarbons; fatty acids such as higher fatty acids and oxy fatty acids; fatty acid amides and bis fatty acid amides. Fatty acid amides such as fatty acid lower alcohol esters, fatty acid polyhydric alcohol esters such as glycerides, fatty acid polyglycol esters, fatty acid fatty alcohol esters (ester waxes), etc .; metal soaps, fatty alcohols, polyhydric acids Examples thereof include alcohols, polyglycols, polyglycerols, partial esters of fatty acids and polyhydric alcohols, fatty acids and polyglycols, and polyglycerol partial esters.

  If necessary, a processing aid can be added to the thermoplastic resin composition of the present invention. Examples of processing aids include (meth) acrylic acid ester copolymers, (meth) acrylic acid ester-styrene copolymers, (meth) acrylic acid ester-styrene-α-methylstyrene copolymers, acrylonitrile- Examples include styrene copolymers, acrylonitrile-styrene- (meth) acrylic acid ester copolymers, acrylonitrile-styrene-α-styrene copolymers, acrylonitrile-styrene-maleimide copolymers, and the like.

  In the thermoplastic resin composition of the present invention, as long as the properties are not impaired, a pigment, an antifogging agent, an antibacterial agent, an antistatic agent, a conductivity imparting agent, a surfactant, a crystal nucleating agent, Various additives such as a heat resistance improver can be added.

  As a blending method of the thermoplastic resin modifier (A) of the present invention into the thermoplastic resin (B), for example, it is carried out by melt kneading by a conventionally known method such as extrusion kneading or roll kneading. it can. In addition, the thermoplastic resin modifier (A) of the present invention and a part of the thermoplastic resin (B) are mixed to prepare a master batch first, and the remainder of the thermoplastic resin (B) is further added and mixed. Multi-stage mixing is also possible.

  Examples of the molding process of the thermoplastic resin composition to which the modifier for thermoplastic resin (A) of the present invention is added include, for example, calendar molding, thermoforming, extrusion blow molding, foam molding, extrusion molding, injection molding, and melting. Examples thereof include spinning. Among these, extrusion blow molding, extrusion molding, and injection molding are preferable. Further, molding processing while foaming is possible, and injection foam molding or extrusion foam molding is particularly preferable.

  Examples of useful molded articles obtained using the thermoplastic resin composition to which the modifier for thermoplastic resins (A) of the present invention is added include, for example, sheets, films and profile molded articles by extrusion molding; extrusion blow molding, Examples thereof include a hollow molded body by injection molding and an injection molded body. Specific examples thereof include automobile bumpers, spoilers, side moldings, ceilings and interior materials, OA equipment casings, window frames, shelf boards, floor materials, wall materials, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. In each description, “part” indicates mass part, and “%” indicates mass%. Various physical properties were measured by the following methods.

(1) Particle size measurement:
Measurement was performed using a CHDF2000 type particle size distribution meter manufactured by MATEC USA using a sample of a dispersion of modifier particles for thermoplastic resin diluted with distilled water. The measurement conditions were standard conditions recommended by MATEC. That is, using a dedicated cartridge cartridge for particle separation and carrier liquid, the liquidity is almost neutral, the flow rate is 1.4 ml / min, the pressure is about 4000 psi (2600 KPa), and the temperature is kept at 35 ° C., the concentration is about 3%. A 0.1 ml diluted latex sample was used for the measurement. As the standard particle size substance, a total of 12 monodisperse polystyrenes having a known particle size manufactured by DUKE in the United States were used in the range of 0.02 μm to 0.8 μm.

(2) Glass transition temperature (Tg):
The glass transition temperature (Tg) of the thermoplastic copolymer (A-2) was calculated using the Fox formula shown below (see Non-Patent Document 1).

1 / Tg = W ₁ / Tg ₁ + W ₂ / Tg ₂ + W ₃ / Tg ₃ +... = ΣW _i / Tg _i
(Here, Tg _i represents the Tg of the i component polymer, and W _i represents the weight fraction of the i component.)
The value described in Non-Patent Document 2 was used as the glass transition temperature (Tg) of the i-component polymer.

(3) Measurement of powder fluidity:
Measurement was carried out using a bulk density meter (manufactured by Tsutsui Rika Kikai Co., Ltd.) in accordance with JIS K6721. In this measurement, after filling the funnel of the bulk density meter with the powder, the powder was allowed to flow through the funnel for 10 seconds, the powder that flowed out was weighed, and an index of powder fluidity (g / 10 sec) did. The diameter of the funnel outlet used is 8 mm.

  The larger the amount of powder that flows out in 10 seconds, the better the fluidity of the powder. In actual work, it means that a powder with good fluidity also has good handleability. Experience has shown that a powder having fluidity of 20 g or less in 10 seconds in this test is inferior in handleability even in actual work.

(4) Measurement of storage stability (cohesiveness) of powder:
An acrylic resin container is filled with 20 g of powder and a 5 kg weight is placed on the container, and the oven is placed in a gear oven (GHPS-222 manufactured by Tabai Co., Ltd.) at 60 ° C. 6 The mixture was left for a period of time and then taken out and cooled at room temperature to prepare a powder block. This powder block is placed on a sieve having a mesh size of 12 mesh, and is crushed with a vibration sieve machine (Micro-type electromagnetic vibration sieve machine M-2, manufactured by Tsutsui Rika Kikai Co., Ltd.), resulting in a crushing amount of 60%. The time of arrival, that is, 60% crushing time was used as an index of storage stability of the powder.

  Experience has shown that the shorter the 60% crushing time, the harder the powder is when the powder is actually stored, and the more easily the powder lump can be broken. In addition, powder that tends to harden hardly returns to its original shape even when the lump is broken. When such powder is added to a thermoplastic resin, it may have poor dispersibility in the thermoplastic resin, appearance of the molded product, or flame retardancy. It tends to cause a decrease. From experience, a powder having a 60% crushing time of 100 seconds or more tends to harden when stored for a long time.

(5) Evaluation of dispersibility in thermoplastic resin:
In the evaluation of the storage stability of the powder of (4), the powder at the time when the 60% crushing time was reached was added to the polycarbonate resin, and a test piece for vertical combustion test having a thickness of 1.6 mm according to UL94 standard Was made. Observation of the presence or absence of aggregates in the prepared specimen was visually performed with transmitted light, and judged according to the following criteria.
○: No aggregates are observed in the specimen.
X: Aggregates were observed in the specimen.

(6) Flammability test:
A vertical combustion test was performed in accordance with the UL94 standard. A test piece having a thickness of 1.6 mm was used.

(7) Izod impact strength test:
Based on ASTM D256, it measured at 23 degreeC using the test piece with 3.2 mm thickness and a notch.

(8) Tensile test:
Tensile strength and tensile elongation were measured according to ASTM D638.

(9) Observation of surface appearance:
The surface appearance of the injection-molded test piece was visually observed and judged according to the following criteria.
○: No irregularities on the surface.
X: There are bumps on the surface.

<Production Example 1: Modifier for thermoplastic resin (A-1)>
143.3 parts by mass of distilled water and 3.0 parts by mass of dipotassium alkenyl succinate were charged into a reaction vessel equipped with a stirring blade, a condenser, a thermocouple, a nitrogen inlet and a dripping port, and then polytetrafluoroethylene (a- 1-1) Particle dispersion (Asahi Fluoropolymers, Fluon AD936 (trade name), polytetrafluoroethylene concentration 60%, average particle size 0.30 μm) 116.7 parts by mass (polytetrafluoroethylene 70 parts by mass) Was charged into a reaction vessel using a rotary pump (manufactured by Johnson Pump, IC30S-D (trade name)). Furthermore, after charging 24 parts by mass of methyl methacrylate, 6 parts by mass of n-butyl acrylate, 2.0 parts by mass of t-butyl hydroperoxide, and 0.2 parts of n-octyl mercaptan as a chain transfer agent, The atmosphere in the reaction vessel was replaced with nitrogen by passing through. Thereafter, when the temperature inside the reaction vessel was raised to 55 ° C. and the internal liquid temperature reached 55 ° C., 0.005 parts by mass of iron (II) sulfate, 0.015 parts by mass of disodium ethylenediaminetetraacetate, Rongalite salt Polymerization of monomer components to obtain a (meth) acrylic acid alkyl ester-based polymer (a-1-2) by adding a mixed solution from 2.0 parts by mass and 10 parts by mass of distilled water and maintaining for 90 minutes Went. Solid separation was not observed throughout the series of operations, and a uniform dispersion of the polytetrafluoroethylene-containing polymer (a-1) was obtained. The resulting dispersion had a solid content of 33.1%. Moreover, the glass transition temperature (Tg) of the (meth) acrylic-acid alkylester polymer (a-1-2) was 56 degreeC by the calculated value.

  The average particle diameter of the (meth) acrylic acid alkyl ester polymer (a-1-2) particles in this dispersion was 0.85 μm. The weight average molecular weight (Mw) of the (meth) acrylic acid alkyl ester polymer (a-1-2) measured by gel permeation chromatography was 25,000.

  100 parts of pure water was added to a reactor equipped with a stirrer, a thermocouple, and a dropping port, and the temperature was raised to 80 ° C. When the internal temperature reaches 80 ° C., 130 parts by mass of an aqueous solution in which 3.0 parts by mass of aluminum sulfate is dissolved and 100 parts by mass of the polytetrafluoroethylene-containing polymer (a-1) dispersion are taken over 20 minutes. The solid was precipitated by dropping. Next, the inside was heated to 98 ° C., and this state was maintained for 20 minutes. Then, this precipitate was separated, filtered, washed and dried to obtain a polytetrafluoroethylene-containing polymer (a-1).

  For 100 parts by mass of the recovered polytetrafluoroethylene-containing polymer (a-1), 1.0 part by mass of silica (manufactured by Nippon Aerosil Co., Ltd., R-972 (trade name)) as the inorganic additive (a-2) Was added to obtain a thermoplastic resin modifier (A-1).

<Production Example 2: Modifier for thermoplastic resin (A-2)>
In a reaction vessel equipped with a stirring blade, a condenser, a thermocouple, a nitrogen inlet, and a dropping port, 143.3 parts by mass of distilled water, 3.0 parts by mass of dipotassium alkenyl succinate, 24 parts by mass of methyl methacrylate, n-acrylic acid n- 6 parts by mass of butyl, 2.0 parts by mass of t-butyl hydroperoxide, 0.2 parts by mass of n-octyl mercaptan as a chain transfer agent were charged, and the atmosphere in the reaction vessel was replaced with nitrogen by passing through a nitrogen stream. . Thereafter, when the temperature inside the system was raised to 55 ° C. and the internal liquid temperature reached 55 ° C., 0.0005 parts by mass of iron (II) sulfate, 0.0015 parts by mass of disodium ethylenediaminetetraacetate, Rongalite salt 0 An aqueous solution in which (meth) acrylic acid alkyl ester-based polymer (a-1-2) particles are dispersed by adding a mixed liquid consisting of 2 parts by mass and 10 parts by mass of distilled water and maintaining the mixture for 90 minutes for polymerization. A dispersion was obtained. The solid content concentration of the aqueous dispersion of the obtained (meth) acrylic acid alkyl ester polymer (a-1-2) particles was 16.2%.

  The average particle size of the (meth) acrylic acid alkyl ester polymer (a-1-2) particles in this aqueous dispersion was 0.070 μm. The weight average molecular weight (Mw) of the (meth) acrylic acid alkyl ester polymer (a-1-2) measured by gel permeation chromatography was 22,000. Moreover, the glass transition temperature (Tg) of the (meth) acrylic-acid alkylester type polymer (a-1-2) was 56 degreeC by the calculated value.

  In this reaction container, 116.7 parts by mass of polytetrafluoroethylene (a-1-1) particle dispersion used in Production Example 1 (70 parts by mass as a solid content) was added to a rotary lobe pump (Toko Sangyo Co., Ltd.). It added from the dropping port using Viking IC30S-D (trade name). After the addition was completed, the particle dispersions were mixed with stirring for 30 minutes to obtain a dispersion of the polytetrafluoroethylene-containing polymer (a-1). Solid separation was not observed through a series of operations, and the solid content of the obtained dispersion was 33.1%.

  100 parts of pure water was added to a stirrer, a thermocouple, and a container with a dropping port, and the temperature was raised to 80 ° C. When the internal temperature reaches 80 ° C., 130 parts by mass of an aqueous solution in which 3.0 parts by mass of aluminum sulfate is dissolved and 100 parts by mass of the polytetrafluoroethylene-containing polymer (a-1) dispersion are taken over 20 minutes. The solid was precipitated by dropping. Next, the inside was heated to 98 ° C., and this state was maintained for 20 minutes. Then, this precipitate was separated, filtered, washed and dried to obtain a polytetrafluoroethylene-containing polymer (a-1).

  With respect to 100 parts by mass of the recovered polytetrafluoroethylene-containing polymer (a-1), calcium carbonate (manufactured by Ishihara Sangyo Co., Ltd., white gloss flower CCR (trade name)) 5.0 as an inorganic additive (a-2) Mass parts were added to obtain a thermoplastic resin modifier (A-2).

<Production Example 3: Modifier for thermoplastic resin (A-3)>
156.7 parts by mass of distilled water and 3.0 parts by mass of dipotassium alkenyl succinate were charged into a reaction vessel equipped with a stirring blade, a condenser, a thermocouple, a nitrogen inlet and a dripping port, and then the poly used in Production Example 1 A reaction vessel containing 83.3 parts by mass of a tetrafluoroethylene (a-1-1) particle dispersion (polytetrafluoroethylene 50 parts by mass) using a rotary pump (Johnson Pump, IC30S-D (trade name)). Was charged. Furthermore, after charging 35 parts by mass of methyl methacrylate, 15 parts by mass of n-butyl acrylate, 2.4 parts by mass of t-butyl hydroperoxide, and 0.25 part of n-octyl mercaptan as a chain transfer agent, The atmosphere in the reaction vessel was replaced with nitrogen by passing through. Thereafter, when the temperature inside the reaction vessel was raised to 55 ° C. and the internal liquid temperature reached 55 ° C., 0.005 parts by mass of iron (II) sulfate, 0.015 parts by mass of disodium ethylenediaminetetraacetate, Rongalite salt A mixture of 2.4 parts by mass and 10 parts by mass of distilled water is added and held for 90 minutes to obtain a (meth) acrylic acid alkyl ester polymer (a-1-2). Polymerization was performed. Solid separation was not observed throughout the series of operations, and a uniform dispersion of the polytetrafluoroethylene-containing polymer (a-1) was obtained. The solid content of the obtained dispersion was 33.3%.

  The average particle diameter of the (meth) acrylic acid alkyl ester polymer (a-1-2) particles in this dispersion was 0.80 μm. The weight average molecular weight (Mw) of the (meth) acrylic acid alkyl ester polymer (a-1-2) measured by gel permeation chromatography was 29,000. Moreover, the glass transition temperature (Tg) of the (meth) acrylic-acid alkylester type polymer (a-1-2) was 55 degreeC by the calculated value.

  220 parts by mass of distilled water and 1.0 part by mass of dipotassium alkenyl succinate were charged into a reaction vessel equipped with a stirring blade, a condenser, a thermocouple, a nitrogen inlet and a dripping port, and then 80 parts by mass of methyl methacrylate and ethyl acrylate. After charging 20 parts by mass, 0.15 parts by mass of potassium persulfate, and 0.03 parts by mass of n-octyl mercaptan as a chain transfer agent, the atmosphere in the reaction vessel was replaced with nitrogen by passing a nitrogen stream. Thereafter, the temperature inside the reaction vessel was raised to 55 ° C., and when the temperature of the internal liquid reached 55 ° C., the reaction vessel was held for 90 minutes to polymerize the organic hard polymer (a-3). The solid content of the obtained organic hard polymer (a-3) dispersion was 30.2%. Moreover, the glass transition temperature (Tg) of the obtained organic hard polymer (a-3) was 69 degreeC by the calculated value.

  100 parts of pure water was added to a reaction vessel equipped with a stirrer, a thermocouple, and a dropping port, and the temperature was raised to 85 ° C. When the internal temperature reached 85 ° C., 130 parts by mass of an aqueous solution in which 4.0 parts by mass of aluminum sulfate was dissolved and 100 parts of a tetrafluoroethylene-containing polymer (a-1) dispersion were dropped over 20 minutes. A solid was precipitated. Next, an aqueous dispersion prepared by adding 20 parts by mass of distilled water to 6.7 parts by mass of the organic hard polymer (a-3) dispersion (2.0 parts by mass as the organic hard polymer) was placed in the reaction vessel. It was added dropwise over 20 minutes. Thereafter, the inside was heated to 98 ° C., and this state was maintained for 20 minutes. Then, this precipitate was separated, filtered, washed and dried to obtain a thermoplastic resin modifier (A-3).

<Production Example 4: Modifier for thermoplastic resin (A-4)>
In a reaction vessel equipped with a stirring blade, a condenser, a thermocouple, a nitrogen inlet, and a dripping port, 148.7 parts by mass of distilled water, 2.5 parts by mass of dipotassium alkenyl succinate, 30.4 parts by mass of methyl methacrylate, acrylic acid 7.6 parts by mass of methyl, 2.5 parts by mass of t-butyl hydroperoxide, 0.3 parts by mass of n-octyl mercaptan as a chain transfer agent were added, and the atmosphere in the reaction vessel was replaced with nitrogen by passing through a nitrogen stream. went. Thereafter, when the temperature in the system was raised to 55 ° C. and the internal liquid temperature reached 55 ° C., 0.0005 parts by mass of iron (II) sulfate, 0.0015 parts by mass of disodium ethylenediaminetetraacetate, Rongalite salt 2 An aqueous dispersion in which (meth) acrylic acid alkyl ester-based polymer (a-1-2) particles are dispersed by adding a mixed solution of 5 parts by mass and 10 parts by mass of distilled water and maintaining the mixture for 90 minutes for polymerization. A liquid was obtained. The solid content concentration of the aqueous dispersion of the obtained (meth) acrylic acid alkyl ester polymer (a-1-2) particles was 19.1%.

  The average particle size of the (meth) acrylic acid alkyl ester polymer (a-1-2) particles in this aqueous dispersion was 0.071 μm. The weight average molecular weight (Mw) of the (meth) acrylic acid alkyl ester polymer (a-1-2) measured by gel permeation chromatography was 35,000. Moreover, the glass transition temperature (Tg) of the (meth) acrylic-acid alkylester type polymer (a-1-2) was 81 degreeC by the calculated value.

  In this reaction vessel, 103.3 parts by mass of polytetrafluoroethylene (a-1-1) particle dispersion liquid used in Production Example 1 (62 parts by mass as a solid content) is a rotary lobe pump (Toko Sangyo Co., Ltd., It added from the dropping port using Viking IC30S-D (trade name). After the addition was completed, the particle dispersions were mixed with stirring for 30 minutes to obtain a dispersion of the polytetrafluoroethylene-containing polymer (a-1). Solid separation was not observed through a series of operations, and the solid content of the obtained dispersion was 33.0%.

  100 parts of pure water was added to a reactor equipped with a stirrer, a thermocouple, and a dropping port, and the temperature was raised to 83 ° C. When the internal temperature reaches 83 ° C., 120 parts by mass of an aqueous solution in which 8.0 parts by mass of calcium acetate is dissolved and 100 parts by mass of the polytetrafluoroethylene-containing polymer (a-1) dispersion are taken over 20 minutes. The solid substance was deposited by dropping. Next, an aqueous solution obtained by adding 39.6 parts by weight of distilled water to 13.2 parts by weight of the organic hard polymer (a-3) dispersion used in Production Example 3 (4.0 parts by weight as the organic hard polymer). The dispersion was added dropwise over 20 minutes. Thereafter, the inside was heated to 98 ° C., and this state was maintained for 20 minutes. Then, this precipitate was separated, filtered, washed and dried to obtain a thermoplastic resin modifier (A-4).

<Production Example 5: Modifier for thermoplastic resin (A-5)>
86.7 parts by mass of polytetrafluoroethylene (A-5-1) particle dispersion used in Example 1 (52 parts by mass as a solid content) was added to a rotary lobe pump (Toko Sangyo Co., Ltd. Viking IC30S-D (product) No.)) was charged into a reaction vessel equipped with a stirring blade, a condenser, a thermocouple, a nitrogen inlet, and a dripping port, and then from 155.4 parts by mass of distilled water and 3.0 parts by mass of dipotassium alkenyl succinate. And a mixture of 38.4 parts by weight of methyl methacrylate, 9.6 parts by weight of n-butyl methacrylate, 0.25 parts by weight of n-octyl mercaptan and 2.5 parts by weight of t-butyl hydroperoxide. Then, the atmosphere in the reaction vessel was replaced with nitrogen by passing a nitrogen stream for 1 hour. The internal temperature was then raised to 55 ° C. When the internal temperature reaches 55 ° C., it consists of 0.001 part by mass of iron (II) sulfate, 0.003 part by mass of disodium ethylenediaminetetraacetate, 0.2 part by mass of Rongalite salt and 10 parts by mass of distilled water. The polytetrafluoroethylene-containing polymer (a- A dispersion of 1) was obtained. Solid separation was not observed through a series of operations, and the solid content of the obtained dispersion was 33.4%.

  The average particle diameter of the (meth) acrylic acid alkyl ester polymer (a-1-2) particles in this dispersion was 0.069 μm. Further, the weight average molecular weight (Mw) of the (meth) acrylic acid alkyl ester polymer measured by gel permeation chromatography was 31,000. Moreover, the glass transition temperature (Tg) of the (meth) acrylic-acid alkylester polymer (a-1-2) was 84 degreeC by the calculated value.

  140 parts by mass of distilled water and 1.5 parts by mass of sodium N-lauroyl sarcosinate were charged into a reaction vessel equipped with a stirring blade, a condenser, a thermocouple, a nitrogen inlet, and a dropping port, and then 30 parts by mass of methyl methacrylate, t -After charging 0.07 mass part of butyl hydroperoxide, nitrogen substitution of the atmosphere in reaction container was performed by letting a nitrogen stream pass.

  Thereafter, when the temperature in the reaction vessel was raised to 55 ° C. and the internal liquid temperature reached 55 ° C., 0.0004 parts by mass of iron (II) sulfate, 0.0012 parts by mass of disodium ethylenediaminetetraacetate, Rongalite salt A mixed liquid consisting of 0.3 part by mass and 10 parts by mass of distilled water was added and held for 60 minutes, and then the internal temperature was raised to 66 ° C. When the internal liquid temperature reached 66 ° C, 33 parts by mass of styrene, 22 parts by mass of n-butyl acrylate, 0.345 parts by mass of t-butyl hydroperoxide, and 0.5 parts by mass of n-octyl mercaptan as a chain transfer agent Part of the mixture was added dropwise from the dropping port over 90 minutes. This state was maintained for 60 minutes after the completion of dropping. After completion of the holding, a mixture of 15 parts by mass of methyl methacrylate and 0.07 parts by mass of t-butyl hydroperoxide was dropped from the dropping port over 30 minutes. After completion of dropping, this state was maintained for 60 minutes to polymerize the organic hard polymer (a-3) to obtain an aqueous dispersion of organic hard polymer (a-3) particles. Separation of solid content was not recognized by a series of operation, and solid content of the obtained dispersion liquid was 40.1%. Moreover, the glass transition temperature of the obtained organic type hard polymer (a-3) was 52 degreeC.

  100 parts of pure water was added to a reactor equipped with a stirrer, a thermocouple, and a dropping port, and the temperature was raised to 81 ° C. When the internal temperature reached 81 ° C., 130 parts by mass of an aqueous solution in which 4 parts by mass of aluminum sulfate was dissolved and 100 parts of the polytetrafluoroethylene-containing polymer (a-1) dispersion were dropped over 20 minutes. A solid was precipitated. Next, an aqueous dispersion obtained by adding 7.5 parts by weight of distilled water to 2.5 parts by weight of the organic hard polymer (a-3) dispersion (1.0 part by weight as the organic hard polymer) was added over 5 minutes. It was dripped. Thereafter, the inside was heated to 98 ° C., and this state was maintained for 20 minutes. Then, this precipitate was separated, filtered, washed and dried to obtain a polytetrafluoroethylene-containing polymer (a-1 '). Thereafter, 0.5 parts by mass of the silica used in Production Example 1 is added to 100 parts by mass of the polytetrafluoroethylene-containing polymer (a-1 ′) to modify the thermoplastic resin modifier (A-5). Got.

<Production Example 6: Modifier for thermoplastic resin (A-6)>
In a reaction vessel equipped with a stirring blade, a condenser, a thermocouple, a nitrogen inlet, and a dripping port, 155.3 parts by mass of distilled water, 3.5 parts by mass of dipotassium alkenyl succinate, 38.4 parts by mass of methyl methacrylate, acrylic acid 9.6 parts by mass of n-butyl, 2.5 parts by mass of t-butyl hydroperoxide, 0.24 parts by mass of n-octyl mercaptan as a chain transfer agent, and passing through a nitrogen stream, nitrogen in the atmosphere in the reaction vessel Replacement was performed. Thereafter, when the temperature in the system was raised to 55 ° C. and the internal liquid temperature reached 55 ° C., 0.0005 parts by mass of iron (II) sulfate, 0.0015 parts by mass of disodium ethylenediaminetetraacetate, Rongalite salt 2 An aqueous dispersion in which (meth) acrylic acid alkyl ester-based polymer (a-1-2) particles are dispersed by adding a mixed solution of 5 parts by mass and 10 parts by mass of distilled water and maintaining the mixture for 90 minutes for polymerization. A liquid was obtained. The solid content concentration of the aqueous dispersion of the obtained (meth) acrylic acid alkyl ester polymer (a-1-2) particles was 22.4%.

  The average particle size of the (meth) acrylic acid alkyl ester polymer (a-1-2) particles in this aqueous dispersion was 0.072 μm. Moreover, it was the weight average molecular weight (Mw) of 29,000 of the (meth) acrylic-acid alkylester type | system | group polymer (a-1-2) measured by the gel permeation chromatography. Moreover, the glass transition temperature (Tg) of the (meth) acrylic-acid alkylester type polymer (a-1-2) was 46 degreeC by the calculated value.

  In this reaction vessel, 86.7 parts by mass of the polytetrafluoroethylene (a-1-1) particle dispersion used in Production Example 1 (52 parts by mass as a solid content) was added to a rotary lobe pump (Toko Sangyo Co., Ltd., It added from the dropping port using Viking IC30S-D (trade name). After the addition was completed, the particle dispersions were mixed with stirring for 30 minutes to obtain a dispersion of the polytetrafluoroethylene-containing polymer (a-1). Solid separation was not observed throughout the series of operations, and the solid content of the obtained dispersion was 33.5%.

  100 parts of pure water was added to a reactor equipped with a stirrer, a thermocouple, and a dropping port, and the temperature was raised to 80 ° C. When the internal temperature reaches 80 ° C., 130 parts by mass of an aqueous solution in which 3.5 parts by mass of aluminum sulfate is dissolved and 100 parts by mass of the polytetrafluoroethylene-containing polymer (a-1) dispersion are taken over 20 minutes. To drop a solid. Next, an aqueous solution obtained by adding 19.8 parts by weight of distilled water to 6.6 parts by weight of the organic hard polymer (a-3) dispersion used in Production Example 3 (2.0 parts by weight as the organic hard polymer). The dispersion was added dropwise over 10 minutes. Thereafter, the inside was heated to 98 ° C., and this state was maintained for 20 minutes. Then, this precipitate was separated, filtered, washed and dried to obtain a polytetrafluoroethylene-containing polymer (a-1 '). Thereafter, 0.2 part by mass of silica used in Production Example 1 is added to 100 parts by mass of the polytetrafluoroethylene-containing polymer (a-1 ′), and a modifier for polytetrafluoroethylene-containing thermoplastic resin is added. (A-6) was obtained.

<Production Example 10: Modifier for thermoplastic resin (A-10)>
In the same manner as in Production Example 1, after obtaining a polytetrafluoroethylene-containing polymer (a-1), an inorganic additive (a-2) was not added, and the thermoplastic resin modifier (A-10) was used as it was. ).

<Production Example 11: Modifier for thermoplastic resin (A-11)>
In the same manner as in Production Example 6, after obtaining a polytetrafluoroethylene-containing polymer (a-1 ′), 100 parts by mass of the polytetrafluoroethylene-containing polymer (a-1 ′) is added to an inorganic additive (a -2) 15 parts by mass of silica was added to obtain a thermoplastic resin modifier (A-11).

<Production Example 12: Modifier for thermoplastic resin (A-12)>
In the same manner as in Production Example 6, when obtaining the polytetrafluoroethylene-containing polymer (a-1 ′), 132.5 parts by mass (organic) of the dispersion of the organic hard polymer (a-3) used in Production Example 3 A thermoplastic resin modifier (A-12) is obtained in the same manner as in Production Example 6 except that an aqueous dispersion in which 397.5 parts by weight of distilled water is added to 40 parts by weight as a hard polymer is used. It was.

<Production Example 13: Modifier for thermoplastic resin (A-13)>
Polymerization of the organic hard polymer (a-3) shown below was performed. 250 parts by mass of distilled water and 1.0 part by mass of sodium N-lauroyl sarcosinate were charged into a reaction vessel equipped with a stirring blade, a condenser, a thermocouple, a nitrogen inlet and a dripping port, and then 30 parts by mass of methyl methacrylate, t -After charging 0.1 mass part of butyl hydroperoxide and 0.03 mass part of n-octyl mercaptan, nitrogen substitution of the atmosphere in the reaction vessel was performed by passing a nitrogen stream. Thereafter, when the temperature in the reaction vessel was raised to 55 ° C. and the internal liquid temperature reached 55 ° C., 0.001 part by mass of iron (II) sulfate, 0.003 part by mass of disodium ethylenediaminetetraacetate, Rongalite salt A mixed liquid consisting of 0.4 parts by mass and 10 parts by mass of distilled water was added and held for 60 minutes, and then the internal temperature was raised to 66 ° C. When the internal liquid temperature reached 66 ° C., 20 parts by mass of n-butyl methacrylate, 30 parts by mass of n-butyl acrylate, 1.5 parts by mass of t-butyl hydroperoxide, 0.5 mass of n-octyl mercaptan Part of the mixture was added dropwise from the dropping port over 90 minutes. This state was maintained for 60 minutes after the completion of dropping. After completion of the holding, a mixture of 20 parts by mass of methyl methacrylate, 0.1 parts by mass of t-butyl hydroperoxide and 0.05 parts by mass of n-octyl mercaptan was dropped from the dropping port over 30 minutes. After completion of dropping, this state was maintained for 60 minutes to polymerize the organic hard polymer (a-3) to obtain an aqueous dispersion of organic hard polymer (a-3) particles. Separation of solid content was not recognized by a series of operation, and solid content of the obtained dispersion liquid was 27.4%. Moreover, the glass transition temperature of the obtained organic hard polymer was 24 degreeC.

  In the same manner as in Production Example 4, the polytetrafluoroethylene-containing polymer (a-1) was coagulated from the mixed aqueous dispersion. An aqueous solution obtained by adding 43.8 parts by mass of distilled water to 14.6 parts by mass of the aqueous dispersion of the organic hard polymer (a-3) (4.0 parts by mass as the organic hard polymer) with respect to this slurry. A thermoplastic resin modifier (A-13) was obtained in the same manner as in Production Example 4 except that the dispersion was added.

<Production Example 14: Modifier for thermoplastic resin (A-14)>
Polymerization of the organic hard polymer (a-3) shown below was performed. 290 parts by mass of distilled water and 1.0 part by mass of dipotassium alkenyl succinate were charged into a reaction vessel equipped with a stirring blade, a condenser, a thermocouple, a nitrogen inlet and a dripping port, and then 90 parts by mass of methyl methacrylate and 10 parts by mass of styrene. And 0.1 parts by mass of t-butyl hydroperoxide were charged, and the atmosphere in the reaction vessel was replaced with nitrogen by passing through a nitrogen stream. Thereafter, when the temperature in the reaction vessel was raised to 55 ° C. and the internal liquid temperature reached 55 ° C., 0.001 part by mass of iron (II) sulfate, 0.003 part by mass of disodium ethylenediaminetetraacetate, Rongalite salt A mixed liquid consisting of 0.1 part by mass and 10 parts by mass of distilled water was added and held for 60 minutes, followed by polymerization to obtain an aqueous dispersion of organic hard polymer (a-3) particles. The obtained dispersion had a solid content of 24.9%. Moreover, the glass transition temperature of the obtained organic hard polymer was 100 ° C.

  In the same manner as in Production Example 4, when the polytetrafluoroethylene-containing polymer (a-1) is recovered from the mixed aqueous dispersion, the aqueous dispersion of the organic hard polymer (a-3) is added to this slurry. After adding an aqueous dispersion in which 48.3 parts by weight of distilled water was added to 16.1 parts by weight (4.0 parts by weight as an organic hard polymer), the temperature of the reaction vessel was raised to 100 ° C. In the same manner as in Production Example 4, a thermoplastic resin modifier (A-14) was obtained.

<Production Example 15: Modifier for thermoplastic resin (A-15)>
In a mixed solution of 70 parts by mass of dodecyl methacrylate and 30 parts by mass of methyl methacrylate, 0.1 part by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved. A mixed solution of 2 parts by weight of sodium dodecylbenzenesulfonate and 300 parts by weight of distilled water was added thereto, stirred at 10000 rpm for 4 minutes with a homomixer, and then passed twice through the homogenizer at a pressure of 30 MPa to obtain stable methacrylic acid. A dodecyl / methyl methacrylate predispersion was obtained. This was charged into a reaction vessel equipped with a stirring blade, a condancer, a thermocouple, and a nitrogen inlet, and the polymerization was started by raising the internal temperature to 80 ° C. under a nitrogen stream, and this state was maintained for 3 hours. To obtain a dispersion of (meth) acrylic acid alkyl ester polymer (a-1-2 ′) particles.

  The solid content of the (meth) acrylic acid alkyl ester polymer (a-1-2 ') particles in this dispersion was 25.1%, and the average particle size was 0.19 μm. The weight average molecular weight (Mw) of the (meth) acrylic acid alkyl ester polymer (a-1-2 ') measured by gel permeation chromatography was 600,000. Further, the glass transition temperature (Tg) of the (meth) acrylic acid alkyl ester polymer (a-1-2 ') was calculated to be -30 ° C.

  In a reaction vessel equipped with a stirring blade, a condenser, a thermocouple, a nitrogen inlet, and a dripping port, 33.3 parts by mass (as solid content) of the polytetrafluoroethylene (a-1-1) particle dispersion used in Production Example 1 20 parts by mass) was charged from the dropping port using a rotary lobe pump (manufactured by Johnson Pump, Viking IC30S-D (trade name)). Subsequently, after charging 239 mass parts (60 mass parts as solid content) of (meth) acrylic-acid alkylester type polymer (a-1-2 '), nitrogen of atmosphere in reaction container is passed through nitrogen stream for 1 hour Replacement was performed. Thereafter, the inside was heated to 80 ° C. When the internal temperature reached 80 ° C, 0.001 part by mass of iron (II) sulfate, 0.003 part by mass of disodium ethylenediaminetetraacetate, 0.24 part by mass of Rongalite salt, 7.7 parts by mass of distilled water After adding the mixed solution, a mixture of 20 parts by mass of methyl methacrylate and 0.1 parts by mass of t-butyl hydroperoxide was added dropwise from the dropping port over 30 minutes, and then held for 1 hour to (meth) acrylic acid. The dispersion of polytetrafluoroethylene-containing polymer (a-1) particles was obtained by polymerizing the monomer component to obtain the alkyl ester polymer (a-1-2). Solid separation was not observed throughout the series of operations, and the resulting dispersion had a solid content of 33.8%. The weight average molecular weight (Mw) of the (meth) acrylic acid alkyl ester polymer (a-1-2) measured by gel permeation chromatography was 400,000. Moreover, the glass transition temperature (Tg) of the (meth) acrylic-acid alkylester type polymer (a-1-2) was -6 degreeC by the calculated value.

  100 parts of pure water was added to a reactor equipped with a stirrer, a thermocouple, and a dropping port, and the internal temperature was raised to 60 ° C. When the internal temperature reached 60 ° C., 120 parts by mass of an aqueous solution in which 8.0 parts by mass of calcium acetate was dissolved and 100 parts by mass of a dispersion of the polytetrafluoroethylene-containing polymer (a-1) particles were 20 parts. The solution was dropped over a period of time to precipitate a solid. Next, an aqueous dispersion obtained by adding 19.8 parts by weight of distilled water to 6.6 parts by weight of the organic hard polymer (a-3) used in Production Example 3 (2.0 parts by weight as the organic hard polymer). After adding, the temperature was raised to 90 ° C. and this state was maintained for 20 minutes. The inorganic additive (a-2) used in Production Example 1 was separated from 100 parts by mass of the polytetrafluoroethylene-containing polymer (a-1 ′) obtained by separating, filtering, washing and drying the precipitate. And 0.3 part by mass of silica was added to obtain a thermoplastic resin modifier (A-15).

<Production Example 16: Modifier for thermoplastic resin (A-16)>
In a reaction vessel equipped with a stirring blade, a condenser, a thermocouple, and a nitrogen inlet, 220 parts by mass of distilled water, 1.0 part by mass of dipotassium alkenyl succinate, 80 parts by mass of methyl methacrylate, 20 parts by mass of n-butyl acrylate, The atmosphere in the reaction vessel was purged with nitrogen by charging 0.0008 parts by mass of n-octyl mercaptan and passing a nitrogen stream for 1 hour. Thereafter, when the temperature inside the system was raised to 55 ° C. and the internal liquid temperature reached 55 ° C., a mixed solution consisting of 0.15 parts by mass of potassium persulfate and 10 parts by mass of distilled water was added and held for 90 minutes. Then, an aqueous dispersion in which (meth) acrylic acid alkyl ester polymer (a-1-2) particles were dispersed was obtained by polymerization. The solid content concentration of the aqueous dispersion of the obtained (meth) acrylic acid alkyl ester polymer (a-1-2) particles was 30.3%.

  The average particle diameter of the (meth) acrylic acid alkyl ester polymer (a-1-2) particles in this aqueous dispersion was 0.110 μm. The weight average molecular weight (Mw) of the (meth) acrylic acid alkyl ester polymer (a-1-2) measured by gel permeation chromatography was 2,700,000. Moreover, the glass transition temperature (Tg) of the (meth) acrylic-acid alkylester type polymer (a-1-2) was 56 degreeC by the calculated value.

  100 parts of pure water was added to a vessel equipped with a stirrer and a thermocouple, and the temperature was raised to 65 ° C. When the internal temperature reached 65 ° C., 130 parts by mass of an aqueous solution in which 2.5 parts by mass of aluminum sulfate was dissolved and 100 parts of a (meth) acrylic acid alkyl ester-based polymer (a-1-2) dispersion were added. It was dripped over 20 minutes and the solid substance was deposited. Next, the temperature inside was raised to 95 ° C., and this state was maintained for 20 minutes. Then, this precipitate was separated, filtered, washed and dried to obtain a thermoplastic resin modifier (A-16).

<Examples 1-6, Comparative Examples 1-8>
The evaluation results of fluidity are shown in Table 1. The polytetrafluoroethylene powder (PTFE powder) used in Comparative Example 1 is Fullon CD1 (trade name) manufactured by Asahi Glass Fluoropolymers Co., Ltd.

<Examples 7 to 12 and Comparative Examples 9 to 16>
The evaluation results for storage stability are shown in Table 2. The polytetrafluoroethylene powder (PTFE powder) used in Comparative Example 9 is Fullon CD1 (trade name) manufactured by Asahi Glass Fluoropolymers Co., Ltd.

＜実施例１３〜１８、比較例１７〜２４＞
実施例７〜１２、比較例９〜１６にて得られた６０％破砕量に到達した時点の粉体を、ポリカーボネート樹脂と表３に示した各割合（質量比）でヘンシェルミキサーにて混合、作製した配合を、シリンダー温度２８０℃に設定した同方向二軸押出機（ＪＳＷ（株）社製ＴＥＸ−３０α（商品名））で賦形し、ペレットを作製した。次いで、このペレットを用いてシリンダー温度２８０℃、金型温度８０℃に設定した射出成形機（山城精機製作所（株）社製ＳＡＶ−６０（商品名））により射出成形を行って、ＵＬ９４規格に従った厚み１．６ｍｍの垂直型燃焼試験用試験片を得た。この試験片を用いた分散性評価結果を表３に示す。

<Examples 13-18, Comparative Examples 17-24>
The powder when reaching the 60% crushed amount obtained in Examples 7 to 12 and Comparative Examples 9 to 16 was mixed with a polycarbonate resin at a ratio (mass ratio) shown in Table 3 with a Henschel mixer, The prepared blend was shaped with a same-direction twin-screw extruder (TEX-30α (trade name) manufactured by JSW Co., Ltd.) set at a cylinder temperature of 280 ° C. to prepare pellets. Next, this pellet was used for injection molding by an injection molding machine (Yamagi Seiki Seisakusho SAV-60 (trade name)) set to a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. Accordingly, a test piece for vertical combustion test having a thickness of 1.6 mm was obtained. Table 3 shows the results of evaluation of dispersibility using this test piece.

・「ＰＣ樹脂」：ポリカーボネート樹脂、三菱エンジニアリングプラスチックス
（株）社製、商品名ユーピロンＳ−２０００Ｆ
・「ＰＴＦＥパウダー」：ポリテトラフルオロエチレン、旭硝子フロロポリマーズ（株）社製、商品名アフロンＣＤ１
＜実施例１９〜２４、比較例２５〜３３＞
表４に示す各成分を各割合（質量比）で混合し、シリンダー温度２８０℃に設定した同方向二軸押出機（ＪＳＷ（株）社製ＴＥＸ−３０α（商品名））で賦形し、ペレットを作製した。次いで、このペレットを用いて、燃焼性試験用はシリンダー温度２８０℃、金型温度８０℃に設定した射出成形機（山城精機製作所（株）社製ＳＡＶ−６０（商品名））、物性評価用はシリンダー温度２８０℃、金型温度８０℃に設定した射出成形機（名機製作所（株）社製Ｍ−１００ＡＩＩ−ＤＭ（商品名））により射出成形を行って、それぞれ試験片を得た。

"PC resin": Polycarbonate resin, manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name Iupilon S-2000F
"PTFE powder": Polytetrafluoroethylene, manufactured by Asahi Glass Fluoropolymers, Inc., trade name Aflon CD1
<Examples 19 to 24, Comparative Examples 25 to 33>
Each component shown in Table 4 was mixed at each ratio (mass ratio), and shaped with the same-direction twin screw extruder (TEX-30α (trade name) manufactured by JSW Co., Ltd.) set at a cylinder temperature of 280 ° C. A pellet was prepared. Next, using this pellet, for the flammability test, an injection molding machine (SAV-60 (trade name) manufactured by Yamashiro Seiki Seisakusho Co., Ltd.) set at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C., for physical property evaluation Was injection-molded with an injection molding machine (M-100AII-DM (trade name) manufactured by Meiki Seisakusho Co., Ltd.) set at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. to obtain test pieces.

<Examples 25-30, Comparative Examples 34-42>
Each component shown in Table 5 was mixed at each ratio (mass ratio), and shaped with the same-direction twin screw extruder (TEX-30α (trade name) manufactured by JSW Corporation) set at a cylinder temperature of 280 ° C. A pellet was prepared. Next, using this pellet, for the flammability test, an injection molding machine (SAV-60 (trade name) manufactured by Yamashiro Seiki Seisakusho Co., Ltd.) set at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C., for physical property evaluation Was injection-molded with an injection molding machine (M-100AII-DM (trade name) manufactured by Meiki Seisakusho Co., Ltd.) set at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. to obtain test pieces.

<Examples 31-36, Comparative Examples 43-51>
Each component shown in Table 6 was mixed at each ratio (mass ratio), and shaped with the same-direction twin-screw extruder (TEX-30α (trade name) manufactured by JSW Co., Ltd.) set at a cylinder temperature of 280 ° C. A pellet was prepared. Next, using this pellet, for the flammability test, an injection molding machine (SAV-60 (trade name) manufactured by Yamashiro Seiki Seisakusho Co., Ltd.) set at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C., for physical property evaluation Was injection-molded with an injection molding machine (M-100AII-DM (trade name) manufactured by Meiki Seisakusho Co., Ltd.) set at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. to obtain test pieces.

<Examples 37 to 42, Comparative Examples 52 to 60>
Each component shown in Table 7 was mixed at each ratio (mass ratio) and shaped with the same-direction twin screw extruder (TEX-30α (trade name) manufactured by JSW Co., Ltd.) set at a cylinder temperature of 260 ° C. A pellet was prepared. Next, using this pellet, for the flammability test, an injection molding machine (SAV-60 (trade name) manufactured by Yamashiro Seiki Co., Ltd.) set at a cylinder temperature of 260 ° C. and a mold temperature of 60 ° C., for physical property evaluation. Were injection molded with an injection molding machine (M-100AII-DM (trade name) manufactured by Meiki Seisakusho Co., Ltd.) set at a cylinder temperature of 260 ° C. and a mold temperature of 60 ° C. to obtain test pieces, respectively.

<Examples 43 to 48, Comparative Examples 61 to 69>
Each component shown in Table 8 was mixed at each ratio (mass ratio), and shaped with the same-direction twin screw extruder (TEX-30α (trade name) manufactured by JSW Co., Ltd.) set at a cylinder temperature of 260 ° C. A pellet was prepared. Next, using this pellet, for the flammability test, an injection molding machine (SAV-60 (trade name) manufactured by Yamashiro Seiki Co., Ltd.) set at a cylinder temperature of 260 ° C. and a mold temperature of 60 ° C., for physical property evaluation. Were injection molded with an injection molding machine (M-100AII-DM (trade name) manufactured by Meiki Seisakusho Co., Ltd.) set at a cylinder temperature of 260 ° C. and a mold temperature of 60 ° C. to obtain test pieces, respectively.

<Examples 49 to 54, Comparative Examples 70 to 78>
Each component shown in Table 9 was mixed at each ratio (mass ratio) and shaped with a same-direction twin-screw extruder (TEX-30α (trade name) manufactured by JSW Co., Ltd.) set at a cylinder temperature of 250 ° C. A pellet was prepared. Next, using this pellet, for the flammability test, an injection molding machine (SAV-60 (trade name) manufactured by Yamashiro Seiki Co., Ltd.) set at a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C., for physical property evaluation. Were injection molded with an injection molding machine (M-100AII-DM (trade name) manufactured by Meiki Seisakusho Co., Ltd.) set at a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. to obtain test pieces, respectively.

<Examples 55-60, Comparative Examples 79-87>
Each component shown in Table 10 was mixed at each ratio (mass ratio), and shaped with the same-direction twin screw extruder (TEX-30α (trade name) manufactured by JSW Co., Ltd.) set at a cylinder temperature of 250 ° C. A pellet was prepared. Next, using this pellet, for the flammability test, an injection molding machine (SAV-60 (trade name) manufactured by Yamashiro Seiki Co., Ltd.) set at a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C., for physical property evaluation. Were injection molded with an injection molding machine (M-100AII-DM (trade name) manufactured by Meiki Seisakusho Co., Ltd.) set at a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. to obtain test pieces, respectively.

<Examples 61-66, Comparative Examples 88-96>
Each component shown in Table 11 was mixed at each ratio (mass ratio) and shaped with a same-direction twin-screw extruder (TEX-30α (trade name) manufactured by JSW Corporation) set at a cylinder temperature of 250 ° C. A pellet was prepared. Next, using this pellet, for the flammability test, an injection molding machine (SAV-60 (trade name) manufactured by Yamashiro Seiki Co., Ltd.) set at a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C., for physical property evaluation. Were injection molded with an injection molding machine (M-100AII-DM (trade name) manufactured by Meiki Seisakusho Co., Ltd.) set at a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. to obtain test pieces, respectively.

<Examples 67 to 72, Comparative Examples 97 to 105>
Each component shown in Table 12 was mixed at each ratio (mass ratio), and shaped with the same-direction twin screw extruder (TEX-30α (trade name) manufactured by JSW Co., Ltd.) set at a cylinder temperature of 250 ° C. A pellet was prepared. Next, using this pellet, for the flammability test, an injection molding machine (SAV-60 (trade name) manufactured by Yamashiro Seiki Co., Ltd.) set at a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C., for physical property evaluation. Were injection molded with an injection molding machine (M-100AII-DM (trade name) manufactured by Meiki Seisakusho Co., Ltd.) set at a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. to obtain test pieces, respectively.

<Examples 73 to 78, Comparative Examples 106 to 114>
Each component shown in Table 13 was mixed at each ratio (mass ratio), and shaped with a unidirectional twin-screw extruder (TEX-30α (trade name) manufactured by JSW Corporation) set at a cylinder temperature of 250 ° C. A pellet was prepared. Next, using this pellet, for the flammability test, an injection molding machine (SAV-60 (trade name) manufactured by Yamashiro Seiki Co., Ltd.) set at a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C., for physical property evaluation. Were injection molded with an injection molding machine (M-100AII-DM (trade name) manufactured by Meiki Seisakusho Co., Ltd.) set at a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. to obtain test pieces, respectively.

<Examples 79 to 84, Comparative Examples 115 to 123>
Each component shown in Table 14 was mixed at each ratio (mass ratio), and shaped with the same-direction twin screw extruder (TEX-30α (trade name) manufactured by JSW Co., Ltd.) set at a cylinder temperature of 220 ° C. A pellet was prepared. Next, using this pellet, the combustibility test is an injection molding machine (SAV-60 (trade name) manufactured by Yamashiro Seiki Co., Ltd.) set at a cylinder temperature of 220 ° C. and a mold temperature of 60 ° C., for physical property evaluation. Were injection molded with an injection molding machine (M-100AII-DM (trade name) manufactured by Meiki Seisakusho Co., Ltd.) set at a cylinder temperature of 220 ° C. and a mold temperature of 60 ° C. to obtain test pieces.

<Examples 85-90 and Comparative Examples 124-132>
Each component shown in Table 15 was mixed at each ratio (mass ratio), and shaped with the same-direction twin screw extruder (TEX-30α (trade name) manufactured by JSW Corporation) set at a cylinder temperature of 280 ° C. A pellet was prepared. Next, using this pellet, for the flammability test, an injection molding machine (SAV-60 (trade name) manufactured by Yamashiro Seiki Seisakusho Co., Ltd.) set at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C., for physical property evaluation Was injection-molded with an injection molding machine (M-100AII-DM (trade name) manufactured by Meiki Seisakusho Co., Ltd.) set at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. to obtain test pieces.

<Examples 91-96, Comparative Examples 133-141>
Each component shown in Table 16 was mixed at each ratio (mass ratio), and shaped with the same-direction twin screw extruder (TEX-30α (trade name) manufactured by JSW Corporation) set at a cylinder temperature of 240 ° C. A pellet was prepared. Next, using this pellet, for the flammability test, an injection molding machine (SAV-60 (trade name) manufactured by Yamashiro Seiki Co., Ltd.) set at a cylinder temperature of 230 ° C. and a mold temperature of 80 ° C., for physical property evaluation. Were injection molded by an injection molding machine (M-100AII-DM (trade name) manufactured by Meiki Seisakusho Co., Ltd.) set at a cylinder temperature of 230 ° C. and a mold temperature of 80 ° C. to obtain test pieces.

<Examples 97 to 102, Comparative Examples 142 to 150>
Each component shown in Table 17 was mixed at each ratio (mass ratio), and shaped with a same-direction twin-screw extruder (TEX-30α (trade name) manufactured by JSW Co., Ltd.) set at a cylinder temperature of 240 ° C. A pellet was prepared. Next, using this pellet, for the flammability test, an injection molding machine (SAV-60 (trade name) manufactured by Yamashiro Seiki Co., Ltd.) set at a cylinder temperature of 230 ° C. and a mold temperature of 80 ° C., for physical property evaluation. Were injection molded by an injection molding machine (M-100AII-DM (trade name) manufactured by Meiki Seisakusho Co., Ltd.) set at a cylinder temperature of 230 ° C. and a mold temperature of 80 ° C. to obtain test pieces.

<Examples 103 to 108, Comparative Examples 151 to 159>
Each component shown in Table 18 was mixed at each ratio (mass ratio), and shaped with a same-direction twin-screw extruder (TEX-30α (trade name) manufactured by JSW Co., Ltd.) set at a cylinder temperature of 240 ° C. A pellet was prepared. Next, using this pellet, for the flammability test, an injection molding machine (SAV-60 (trade name) manufactured by Yamashiro Seiki Co., Ltd.) set at a cylinder temperature of 240 ° C. and a mold temperature of 60 ° C., for physical property evaluation Were injection molded by an injection molding machine (M-100AII-DM (trade name) manufactured by Meiki Seisakusho Co., Ltd.) set at a cylinder temperature of 240 ° C. and a mold temperature of 60 ° C. to obtain test pieces.

<Examples 109 to 114, Comparative Examples 160 to 168>
Each component shown in Table 19 was mixed at each ratio (mass ratio), and shaped with the same-direction twin screw extruder (TEX-30α (trade name) manufactured by JSW Co., Ltd.) set at a cylinder temperature of 230 ° C. A pellet was prepared. Next, using this pellet, for the flammability test, an injection molding machine (SAV-60 (trade name) manufactured by Yamashiro Seiki Seisakusho Co., Ltd.) set at a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C., for physical property evaluation Were injection molded with an injection molding machine (M-100AII-DM (trade name) manufactured by Meiki Seisakusho Co., Ltd.) set at a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C. to obtain test pieces, respectively.

<Examples 115 to 120, Comparative Examples 169 to 177>
Each component shown in Table 20 was mixed at each ratio (mass ratio) and shaped with a same-direction twin-screw extruder (TEX-30α (trade name) manufactured by JSW Co., Ltd.) set at a cylinder temperature of 230 ° C. A pellet was prepared. Next, using this pellet, for the flammability test, an injection molding machine (SAV-60 (trade name) manufactured by Yamashiro Seiki Seisakusho Co., Ltd.) set at a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C., for physical property evaluation Were injection molded with an injection molding machine (M-100AII-DM (trade name) manufactured by Meiki Seisakusho Co., Ltd.) set at a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C. to obtain test pieces, respectively.

  Tables 4 to 20 show the results of performing a vertical combustion test, Izod impact strength, tensile strength and tensile elongation according to UL-94 standards from the obtained test pieces.

表４〜表２０中の配合成分として具体的には、以下のものを使用した。
・「ＰＣ樹脂」：ポリカーボネート樹脂、三菱エンジニアリングプラスチックス
（株）社製、商品名ユーピロンＳ−２０００Ｆ
・「ＰＢＴ樹脂」：ポリブチレンテレフタレート樹脂、三菱レイヨン（株）社製、商品名タフペットＮ１０００
・「ＰＰＥ樹脂」：ポリフェニレンエーテル樹脂、用いたポリフェニレンエーテル樹脂は、ポリ（２，６−ジメチル−１，４−フェニレン）エーテルであり、還元粘度は２５℃における０．１％クロロホルム溶液で、ウベローデ型粘度計にて測定したところ、０．５９であった。
・「ＰＳ樹脂」：ポリスチレン樹脂、日本ポリスチレン（株）社製、商品名Ｇ４４０Ｋ
・「Ｎｙ６樹脂」：ポリアミド樹脂、宇部興産（株）社製、商品名ＵＢＥナイロン１０１３Ｂ
・「ＰＰ樹脂」：ポリプロピレン樹脂、日本ポリケム（株）社製、商品名ノバテックＰＰ ＢＣ６
・「ＰＥ樹脂」：ポリエチレン樹脂、日本ポリケム（株）社製、商品名ノバテックＬＤ ＬＣ５２５
・「グラフト共重合体１」：ＡＢＳグラフト共重合体、三菱レイヨン（株）社製、商品名Ｒ−８０
・「グラフト共重合体２」：アクリロニトリル−ブチルアクリレート−スチレン）グラフト共重合体、三菱レイヨン（株）社製、商品名ＭＵＸ−８０
・「グラフト共重合体３」：アクリロニトリル−ブチルアクリレート−シリコーン）グラフト共重合体、三菱レイヨン（株）社製、商品名ＲＫ−２００
・「ビニル系共重合体」：アクリロニトリル-スチレン共重合体、三菱レイヨン（株）社製、商品名ＡＰ−２０
・「難燃剤１」：トリフェニルホスフェート、大八化学工業（株）社製、商品名
ＴＰＰ
・「難燃剤２」：テトラビスフェノールＡのカーボネートオリゴマー、帝人化成（株）社製、商品名ファイヤーガードＦＧ−７５００
・「難燃剤３」：パーフルオロブタンスルホン酸ナトリウム、大日本インキ化学工業（株）社製、商品名メガファックＦ１１４
・「難燃剤４」：ハロゲン化エポキシオリゴマー、Ｂｒｏｍｉｎｅ Ｃｏｍｐｏｕｎｄｓ Ｌｔｄ．製、商品名Ｆ２４００
・「難燃剤５」：赤燐、リン化学工業（株）製、商品名ノーバレッド１２００
・「難燃剤６」：水酸化マグネシウム、協和化学工業（株）製、商品名キスマ５Ａ
・「難燃助剤」：三酸化アンチモン、日本精鉱（株）社製、商品名パトックスＭ
・「ＰＴＦＥパウダー１」：ポリテトラフルオロエチレン、旭硝子（株）社製、
商品名アフロンＰＴＦＥ ＣＤ−１。
・「ＰＴＦＥパウダー２」：ポリテトラフルオロエチレン、ダイキン（株）社製、商品名Ｆ２０１Ｌ。

Specifically, the following components were used as the blending components in Tables 4 to 20.
"PC resin": Polycarbonate resin, manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name Iupilon S-2000F
"PBT resin": Polybutylene terephthalate resin, manufactured by Mitsubishi Rayon Co., Ltd., trade name Toughpet N1000
"PPE resin": polyphenylene ether resin, the polyphenylene ether resin used is poly (2,6-dimethyl-1,4-phenylene) ether, and the reduced viscosity is 0.1% chloroform solution at 25 ° C. It was 0.59 when measured with a type viscometer.
"PS resin": Polystyrene resin, manufactured by Nippon Polystyrene Co., Ltd., trade name G440K
"Ny6 resin": Polyamide resin, manufactured by Ube Industries, Ltd., trade name UBE nylon 1013B
"PP resin": polypropylene resin, manufactured by Nippon Polychem Co., Ltd., trade name Novatec PP BC6
"PE resin": Polyethylene resin, manufactured by Nippon Polychem Co., Ltd., trade name Novatec LD LC525
"Graft copolymer 1": ABS graft copolymer, manufactured by Mitsubishi Rayon Co., Ltd., trade name R-80
"" Graft copolymer 2 ": acrylonitrile-butyl acrylate-styrene) graft copolymer, manufactured by Mitsubishi Rayon Co., Ltd., trade name MUX-80
"Graft copolymer 3": acrylonitrile-butyl acrylate-silicone) graft copolymer, manufactured by Mitsubishi Rayon Co., Ltd., trade name RK-200
"Vinyl copolymer": Acrylonitrile-styrene copolymer, manufactured by Mitsubishi Rayon Co., Ltd., trade name AP-20
・ "Flame Retardant 1": Triphenyl phosphate, manufactured by Daihachi Chemical Industry Co., Ltd., trade name TPP
"Flame Retardant 2": Tetrabisphenol A carbonate oligomer, manufactured by Teijin Chemicals Ltd., trade name Fireguard FG-7500
"Flame Retardant 3": Sodium perfluorobutane sulfonate, manufactured by Dainippon Ink & Chemicals, Inc., trade name MegaFuck F114
“Flame Retardant 4”: halogenated epoxy oligomer, Bromine Compounds Ltd. Product name F2400
"Flame Retardant 5": Red phosphorus, manufactured by Phosphorus Chemical Industry Co., Ltd., trade name NOVARED 1200
"Flame retardant 6": Magnesium hydroxide, manufactured by Kyowa Chemical Industry Co., Ltd., trade name Kisuma 5A
・ "Flame retardant aid": Antimony trioxide, manufactured by Nippon Seiko Co., Ltd., trade name Patox M
"PTFE powder 1": polytetrafluoroethylene, manufactured by Asahi Glass Co., Ltd.
Product name Aflon PTFE CD-1.
"PTFE powder 2": Polytetrafluoroethylene, manufactured by Daikin Corporation, trade name F201L.

<Examples 121 to 125, Comparative Examples 178 to 187>
Composition obtained by adding the modifier for thermoplastic resin (A-6) obtained in Production Example 6 and polytetrafluoroethylene (PTFE) [addition amount: 0.3 parts of polytetrafluoroethylene with respect to 100 parts of the thermoplastic resin. The amount to be a part] and a composition to which it was not added were prepared for comparison, and bottle formation was performed with a blow molding machine having a screw diameter of 40 mm. The evaluation results are shown in Table 21.

表２１に示す各樹脂として具体的に使用した樹脂、ボトル成形条件、および評価方法を以下に記す。
・「ＡＢＳ樹脂」：三菱レイヨン（株）社製、商品名ダイヤペット３００１。成形条件：シリンダー温度（Ｃ１）１８０℃、（Ｃ２）２００℃、（Ｃ３）２００℃、ヘッド２００℃、ダイス２００℃
・「ＰＣ樹脂」：ポリカーボネート樹脂、三菱エンジニアリングプラスチックス（株）社製、商品名ノバレックス７０２２Ａ。成形条件：シリンダー温度（Ｃ１）２３０℃、（Ｃ２）２６０℃、（Ｃ３）２７０℃、ヘッド２７０℃、ダイス２８０℃
・「ＰＥＴ樹脂」：ポリエチレンテレフタレート樹脂、三菱レイヨン（株）社製、商品名ダイヤナイトＡ−２００。成形条件：シリンダー温度（Ｃ１）２８０℃、（Ｃ２）２８０℃、（Ｃ３）２８０℃、ヘッド２６０℃、ダイス２６０℃
・「ＰＳ樹脂」：ポリスチレン樹脂、日本ポリスチレン（株）社製、商品名Ｇ４４０Ｋ。成形条件：シリンダー温度（Ｃ１）１６０℃、（Ｃ２）１８０℃、（Ｃ３）２００℃、ヘッド：２００℃、ダイス：２１０℃
・「ＰＥ樹脂」：ポリエチレン樹脂、三井化学（株）社製、商品名ハイゼックス７０００Ｆ。成形条件：シリンダー温度（Ｃ１）１５０℃、（Ｃ２）１６５℃、（Ｃ３）１７５℃、ヘッド１７５℃、ダイス１７５℃
・「ＰＴＦＥパウダー」：ポリテトラフルオロエチレン、旭硝子フロロポリマーズ（株）社製、商品名アフロンＣＤ１
（ａ）「成型時のドローダウン」
成形時におけるパリソンのドローダウンを、以下の基準に従い、目視にて判定
した。
○：ダイスウェルが大きくドローダウン無し。
×：ダイスウェルが小さくドローダウン有り。
（ｂ）「ボトルの外観」
得られたボトルの外観を、以下の基準に従い、肉眼により判定した。
○：光沢が良好で、かつ肌荒れが無い。
×：光沢に乏しく、肌荒れが目立つ。

The resins, bottle molding conditions, and evaluation methods specifically used as the resins shown in Table 21 are described below.
"ABS resin": Mitsubishi Rayon Co., Ltd., trade name Diapet 3001 Molding conditions: cylinder temperature (C1) 180 ° C, (C2) 200 ° C, (C3) 200 ° C, head 200 ° C, dice 200 ° C
"PC resin": polycarbonate resin, manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name NOVAREX 7022A. Molding conditions: cylinder temperature (C1) 230 ° C, (C2) 260 ° C, (C3) 270 ° C, head 270 ° C, die 280 ° C
"PET resin": Polyethylene terephthalate resin, manufactured by Mitsubishi Rayon Co., Ltd., trade name Dianite A-200. Molding conditions: cylinder temperature (C1) 280 ° C, (C2) 280 ° C, (C3) 280 ° C, head 260 ° C, die 260 ° C
"PS resin": Polystyrene resin, manufactured by Nippon Polystyrene Co., Ltd., trade name G440K. Molding conditions: cylinder temperature (C1) 160 ° C, (C2) 180 ° C, (C3) 200 ° C, head: 200 ° C, die: 210 ° C
"PE resin": Polyethylene resin, manufactured by Mitsui Chemicals, Inc., trade name HYEX 7000F. Molding conditions: cylinder temperature (C1) 150 ° C., (C2) 165 ° C., (C3) 175 ° C., head 175 ° C., die 175 ° C.
"PTFE powder": Polytetrafluoroethylene, manufactured by Asahi Glass Fluoropolymers, Inc., trade name Aflon CD1
(A) "Drawdown during molding"
The drawdown of the parison during molding was determined visually according to the following criteria.
○: Large die swell and no drawdown.
X: Die swell is small and there is a drawdown.
(B) “Appearance of the bottle”
The appearance of the obtained bottle was determined by the naked eye according to the following criteria.
○: Good gloss and no rough skin.
X: Poor luster and rough skin are conspicuous.

<Examples 126 to 157, Comparative Examples 188 to 193>
Each component shown in Tables 22 and 23 was mixed at each ratio, and extrusion was carried out with a 50 mm single-screw extruder (trade name) manufactured by IKG Co., Ltd. set at a cylinder temperature of 230 ° C., and the width was 80 mm and the thickness was A sheet of 3 mm thermoplastic resin composition was prepared.

About the obtained sheet | seat, the following items were evaluated.
-Surface appearance: The obtained sheet was visually observed and judged according to the following criteria.
○: Rough skin, fluff, and no occurrence of irregularities considered to be a poor dispersion of PTFE.
X: Rough skin, fluff, and occurrence of irregularities that seem to be poor dispersion of PTFE.
Plate-out: Using a two-roll mill, the dirt on the roll surface during molding was observed.
○: Roll surface is not dirty △: Roll surface is slightly dirty ×: Roll surface is very dirty

表２２、２３中の配合成分として具体的には、以下のものを使用した。
・「ＰＰ樹脂１」：ポリプロピレン樹脂、日本ポリケム（株）社製、商品名ノバテックＰＰ ＢＣ０６Ｃ、成形温度：２３０℃
・「ＰＰ樹脂２」：ポリプロピレン樹脂、日本ポリケム（株）社製、商品名ノバテックＰＰ ＦＹ−６Ｃ、成形温度：２３０℃
・「ＰＥ樹脂１」：ポリエチレン樹脂、日本ポリケム（株）社製、商品名ノバテックＨＤ ＨＹ５４０、成形温度：２１０℃
・「ＰＥ樹脂２」：ポリエチレン樹脂、日本ポリケム（株）社製、商品名ノバテックＬＤ ＬＪ８０１Ｎ、成形温度：２１０℃
・「ＰＳ樹脂」：ポリスチレン樹脂、日本ポリスチレン（株）社製、商品名Ｇ４４０Ｋ、成形温度：２３０℃。
・「ＡＢＳ樹脂」：ゴム強化したアクリロニトリル／スチレン共重合体、三菱レイヨン（株）社製、商品名ダイヤペット、成形温度：２００℃。
・「ＰＥＴ樹脂」：ポリエチレンテレフタレート樹脂、三菱レイヨン（株）社製、商品名ダイヤナイトＰＡ−２００、成形温度：２５０℃。
・「生分解性樹脂」：ポリ乳酸系樹脂、島津製作所（株）社製、商品名ラクティ９４００、成形温度：２２０℃。
・「リサイクルＰＰ樹脂」：ＰＰ樹脂１を押出、賦形、粉砕のサイクルを２回繰り返したものを用いた。成形温度：２３０℃
・「バンパー粉砕品」：ＰＰ樹脂を主成分とする自動車バンパーを破砕、ペレット状にしたものである。本発明では具体例としてＴＳＯＰを用いた。成形温度：２４０℃。
・「リサイクルＰＥＴ樹脂」：分別回収された飲料用等の使用済みＰＥＴボトルからＰＥＴ以外の素材を除去したのち、弱アルカリ性水溶液および水にて洗浄してから湿式粉砕を行ったのち、比重差を利用してＰＥＴ樹脂以外の樹脂や金属片を分離する事によって得られたＰＥＴボトルの粉砕品。成形温度：２５０℃。
・「ＰＴＦＥパウダー」：ポリテトラフルオロエチレン、旭硝子フロロポリマーズ（株）社製、商品名アフロンＣＤ１
＜実施例１５８〜１７４、比較例１９４〜１９６＞
表２４に示す各成分を各割合で混合し、５０ｍｍ単軸押出機（ＩＫＧ（株）社製（商品名））にて押出発泡成形を行い、幅８０ｍｍ、厚み５ｍｍの発泡体シートを作製した。

Specifically, the following components were used as the formulation components in Tables 22 and 23.
"PP resin 1": polypropylene resin, manufactured by Nippon Polychem Co., Ltd., trade name Novatec PP BC06C, molding temperature: 230 ° C
"PP resin 2": polypropylene resin, manufactured by Nippon Polychem Co., Ltd., trade name Novatec PP FY-6C, molding temperature: 230 ° C
"PE resin 1": polyethylene resin, manufactured by Nippon Polychem Co., Ltd., trade name Novatec HD HY540, molding temperature: 210 ° C
"PE resin 2": polyethylene resin, manufactured by Nippon Polychem Co., Ltd., trade name Novatec LD LJ801N, molding temperature: 210 ° C
“PS resin”: polystyrene resin, manufactured by Nippon Polystyrene Co., Ltd., trade name G440K, molding temperature: 230 ° C.
“ABS resin”: rubber-reinforced acrylonitrile / styrene copolymer, manufactured by Mitsubishi Rayon Co., Ltd., trade name Diapet, molding temperature: 200 ° C.
“PET resin”: polyethylene terephthalate resin, manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dianite PA-200, molding temperature: 250 ° C.
“Biodegradable resin”: polylactic acid resin, manufactured by Shimadzu Corporation, trade name Lacty 9400, molding temperature: 220 ° C.
“Recycled PP resin”: PP resin 1 was used by repeating extrusion, shaping, and grinding cycles twice. Molding temperature: 230 ° C
“Bumper pulverized product”: A bumper of a car bumper mainly composed of PP resin. In the present invention, TSOP is used as a specific example. Molding temperature: 240 ° C.
・ "Recycled PET resin": After removing materials other than PET from used PET bottles for beverages that have been separated and collected, after washing with weak alkaline aqueous solution and water, wet grinding, the difference in specific gravity is A pulverized product of PET bottles obtained by separating resin and metal pieces other than PET resin. Molding temperature: 250 ° C.
"PTFE powder": Polytetrafluoroethylene, manufactured by Asahi Glass Fluoropolymers, Inc., trade name Aflon CD1
<Examples 158 to 174, Comparative Examples 194 to 196>
Each component shown in Table 24 was mixed at each ratio, and extrusion foaming was performed with a 50 mm single screw extruder (product name, manufactured by IKG Corporation) to produce a foam sheet having a width of 80 mm and a thickness of 5 mm. .

About the obtained foam sheet, the following items were evaluated.
-Foamed cell state in the molded product: The cross section of the foam sheet was observed and judged according to the following criteria.
○: The ratio of the cell size between the vicinity of the surface of the sheet and the central portion is less than twice. ×: The ratio of the cell size between the vicinity of the surface of the sheet and the central portion exceeds twice. Surface appearance: The surface of the foam sheet was visually observed and judged according to the following criteria.
○: No trace of bubble breakage is observed on the surface of the sheet, and the surface is smooth.
X: Traces of bubble breakage are observed on the surface of the sheet, and the surface is uneven.

表２４中の配合成分として具体的には以下のものを使用した。
・「ＰＰ樹脂」：ポリプロピレン樹脂、日本ポリケム（株）社製、商品名ノバテックＰＰ ＦＹ−６Ｃ、成形温度：２３０℃
・「ＰＥ樹脂１」：ポリエチレン樹脂、日本ポリケム（株）社製、商品名ノバテックＨＤ ＨＪ５８０、成形温度：２１０℃
・「ＰＥ樹脂２」：ポリエチレン樹脂、日本ポリケム（株）社製、商品名ノバテックＬＤ ＬＣ７２０、成形温度：２１０℃
・「ＰＥ樹脂３」：ポリエチレン樹脂、日本ポリケム（株）社製、商品名ノバテックＬＬ ＵＪ３７０、成形温度：２１０℃
・「ＰＥＴ樹脂」：ポリエチレンテレフタレート樹脂、三菱レイヨン（株）社製、商品名ダイヤナイトＫＲ−５６０、成形温度：２５０℃
・「リサイクルＰＰ樹脂」：ＰＰ樹脂１を押出、賦形、粉砕のサイクルを２回繰り返したものを用いた。成形温度：２３０℃
・「リサイクルＰＥＴ樹脂」：分別回収された飲料用等の使用済みＰＥＴボトルからＰＥＴ以外の素材を除去したのち、弱アルカリ性水溶液および水にて洗浄してから湿式粉砕を行ったのち、比重差を利用してＰＥＴ樹脂以外の樹脂や金属片を分離する事によって得られたＰＥＴボトルの粉砕品。成形温度：２５０℃。
・「ＰＳ樹脂」：ポリスチレン樹脂、日本ポリスチレン（株）社製、商品名Ｇ４４０Ｋ、成形温度：２３０℃。
・「ＡＢＳ樹脂」：ゴム強化したアクリロニトリル／スチレン共重合体、三菱レイヨン（株）社製、商品名ダイヤペット３００１、成形温度：２００℃。
・「ＰＴＦＥパウダー」：ポリテトラフルオロエチレン、旭硝子フロロポリマーズ（株）社製、商品名アフロンＣＤ１

Specifically, the following ingredients were used as blending components in Table 24.
"PP resin": polypropylene resin, manufactured by Nippon Polychem Co., Ltd., trade name Novatec PP FY-6C, molding temperature: 230 ° C
"PE resin 1": Polyethylene resin, manufactured by Nippon Polychem Co., Ltd., trade name Novatec HD HJ580, molding temperature: 210 ° C
"PE resin 2": polyethylene resin, manufactured by Nippon Polychem Co., Ltd., trade name Novatec LD LC720, molding temperature: 210 ° C
"PE resin 3": polyethylene resin, manufactured by Nippon Polychem Co., Ltd., trade name Novatec LL UJ370, molding temperature: 210 ° C
"PET resin": polyethylene terephthalate resin, manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dianite KR-560, molding temperature: 250 ° C
“Recycled PP resin”: PP resin 1 was used by repeating extrusion, shaping, and grinding cycles twice. Molding temperature: 230 ° C
・ "Recycled PET resin": After removing materials other than PET from used PET bottles for beverages that have been separated and collected, after washing with weak alkaline aqueous solution and water, wet grinding, the difference in specific gravity is A pulverized product of PET bottles obtained by separating resin and metal pieces other than PET resin. Molding temperature: 250 ° C.
“PS resin”: polystyrene resin, manufactured by Nippon Polystyrene Co., Ltd., trade name G440K, molding temperature: 230 ° C.
“ABS resin”: rubber-reinforced acrylonitrile / styrene copolymer, manufactured by Mitsubishi Rayon Co., Ltd., trade name Diapet 3001, molding temperature: 200 ° C.
"PTFE powder": Polytetrafluoroethylene, manufactured by Asahi Glass Fluoropolymers, Inc., trade name Aflon CD1

Claims (34)

  A monomer component containing polytetrafluoroethylene (a-1-1), methyl methacrylate, and a (meth) acrylic acid alkyl ester having a C 1-4 alkyl group excluding methyl methacrylate is used in combination. 100 parts by mass of polymerized polytetrafluoroethylene-containing polymer (a-1) made of (meth) acrylic acid alkyl ester polymer (a-1-2) having a glass transition temperature (Tg) of 40 to 85 ° C. A thermoplastic resin modifier (A) containing 0.01 to 10 parts by mass of an inorganic additive (a-2).   Obtained by forming the (meth) acrylic acid alkyl ester-based polymer (a-1-2) particles by emulsion polymerization in an aqueous dispersion in which the polytetrafluoroethylene (a-1-1) particles are dispersed. The thermoplastic resin according to claim 1, obtained by blending the inorganic additive (a-2) with a polytetrafluoroethylene-containing polymer (a-1) obtained by coagulating or spray-drying the solid content of the mixed aqueous dispersion. Modifier (A).   An aqueous dispersion in which the (meth) acrylic acid alkyl ester polymer (a-1-2) particles are formed by emulsion polymerization, and an aqueous dispersion in which the polytetrafluoroethylene (a-1-1) particles are dispersed. And the inorganic additive (a-2) is blended with the polytetrafluoroethylene-containing polymer (a-1) obtained by coagulating or spray-drying the solid content of the resulting mixed aqueous dispersion. The modifier for thermoplastic resins according to 1, (A).   The average particle diameter in the aqueous dispersion of the (meth) acrylic acid alkyl ester polymer (a-1-2) is 0.05 to 1.0 μm, and is measured by gel permeation chromatography ( The modifier for thermoplastic resins (A) according to any one of claims 1 to 3, wherein the weight average molecular weight of the (meth) acrylic acid alkyl ester polymer is 20,000 to 5,000,000.   The content of the polytetrafluoroethylene (a-1-1) is the sum of the polytetrafluoroethylene (a-1-1) and the (meth) acrylic acid alkyl ester polymer (a-1-2). It is 0.01-70 mass parts when it is set as 100 mass parts, The modifier (A) for thermoplastic resins as described in any one of Claims 1-4.   The inorganic additive (a-2) is calcium carbonate, talc, magnesium carbonate, mica, kaolin, calcium sulfate, barium sulfate, aluminum hydroxide, magnesium hydroxide, silica, clay, zeolite, talc, wollastonite, The thermoplastic resin modifier (A) according to any one of claims 1 to 5, which is at least one selected from the group consisting of glass, graphite, fibers, powders or beads.   A monomer component containing polytetrafluoroethylene (a-1-1), methyl methacrylate, and a (meth) acrylic acid alkyl ester having a C 1-4 alkyl group excluding methyl methacrylate is used in combination. 100 parts by mass of a polytetrafluoroethylene-containing polymer (a-1) comprising a polymerized (meth) acrylic acid alkyl ester polymer (a-1-2) having a polymerized glass transition temperature (Tg) of 40 to 85 ° C .; The modifier for thermoplastic resins (A) containing 0.01-10 mass parts of organic type hard polymers (a-3).   Obtained by forming the (meth) acrylic acid alkyl ester-based polymer (a-1-2) particles by emulsion polymerization in an aqueous dispersion in which the polytetrafluoroethylene (a-1-1) particles are dispersed. Obtained by adding an aqueous dispersion in which the organic hard polymer (a-3) particles are dispersed to a slurry of a polytetrafluoroethylene-containing polymer (a-1) obtained by coagulating the solid content of the mixed aqueous dispersion. The modifier for thermoplastic resins (A) according to claim 7.   An aqueous dispersion in which the (meth) acrylic acid alkyl ester polymer (a-1-2) particles are formed by emulsion polymerization, and an aqueous dispersion in which the polytetrafluoroethylene (a-1-1) particles are dispersed. Aqueous dispersion in which the organic hard polymer (a-3) particles are dispersed in a slurry of polytetrafluoroethylene-containing polymer (a-1) in which the solid content of the resulting mixed aqueous dispersion is coagulated. The modifier for thermoplastic resins (A) according to claim 7, obtained by adding a liquid.   Obtained by forming the (meth) acrylic acid alkyl ester-based polymer (a-1-2) particles by emulsion polymerization in an aqueous dispersion in which the polytetrafluoroethylene (a-1-1) particles are dispersed. The thermoplastic resin modifier (A) according to claim 7, which is obtained by mixing the mixed aqueous dispersion and the aqueous dispersion in which the organic hard polymer (a-3) particles are dispersed and then spray drying.   Obtained by forming the (meth) acrylic acid alkyl ester-based polymer (a-1-2) particles by emulsion polymerization in an aqueous dispersion in which the polytetrafluoroethylene (a-1-1) particles are dispersed. The thermoplastic resin modifier (A) according to claim 7, which is obtained by simultaneously spray-drying the mixed aqueous dispersion and the aqueous dispersion in which the organic hard polymer (a-3) particles are dispersed.   An aqueous dispersion in which the (meth) acrylic acid alkyl ester polymer (a-1-2) particles are formed by emulsion polymerization, and an aqueous dispersion in which the polytetrafluoroethylene (a-1-1) particles are dispersed. And the resulting mixed aqueous dispersion and the aqueous dispersion in which the organic hard polymer (a-3) particles are dispersed are mixed and then spray-dried to obtain the thermoplastic resin for thermoplastic resin according to claim 7. Modifier (A).   An aqueous dispersion in which the (meth) acrylic acid alkyl ester polymer (a-1-2) particles are formed by emulsion polymerization, and an aqueous dispersion in which the polytetrafluoroethylene (a-1-1) particles are dispersed. And the resulting mixed aqueous dispersion and the aqueous dispersion in which the organic hard polymer (a-3) particles are dispersed are spray-dried simultaneously to modify the thermoplastic resin according to claim 7. Agent (A).   The average particle diameter in the aqueous dispersion of the (meth) acrylic acid alkyl ester-based polymer (a-1-2) is 0.05 to 1.0 μm, and is measured by gel permeation chromatography ( The modifier for thermoplastic resins (A) according to any one of claims 7 to 13, wherein the weight average molecular weight of the (meth) acrylic acid alkyl ester polymer is 20,000 to 5,000,000.   The content of the polytetrafluoroethylene (a-1-1) is the sum of the polytetrafluoroethylene (a-1-1) and the (meth) acrylic acid alkyl ester polymer (a-1-2). The thermoplastic resin modifier (A) according to any one of claims 7 to 14, which is 0.01 to 70 parts by mass when defined as 100 parts by mass.   The organic hard polymer (a-3) is a hard thermoplastic polymer having a glass transition temperature (Tg) of 50 to 98 ° C obtained by emulsion polymerization of one or more vinyl monomers. Item 15. The thermoplastic resin modifier (A) according to any one of Items 7 to 15.   The thermoplastic resin modifier (A) according to claim 16, wherein the vinyl monomer is a monomer selected from a C1-C4 (meth) acrylic acid alkyl ester and an aromatic alkenyl compound.   A monomer component containing polytetrafluoroethylene (a-1-1), methyl methacrylate, and a (meth) acrylic acid alkyl ester having a C 1-4 alkyl group excluding methyl methacrylate is used in combination. 100 parts by mass of a polytetrafluoroethylene-containing polymer (a-1) comprising a polymerized (meth) acrylic acid alkyl ester polymer (a-1-2) having a polymerized glass transition temperature (Tg) of 40 to 85 ° C .; A thermoplastic resin modifier (A) comprising 0.01 to 10 parts by mass of the inorganic additive (a-2) and the organic hard polymer (a-3) in total.   Obtained by forming the (meth) acrylic acid alkyl ester-based polymer (a-1-2) particles by emulsion polymerization in an aqueous dispersion in which the polytetrafluoroethylene (a-1-1) particles are dispersed. Obtained by mixing an aqueous dispersion in which the organic hard polymer (a-3) particles are dispersed in a slurry of a polytetrafluoroethylene-containing polymer (a-1) obtained by coagulating the solid content of the mixed aqueous dispersion. The thermoplastic resin modifier (A) according to claim 18, obtained by blending the inorganic additive (a-2) with a polytetrafluoroethylene-containing polymer (a-1 ').   An aqueous dispersion in which the (meth) acrylic acid alkyl ester polymer (a-1-2) particles are formed by emulsion polymerization, and an aqueous dispersion in which the polytetrafluoroethylene (a-1-1) particles are dispersed. And the aqueous dispersion of the organic hard polymer (a-3) particles to a slurry of the polytetrafluoroethylene-containing polymer (a-1) obtained by coagulating the solid content of the resulting mixed aqueous dispersion. The modifier for thermoplastic resins (A) according to claim 18, which is obtained by mixing and blending the resulting polytetrafluoroethylene-containing polymer (a-1 ') with the inorganic additive (a-2).   Obtained by forming the (meth) acrylic acid alkyl ester-based polymer (a-1-2) particles by emulsion polymerization in an aqueous dispersion in which the polytetrafluoroethylene (a-1-1) particles are dispersed. The mixed aqueous dispersion and the aqueous dispersion in which the organic hard polymer (a-3) particles are dispersed are mixed and then spray-dried, and an inorganic additive is added to the resulting polytetrafluoroethylene-containing polymer (a-1 ′). The modifier (A) for thermoplastic resins according to claim 18, obtained by blending (a-2).   Obtained by forming the (meth) acrylic acid alkyl ester-based polymer (a-1-2) particles by emulsion polymerization in an aqueous dispersion in which the polytetrafluoroethylene (a-1-1) particles are dispersed. The mixed aqueous dispersion and the aqueous dispersion in which the organic hard polymer (a-3) particles are dispersed are simultaneously spray-dried, and the resulting polytetrafluoroethylene-containing polymer (a-1 ′) is added with an inorganic additive (a The modifier for thermoplastic resins (A) according to claim 18, obtained by blending -2).   An aqueous dispersion in which the (meth) acrylic acid alkyl ester polymer (a-1-2) particles are formed by emulsion polymerization, and an aqueous dispersion in which the polytetrafluoroethylene (a-1-1) particles are dispersed. And the resulting mixed aqueous dispersion and the aqueous dispersion in which the organic hard polymer (a-3) particles are dispersed are mixed and then spray-dried, and the resulting polytetrafluoroethylene-containing polymer (a-1) is mixed. The modifier for thermoplastic resins (A) according to claim 18, obtained by blending an inorganic additive (a-2) with ').   An aqueous dispersion in which the (meth) acrylic acid alkyl ester polymer (a-1-2) particles are formed by emulsion polymerization, and an aqueous dispersion in which the polytetrafluoroethylene (a-1-1) particles are dispersed. And the resulting mixed aqueous dispersion and the aqueous dispersion in which the organic hard polymer (a-3) particles are dispersed are simultaneously spray-dried, and the resulting polytetrafluoroethylene-containing polymer (a-1 ′) The modifier for thermoplastic resins (A) according to claim 18, which is obtained by blending an inorganic additive (a-2) with AA.   The average particle diameter in the aqueous dispersion of the (meth) acrylic acid alkyl ester-based polymer (a-1-2) is 0.05 to 1.0 μm, and is measured by gel permeation chromatography ( The modifier for thermoplastic resins (A) according to any one of claims 18 to 24, wherein the weight average molecular weight of the (meth) acrylic acid alkyl ester-based polymer is 20,000 to 5,000,000.   The content of the polytetrafluoroethylene (a-1-1) is the sum of the polytetrafluoroethylene (a-1-1) and the (meth) acrylic acid alkyl ester polymer (a-1-2). 26. The thermoplastic resin modifier (A) according to any one of claims 18 to 25, wherein the content is 100 to 70 parts by mass.   The inorganic additive (a-2) is calcium carbonate, talc, magnesium carbonate, mica, kaolin, calcium sulfate, barium sulfate, aluminum hydroxide, magnesium hydroxide, silica, clay, zeolite, talc, wollastonite, 27. The thermoplastic resin modifier (A) according to any one of claims 18 to 26, which is at least one selected from the group consisting of glass, graphite, fibers, powders or beads.   The organic hard polymer (a-3) is a hard thermoplastic polymer having a glass transition temperature (Tg) of 50 to 98 ° C obtained by emulsion polymerization of one or more vinyl monomers. Item 28. The thermoplastic resin modifier (A) according to any one of Items 18 to 27.   29. The thermoplastic resin modifier according to claim 28, wherein the vinyl monomer is a monomer selected from a C1-C4 (meth) acrylic acid alkyl ester and an aromatic alkenyl compound.   The thermoplastic resin according to any one of claims 1 to 29, wherein the polytetrafluoroethylene (a-1-1) is 0.001 to 20 parts by mass per 100 parts by mass of the thermoplastic resin (B). The thermoplastic resin composition which added the modifier (A).   Furthermore, the thermoplastic resin composition of Claim 30 containing a flame retardant (C).   The thermoplastic resin composition according to claim 30 or 31, further comprising a filler (D).   A molded article obtained by injection molding, extrusion molding or extrusion blow molding the thermoplastic resin composition according to any one of claims 30 to 32.   33. A molded article obtained by injection foam molding or extrusion foam molding of the thermoplastic resin composition according to any one of claims 30 to 32.