WO1994007923A1 - Latex de particules polymeres dieniques, procede pour la production de ce latex, et procede pour produire une resine thermoplastique contenant du caoutchouc a partir de ces particules polymeres - Google Patents

Latex de particules polymeres dieniques, procede pour la production de ce latex, et procede pour produire une resine thermoplastique contenant du caoutchouc a partir de ces particules polymeres Download PDF

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Publication number
WO1994007923A1
WO1994007923A1 PCT/JP1993/001376 JP9301376W WO9407923A1 WO 1994007923 A1 WO1994007923 A1 WO 1994007923A1 JP 9301376 W JP9301376 W JP 9301376W WO 9407923 A1 WO9407923 A1 WO 9407923A1
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Prior art keywords
polymer particles
gen
based polymer
monomer
latex
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Application number
PCT/JP1993/001376
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English (en)
Japanese (ja)
Inventor
Katsumi Kurosu
Akira Tsuchiya
Toshiaki Aida
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Nippon Zeon Co., Ltd.
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Publication date
Application filed by Nippon Zeon Co., Ltd. filed Critical Nippon Zeon Co., Ltd.
Publication of WO1994007923A1 publication Critical patent/WO1994007923A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers

Definitions

  • Latex of gen-based polymer particles and method for producing the same
  • the present invention relates to a latex of gen-based polymer particles and a method for producing the same, and more particularly to a latex of gen-based polymer particles having a large average particle size and a narrow particle size distribution, and a method for producing the same.
  • the present invention also relates to a method for producing a rubber-containing thermoplastic resin using the above-mentioned gen-based polymer particles. More specifically, the present invention relates to a rubber-containing thermoplastic resin having both high surface gloss and high impact strength and excellent in its balance. Related to the production method.
  • a method of producing a polymer latex having a large particle size by emulsion polymerization for example, a method of adding an inorganic electrolyte to a polymerization system.
  • a method of lowering the pH of emulsion in polymerization is known.
  • the average particle diameter of non-gen polymer particles is 0.2 ⁇ m or more and 0.85 to 1.15 Twice as large Particles having a ratio of particles of 85% or more can be easily obtained by the above method.
  • the average particle size of the polymer particles constituting the polymer particles is 0.2 m or more and 0.7 to 1.3 times the average particle size. Particles with a particle size of only about 90% can be obtained, and those with a particle size in the narrow range of 0.85-1.15 times exceed 80%. Can not be obtained.
  • rubber-containing thermoplastic resins such as ABS resins generally have excellent characteristics such as excellent mechanical strength and moldability, and are used in a wide range of fields such as home appliances and automobiles.
  • demand for rubber-containing thermoplastic resins that provide molded articles with extremely high surface gloss is increasing in order to increase commercial value.
  • the average particle size is 0.1 l / z m or more
  • the proportion of particles having a particle size of less than 0. IB m and 0.7 to 1.3 times the average particle size is about 90%, or 0.85 to 1.15
  • the rubber-containing thermoplastic resin obtained by this method either the surface gloss or the impact resistance was low, and the balance between them was insufficient.
  • a first object of the present invention is to provide a latex of gen-based polymer particles having a large average particle size and an extremely narrow particle size distribution, and a method for producing the same.
  • a second object of the present invention is to provide a method for producing a rubber-containing thermoplastic resin which has both high surface gloss and high shochu impact strength, and has an excellent balance between them.
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a monomer composition containing a conjugated diene monomer in the presence of a seed latex having an emulsifier coverage of a specific value or less. It has been found that the first object can be achieved by polymerization.
  • gen-based polymer particles having an average particle size and a particle size distribution defined in a specific range contain an ethylenically unsaturated nitrile 1 ⁇ monomer and an aromatic vinyl monomer. It has been found that the second object can be achieved by performing a graft polymerization of the resulting monomer mixture.
  • the present invention has been completed based on these findings.
  • the average particle diameter is 0.1 to 0.5 m
  • the monodispersity ratio is 15% or less
  • the average particle diameter is 0.85 to 1
  • a latex of gen-based polymer particles wherein the ratio of particles having a particle diameter in the range of 15 times is 85% or more.
  • a conjugated diene monomer is contained in the presence of 0.2 to 30 parts by weight (solid conversion) of a seed latex having an emulsifier coverage of 85% or less. 100 parts by weight of the monomer composition to be produced is provided, and a method for producing a latex of the gen-based polymer particles is provided.
  • the gen-based polymer particles constituting the latex are mixed with a monomer mixture containing an ethylenically unsaturated nitrile monomer and an aromatic vinyl monomer.
  • the present invention provides a method for producing a rubber-containing thermoplastic resin, which comprises subjecting a product to graft polymerization.
  • the gen-based polymer particles constituting the latex have an average particle diameter of 0.1 to 0.5 m, preferably 0.15 to 0.5. m, more preferably from 0.23 to 0.5 m. If the average particle diameter of the gen-based polymer particles is smaller than 0.1 ⁇ m, the impact resistance of the rubber-containing thermoplastic resin obtained by graph-polymerizing the gen-based polymer particles is reduced, and conversely, 0.1. If it is larger than 5 m, the surface gloss of the rubber-containing thermoplastic resin decreases.
  • Figure 1 is a graph showing the relationship between the amount of emulsifier added and the surface tension.
  • the particle size distribution of the gen-based polymer particles is such that particles having a particle size in the range of 0.85 to 1.15 times the average particle size have a harmful ij ratio of 8 5. % Or more, and preferably 90% or more. If it is less than 85%, the balance between the surface gloss of the rubber-containing thermoplastic resin and the impact resistance becomes poor. In addition, when the particle size distribution is expressed by a monodispersity ratio, it is necessary that it be 15% or less, and preferably 10% or less. If the content exceeds 15%, the balance between the surface gloss and the impact strength of the rubber-containing thermoplastic resin becomes poor.o
  • a monomer mixture containing a conjugated diene monomer is polymerized in the presence of a silica latex.
  • the latex used in the production of the gen-based polymer particle latex is a latex of a polymer in which the polymer constituting the latex has an emulsifier coverage of 85% or less, preferably 60% or less. is there.
  • the emulsifier coverage refers to the ratio of the amount of the emulsifier contained in the Sea Dratex to the amount of the emulsifier capable of covering the particle surface of the polymer constituting the Sea Dra Tex. The evaluation method will be described later.
  • Non-ionic emulsifiers such as polyoxyethylene alkylene ether, polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl ester and polyoxyethylene sorbin alkyl ester; emulsifier; myristiminic acid And fatty acids such as palmitic acid, oleic acid, and linolenic acid, and salts thereof, anionic emulsifiers such as alkylarylsulfonates, higher alcohol esters, and alkylsulfosuccinic acids. .
  • S—Sulfoester of unsaturated carboxylic acid, H—Sulfate of unsaturated carboxylic acid Copolymerizable emulsifiers containing a double bond such as stell and sulfoalkylaryl ether can also be used.
  • These emulsifiers can be used alone or in combination of two or more.
  • an alkali metal salt of a higher fatty acid such as rosin acid, oleic acid, or stearic acid is used among these emulsifiers, it is easy to obtain gen-based polymer particles having a narrow particle size distribution, which is the object of the present invention. I like it.
  • those having an average particle diameter of the polymer particles constituting it of usually 0.03 to 2 m, preferably 0.04 to 0.12 m are used. If it is less than 0.03 m, the reaction time becomes longer. Conversely, if it exceeds 0.2 / m, the particle size distribution of the gen-based polymer particles becomes wide.
  • the monomer used in the production of seed latex is not particularly limited, and for example, conjugated diene monomers such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene; styrene, and -Aromatic vinyl quasimers such as methylstyrene; (meth) ethylenically unsaturated monocarboxylic acids such as acrylic acid; ethylenically unsaturated polycarboxylic acids such as maleic acid and itaconic acid; Ethylenically unsaturated polyvalent carboxylic acid partial esters such as monomethyl maleate and monoethyl itaconate; (meth) methyl acrylate,
  • Ethylenically unsaturated carboxylic acid esters such as ethyl acrylate; single ethylenically unsaturated carboxylic acid esters such as acrylonitrile and methacrylonitrile Fluoroalkyl vinyl ethers such as fluoroethyl vinyl ether; Vinyl pyridine; Vinyl norbornene, dicyclopentene, 1, 4-hydroxy Non-conjugated diene monomers such asowski; monoolefins such as ethylene and propylene; and ethylenically unsaturated carboxylic acid amides such as (meta) acrylamide. These can be used alone or in combination of two or more. Among these monomers, conjugated diene monomers such as 1,3-butadiene are preferred.
  • the method for producing seed latex is not particularly limited. Usually, it can be produced by an emulsion polymerization method, but can also be produced by a phase inversion method.
  • the monomer composition containing a conjugated gen monomer used in the method for producing a latex of gen-based polymer particles according to the present invention may be a conjugated gen monomer alone or in combination with a conjugated gen monomer. It is a mixture of body and body.
  • conjugated diene monomers examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentene, ⁇ ⁇ ⁇ ⁇ ⁇ An example of this is a mouthpiece. Of these monomers, 1, 3 — butylbenzene is preferred.
  • the conjugated diene monomer is used in an amount of at least 50% by weight, preferably at least 70% by weight, more preferably at least 100% by weight, of the monomer composition containing the co-active diene monomer. It is.
  • ethylenically unsaturated monomers include, for example, aromatic vinyl monomers such as styrene, dimethylstyrene, and divinylbenzene; and ethylenic monomers such as (meth) acrylic acid.
  • the ratio of the amount of the Sea Doratex to the monomer composition containing the conjugated gen monomer is 100 parts by weight of the monomer composition containing the conjugated gen monomer, and The amount is 0.2 to 30 parts by weight, preferably 0.5 to 25 parts by weight. When the amount is less than 0.2 parts by weight, the polymerization stability of the gen-based polymer particles is poor. When the amount exceeds 30 parts by weight, the particle distribution of the gen-based polymer particles becomes wide.
  • an emulsifier is added in order to improve the polymerization stability of the latex of the diene polymer particles of the present invention.
  • the emulsifier coverage of the latex of the body particles is 85% or less, preferably 60% or less. Addition of an emulsifier in an amount exceeding 85% broadens the particle size distribution of the gen-based polymer particles of the present invention.
  • the method for producing the rubber-containing thermoplastic resin of the present invention is characterized in that the gen-based ffi-combined particles constituting the latex of the gen-polymer particles are added to an ethylenically unsaturated nitrile monomer and an aromatic vinyl monomer. To It is to polymerize the contained monomer mixture.
  • the gen-based polymer particles (1) an average particle diameter of 0.15 to 0.5 ⁇ m, preferably 0.23 to 0.5 ⁇ m, more preferably (2) the monodispersity ratio is 15% or less, preferably 10% or less, and (3) the average particle diameter is 0.85.
  • Gen-based polymer particles (A) having a particle size in the range of 15 times or more, preferably 85% or more, preferably 90% or more, and an average particle size of 0.0 8 to 0.22 m, preferably 0.1 to 0.2 m, which is composed of the gen-based polymer particles (B) and from the average particle diameter of the gen-based polymer particles (A).
  • the rubber-containing thermoplastic resin can be used. It is preferable to use the mixed particles because the balance between the impact resistance and the surface gloss increases.
  • the weight ratio between the gen-based polymer particles (A) and the gen-based polymer particles (B) is usually 5Z95 to 85/15, preferably 10/90. ⁇ 70/30.
  • Examples of the ethylenically unsaturated nitrile monomer include acrylonitrile and methacrylonitrile, and two or more kinds may be used as a mixture. Of these ethylenically unsaturated nitrile monomers, acrylonitrile is preferred.
  • the amount of the ethylenically unsaturated ditolyl monomer is usually from 2 to 50% by weight of the monomer mixture used in the graft polymerization to improve the solvent resistance of the rubber-containing thermoplastic resin. %.
  • aromatic vinyl monomer examples include styrene and permethylstyrene. Examples thereof include len, vinyltoluene, and styrogenated styrene, and these may be used in combination of two or more. These aromatic vinyls! Of the Ji-mers, styrene is preferred.
  • the amount of the aromatic vinyl monomer is usually 10 to 90% by weight of the monomer mixture used for the graft polymerization in order to improve the hardness of the rubber-containing thermoplastic resin.
  • (meth) acrylic acid ester monomers such as (meth) methyl acrylate, (meth) ethyl acrylate, and (meth) butyl acrylate; vinyl chloride; Halogenated vinyl such as vinyl acetate; vinyl carboxylate monomer such as vinyl acetate; and ethylenically unsaturated carboxylic acid monomer such as methyl acrylate and acrylate.
  • the amount of these monomers is usually not more than 70% by weight of the monomer mixture used for the graft polymerization.
  • the weight ratio between the gen-based polymer particles (or mixed particles) and the monomer mixture to be subjected to the graft polymerization is usually 5Z95 to 75/25, preferably 30/70. ⁇ 65/35. If the ratio of the gen-based polymer particles is less than 5% by weight, the gloss and impact strength of the rubber-containing thermoplastic resin become insufficient. Conversely, if it exceeds 75% by weight, the gloss of the rubber-containing thermoplastic resin is significantly reduced.
  • the graft polymerization is performed using a known polymerization technique.
  • the latex of the ene-based polymer particles is charged into a reactor, and the mixture contains an ethylenically unsaturated monomer and an aromatic vinyl monomer.
  • the resulting monomer mixture is added for polymerization.
  • a coagulant is added to the polymerization reaction system, and the coagulated material is filtered, dehydrated and dried to obtain a rubber-containing thermoplastic resin.
  • a coloring agent, a stabilizer, an antistatic agent, a plasticizer, and the like may be appropriately added to the rubber-containing thermoplastic resin obtained by the present invention.
  • the rubber-containing thermoplastic resin obtained by the present invention can be used alone as a material or the like for producing a molded article.
  • heat treatment such as polyvinyl chloride, polyvinyl acetate, polyamide, polyacryl, polyolefin, polyester, acrylonitrile-relu-styrene copolymer (AS resin), and polycarbonate Can be used in combination with a plastic resin.
  • Gen-based polymer particles were stained with osmic acid, photographed with a transmission electron microscope, and 350 particles were randomly selected from the photograph to measure the particle diameter.
  • the average particle diameter is represented by the value (m) obtained by dividing the sum of the measured values by the number of measured particles, and the monodispersity ratio is the value (%) obtained by dividing the standard deviation of the measured values by the average particle diameter and multiplying by 100. Represent.
  • a certain amount (w.) Of the rubber-containing thermoplastic resin is poured into acetonitrile, stirred for 2 hours with a stirrer, and then the solution is centrifuged at 23,000 rpm using a centrifuge. Centrifuged for minutes. The separated insolubles were dried for 1 D at 120 ° C using a vacuum dryer and weighed.
  • rubber-containing thermoplastic resin 100 parts of rubber-containing thermoplastic resin is AS resin (acrylonitrile content: 30%, intrinsic viscosity of methyl ethyl ketone at 30 ° C)
  • the mixture was pelletized at 200 ° C. using a 4 O mZm extruder.
  • a 90 mm ⁇ 50 mm ⁇ 3 mm plate was produced at a mold temperature of 40 ° C. using an injection molding machine (Nissei Resin Industry Co., Ltd., NC—800 PZ).
  • the plate was measured using a GROSS meter (manufactured by MURAKAMI COLOR RESERCH LABORATORY, GIVI-26D) at an incident angle of 60 degrees.
  • the above plate was measured under the conditions of 14 inches, notched, 50% R.II. and 23 ° C. according to ASTM D-256.
  • Example 1 Same as Example 1 except that the polymerization recipe shown in Table 1 or Table 2 was followed.
  • a latex of gen-based polymer particles was obtained by the same method.
  • Tables 1 and 2 show the physical properties of the latex of these gen-based polymer particles.
  • a latex of gen-based polymer particles was obtained in the same manner as in Reference Example 5, except that the charged amount of soft water was changed to 75 parts.
  • Table 2 shows the physical properties of the latex of the gen-based polymer particles.
  • Average particle size 0.12 0.14 0.09 0.17 0.08 0.30 Monodispersity ratio 5.5 10.1 17.6 20.3 20.2 28.0 0.7 to 1.3 times the average particle size
  • Average particle size 0.19 m, latex of polybutadiene particles having a ratio of 98.9% of particles within the range of 0.85 to 1.15 times the average particle size 45 parts 20 parts of styrene, 7.5 parts of acrylonitrile, 0.8 part of potassium rosinate, 0.2 parts of t-dodecylmercaptan and 130 parts of ion-exchanged water
  • the mixture was charged into a jacket and a reactor equipped with a stirrer. After replacing the air inside with nitrogen, the internal temperature was raised to 60 ° C, and 10 parts of water and sodium pyrophosphate were added.
  • a mixture of 0.4 part of chromium, 0.5 part of dextros, 0.01 part of ferrous sulfate and 0.05 part of peroxide at the mouth of a cumenehydride was added and reacted (first stage).
  • thermoplastic resin emulsion To the resulting rubber-containing thermoplastic resin emulsion was added 0.5 part of 2,2'-methylenebis (4-methyl-16-butylphenol) as an anti-aging agent and coagulated. Separation of coagulated material from water After releasing, washing with water, dehydrating and drying, a rubber-containing thermoplastic resin was obtained.
  • a rubber-containing thermoplastic resin was obtained in the same manner as in Example 10, except that the latex of the gen-based polymer particles and the composition of the monomer to be polymerized were changed to the formulations shown in Table 3.
  • Table 3 shows the evaluation results of the rubber-containing thermoplastic resins obtained in Examples 10 to 14 and Comparative Examples 5 to 7.
  • the ratio of particles having an average particle diameter of 0.1 to 0.5 m and within a range of 0.85 to 1.1 times the average particle diameter is 85% or more. It can be seen that the rubber-containing thermoplastic resin obtained by graft polymerization of the gen-based polymer particles has a good balance between the surface gloss and the impact resistance.
  • Example 10 in place of the latex of polybutadiene particles, the ratio of particles having an average particle diameter of 0.32 m and within a range of 0.85 to 1.15 times the average particle diameter was 99%. 13.5 parts (solid content conversion) of 3% of boribenien particles with an average particle diameter of 0.13 ⁇ m and 0.85-1.15 times the average particle diameter
  • the rubber-containing heat was the same as in Example 10 except that the polybutene particles in the range of 96.3% were replaced with 31.5 parts (converted to solid content) of latex particles.
  • a plastic resin was obtained.
  • a rubber-containing thermoplastic resin was obtained in the same manner as in Example 15 except that the latex of the gen-based polymer particles and the formulation of the monomer to be polymerized were changed to the formulation shown in Table 4.
  • a latex of gen-based polymer particles having a large average particle size and a narrow particle size distribution is provided, and a rubber-containing thermoplastic resin obtained from the gen-based polymer particles constituting the latex is provided.
  • a rubber-containing thermoplastic resin obtained from the gen-based polymer particles constituting the latex is provided.
  • This rubber-containing thermoplastic resin is used in applications such as home appliances and vehicles.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention se rapporte à un latex de particules polymères diéniques, où le diamètre particulaire moyen est de 0,1 à 0,5 νm, le rapport de monodispersité est de 15 % ou moins et la proportion des particules ayant des diamètres 0,85 à 1,15 fois égaux au diamètre particulaire moyen est de 85 % ou plus. On produit ce latex en polymérisant une composition monomère contenant un monomère de diène conjugué en présence d'un latex de germination dont la couverture par émulsifiant est de 85 % ou moins. On produit une résine thermoplastique contenant du caoutchouc en greffant un mélange d'un monomère de nitrile éthyléniquement insaturé avec un monomère de vinyle aromatique sur les particules polymères diéniques, de préférence un mélange de celles-ci avec d'autres particules polymères diéniques ayant des diamètres particulaires moyens inférieurs d'au moins 0,05 νm à ceux des premières particules polymères diéniques.
PCT/JP1993/001376 1992-09-28 1993-09-28 Latex de particules polymeres dieniques, procede pour la production de ce latex, et procede pour produire une resine thermoplastique contenant du caoutchouc a partir de ces particules polymeres WO1994007923A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP28248492 1992-09-28
JP4/282484 1992-09-28
JP5/89136 1993-03-24
JP8913693 1993-03-24
JP21091493 1993-08-03
JP5/210914 1993-08-03

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WO1994007923A1 true WO1994007923A1 (fr) 1994-04-14

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PCT/JP1993/001376 WO1994007923A1 (fr) 1992-09-28 1993-09-28 Latex de particules polymeres dieniques, procede pour la production de ce latex, et procede pour produire une resine thermoplastique contenant du caoutchouc a partir de ces particules polymeres

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003524040A (ja) * 2000-02-23 2003-08-12 バイエル アクチェンゲゼルシャフト 改良された特性の不変性を有するポリマー組成物
JP2003524052A (ja) * 2000-02-23 2003-08-12 バイエル アクチェンゲゼルシャフト 改良された加工性と高い光沢を有するａｂｓ成形材料
JP2003528170A (ja) * 2000-02-23 2003-09-24 バイエル アクチェンゲゼルシャフト 改良された一定の性質を有するポリマー組成物
KR100464698B1 (ko) * 2001-12-20 2005-01-05 제일모직주식회사 중입자경 고무라텍스를 이용한 응집입자 제조방법
US10017586B2 (en) 2009-04-29 2018-07-10 Life Technologies As Monodisperse submicron polymer particles
JP2019019311A (ja) * 2017-07-20 2019-02-07 旭化成株式会社 熱可塑性樹脂組成物及びその成形品

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6348313A (ja) * 1986-08-18 1988-03-01 Nippon Zeon Co Ltd 大粒径ブタジエン系重合体ラテツクスの製造方法
JPS63308002A (ja) * 1987-06-09 1988-12-15 Kanebo N S C Kk 高固形分乳化重合体組成物の製法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6348313A (ja) * 1986-08-18 1988-03-01 Nippon Zeon Co Ltd 大粒径ブタジエン系重合体ラテツクスの製造方法
JPS63308002A (ja) * 1987-06-09 1988-12-15 Kanebo N S C Kk 高固形分乳化重合体組成物の製法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003524040A (ja) * 2000-02-23 2003-08-12 バイエル アクチェンゲゼルシャフト 改良された特性の不変性を有するポリマー組成物
JP2003524052A (ja) * 2000-02-23 2003-08-12 バイエル アクチェンゲゼルシャフト 改良された加工性と高い光沢を有するａｂｓ成形材料
JP2003528170A (ja) * 2000-02-23 2003-09-24 バイエル アクチェンゲゼルシャフト 改良された一定の性質を有するポリマー組成物
KR100464698B1 (ko) * 2001-12-20 2005-01-05 제일모직주식회사 중입자경 고무라텍스를 이용한 응집입자 제조방법
US10017586B2 (en) 2009-04-29 2018-07-10 Life Technologies As Monodisperse submicron polymer particles
JP2019019311A (ja) * 2017-07-20 2019-02-07 旭化成株式会社 熱可塑性樹脂組成物及びその成形品

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