WO2003102076A1 - Composition de resine thermoplastique - Google Patents

Composition de resine thermoplastique Download PDF

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Publication number
WO2003102076A1
WO2003102076A1 PCT/JP2003/007038 JP0307038W WO03102076A1 WO 2003102076 A1 WO2003102076 A1 WO 2003102076A1 JP 0307038 W JP0307038 W JP 0307038W WO 03102076 A1 WO03102076 A1 WO 03102076A1
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Prior art keywords
mass
styrene
copolymer
resin composition
meth
Prior art date
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PCT/JP2003/007038
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English (en)
Japanese (ja)
Inventor
Tetsuo Noguchi
Yoshiaki Katoh
Original Assignee
Denki Kagaku Kogyo Kabushiki Kaisha
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Application filed by Denki Kagaku Kogyo Kabushiki Kaisha filed Critical Denki Kagaku Kogyo Kabushiki Kaisha
Priority to KR1020047019598A priority Critical patent/KR101050701B1/ko
Priority to AU2003241990A priority patent/AU2003241990A1/en
Priority to JP2004510323A priority patent/JP4534075B2/ja
Publication of WO2003102076A1 publication Critical patent/WO2003102076A1/fr
Priority to HK05111790A priority patent/HK1079807A1/xx

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers

Definitions

  • the present invention relates to a thermoplastic resin composition capable of obtaining a molded article having excellent transparency and exhibiting excellent impact resistance and molding workability even in an extremely thin wall.
  • thermoplastic resin composition having excellent impact resistance and transparency can be obtained by mixing an MBS-based polymer obtained by polymerization with a rubber-modified styrene-based polymer. 4 6—3 2 7 4 8 Publication).
  • MBS-based polymer obtained by polymerization with a rubber-modified styrene-based polymer. 4 6—3 2 7 4 8 Publication.
  • these thermoplastic resin compositions are certainly excellent in impact resistance, they have a drawback that good transparency cannot be obtained depending on molding conditions.
  • Japanese Patent Application Laid-Open No. 2001-226647 discloses a continuous phase of a specific styrene- (meth) acrylate copolymer and a specific graft copolymer.
  • a rubber-modified styrene resin composition comprising a polymer dispersed phase has been proposed.
  • impact resistance or moldability was not necessarily sufficient.
  • the present invention provides a thermoplastic resin composition which has excellent transparency and can obtain a molded article exhibiting excellent impact resistance and molding workability even in an extremely thin wall. Things. Disclosure of the invention
  • the present inventors have conducted intensive studies to solve such problems, and as a result, have found that a continuous phase of a specific styrene- (meth) acrylate copolymer and a dispersed phase of a specific graft copolymer are obtained.
  • the present inventors have found that the above-mentioned problems can be solved by a thermoplastic resin composition containing a specific amount of an organic polysiloxane in a rubber-modified styrenic resin composition composed of the following, and completed the present invention. .
  • the present invention has the following features.
  • Styrene- (meth) acrylate-based copolymers which are copolymers of vinyl monomers that can be copolymerized with these monomers and are used as necessary
  • a rubber-modified styrenic resin composition containing 40 to 20% by mass of a dispersed phase of a graft copolymer
  • the volume average particle diameter of the dispersed phase is 0.3 to 0.6 zm
  • the weight average molecular weight (Mw) of the continuous phase and X of the formula (1) obtained from the constituent monomer unit are expressed by the formula (2)
  • a thermoplastic resin composition comprising 0.005 to 0.05 parts by mass of an organic polysiloxane with respect to 100 parts by mass of the resin composition.
  • X star summer average molecular weight (Mw) X V styrene monomer unit (% by mass) (1)
  • the rubber-modified styrenic resin composition comprises: (I) 60 to 70% by mass of a continuous phase of a styrene- (meth) acrylate copolymer; and (II) 40 to 70% by mass of a dispersed phase of a graft copolymer.
  • the thermoplastic resin composition according to the above 1, containing 30% by mass.
  • the thermoplastic resin composition according to the above 1 or 2 comprising 0.1 to 2.5 parts by mass of an ester lubricant relative to 100 parts by mass of the rubber-modified styrene resin composition.
  • thermoplastic resin composition according to the above item 3 wherein the ester lubricant is a hardened castor oil.
  • thermoplastic resin composition according to any one of the above items 1 to 4, wherein the organic polysiloxane is polydimethylsiloxane.
  • the continuous phase is composed of 20 to 70% by mass of a styrene-based monomer unit, 30 to 80% by mass of a (meth) acrylate-based monomer unit, and, if necessary, Any of the above-mentioned 1 to 5, which is a styrene-mono (meth) acrylate ester copolymer, which is a copolymer of 0 to 10% by mass of a vinyl monomer unit copolymerizable with a monomer.
  • Item 2 The thermoplastic resin composition according to item 1.
  • the dispersed phase is composed of 30 to 80 parts by mass of a rubbery elastomer of polybutadiene and Z or styrene-butadiene copolymer, 20 to 70% by mass of styrene-based monomer units, and (acrylic) acrylic.
  • the continuous phase is composed of 20 to 70% by mass of a styrene-based monomer unit, 30 to 80% by mass of a (meth) acrylate-based monomer unit, and used as necessary.
  • a styrene- (meth) acrylate-based copolymer which is a copolymer of 0 to 10% by mass of a vinyl-based monomer unit copolymerizable with a monomer, and in which a polybutadiene and And / or 30 to 80 parts by mass of a styrene-butadiene copolymer rubber-like elastic material, 20 to 70% by mass of a styrene monomer unit, and 30 to 70% by mass of a (meth) acrylic acid ester monomer unit Styrene mono (meth) acryl, which is a copolymer of 80% by mass and 0 to 10% by mass of a vinyl monomer unit copolymerizable with these monomers and used as necessary.
  • the above-mentioned 1 is a graft copolymer in which 20 to 70 parts by mass of an acid ester copolymer is grafted. According to any one of Itaru 5 Thermoplastic resin composition. BEST MODE FOR CARRYING OUT THE INVENTION
  • the styrene- (meth) acrylate-based copolymer constituting the continuous phase of the rubber-modified styrene-based resin composition of the present invention includes styrene-based monomers, (meth) acrylate-based monomers, and It is a copolymer of a vinyl monomer that can be used as necessary and that can be copolymerized with these monomers.
  • the graft copolymer constituting the dispersed phase of the rubber-modified styrenic resin composition of the present invention includes: a rubbery elastic body, a styrene-based monomer, a (meth) acrylate-based monomer, and A graft copolymer obtained by grafting a styrene- (meth) acrylate copolymer, which is a copolymer of a vinyl monomer copolymerizable with these monomers and used as necessary. is there.
  • Styrene monomers used in the continuous phase and the dispersed phase of the present invention include styrene, ⁇ -methylstyrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, ethylstyrene, -t-butylstyrene and the like. And styrene is preferred. These styrene monomers may be used alone or in combination of two or more.
  • Examples of the (meth) acrylate monomer used in the present invention include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and other methyl acrylates, methyl acrylate, and ethyl acrylate.
  • acrylate esters such as n-butyl acrylate, 2-methylhexyl acrylate, 21-ethylhexyl acrylate, and decyl acrylate, and are preferably methyl methacrylate or n-butyl acrylate. And particularly preferably methyl methacrylate.
  • These (ester) acrylate monomers may be used alone or in combination of two or more.
  • vinyl monomers that can be copolymerized with these monomers include acrylic acid, methacrylic acid, acrylonitrile, and methacrylic acid. Lonitrile, N-phenylmaleimide, N-cyclohexylmaleimide and the like.
  • Examples of the rubber-like elastic material used in the present invention include polybutadiene, styrene-butene diene block copolymer, and styrene-butadiene random copolymer.
  • the styrene monomer unit amount in the styrene-butadiene block copolymer or the styrene-butanediene random copolymer is preferably 60% by mass or less, particularly preferably 25% by mass or less (where 0 is Is not included) in order to obtain good impact resistance and transparency of the rubber-modified styrenic resin composition.
  • the rubber-modified styrenic resin composition of the present invention has a continuous phase of 60 to 80% by mass of a styrene- (meth) acrylate copolymer and a dispersed phase of 40 to 20% by mass of a graft copolymer.
  • % Preferably 60 to 70% by mass of a continuous phase of a styrene- (meth) acrylate ester copolymer, and 40 to 30% by mass of a dispersed phase of a graft copolymer. I do.
  • the dispersed phase of the graft copolymer is less than 20% by mass, the impact resistance of a thin-walled molded product is insufficient, and when it exceeds 40% by mass, the molding processability becomes insufficient.
  • the mass ratio between the continuous phase and the dispersed phase was determined by stirring the rubber-modified styrene resin composition (mass A) in methyl ethyl ketone (MEK) at a temperature of 23 ° C for 24 hours. Then, the insoluble matter in MEK is separated by a centrifugal separator, and the dried matter is vacuum-dried, and the mass is measured (assuming the mass is B), which is obtained by the following equations (3) and (4).
  • Dispersed phase (% by mass) 2 'X 100
  • the dispersed phase of the graft copolymer has a volume average particle diameter of preferably 0.3 0.6 m, particularly preferably 0.3 0.45 m. If the volume average particle diameter is less than 0.3 m, the impact resistance of a thin-walled molded product is insufficient, and if it exceeds 0.6 m, the transparency is inferior.
  • the weight average molecular weight (Mw) and X of the formula (1) obtained from its constituent units are within the range of the formula (2). is necessary.
  • the weight average molecular weight of the continuous phase described here is the weight average molecular weight in terms of polystyrene obtained by measuring the MEK-soluble component of the rubber-modified styrene resin composition by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the amount of each monomer unit constituting the continuous phase styrene- (meth) acrylate copolymer is not particularly limited as long as the above conditions are satisfied.
  • the unit is preferably 270% by mass, particularly preferably 240% by mass, and the (meth) acrylate monomer unit is preferably 380% by mass, particularly preferably 680% by mass.
  • the amount of the vinyl monomer unit copolymerizable with these monomers, which is used as necessary, is preferably 0% by mass, particularly preferably 0.5% by mass.
  • the amounts of the rubber-like elastic body and each monomer unit constituting the graft copolymer of the dispersed phase are not particularly limited as long as the above conditions are satisfied.
  • the rubbery elastic body is contained in an amount of 30 to 80 parts by mass, preferably 50 to 75 parts by mass, particularly preferably 50 to 70 parts by mass, and the styrene monomer unit is preferably 20 to 70 parts by mass.
  • Acrylic ester copolymer is preferably a graft copolymer having a mass of 20 to 70 parts by mass, preferably 25 to 50 parts by mass, particularly preferably 30 to 50 parts by mass.
  • the rubber-modified styrenic resin composition of the present invention can be produced by a known technique such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, a bulk-one suspension polymerization method, and an emulsion polymerization method.
  • a known technique such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, a bulk-one suspension polymerization method, and an emulsion polymerization method.
  • any of a palindrome polymerization method and a continuous polymerization method can be used.
  • the thermoplastic resin composition of the present invention contains an organic polysiloxane.
  • the organic polysiloxane include polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, and the like, and polydimethylsiloxane is preferable.
  • a modified type in which an epoxy group, an amino group, a propyloxyl group, a hydroxyl group, a methacryl group, or the like is introduced into the terminal or the molecule of the organic polysiloxane can be used.
  • These organic polysiloxanes may be used alone or in combination of two or more.
  • thermoplastic resin composition of the present invention preferably uses the organopolysiloxane and the ester-based lubricant in combination to improve the balance between transparency, impact resistance, and moldability.
  • ester-based lubricant include fatty acid polyhydric alcohol esters such as hydrogenated castor oil, fatty acid lower alcohol esters such as butyl stearate, and fatty acid polyglycol esters such as polyethylene glycol monostearate. Hardened castor oil.
  • the content of the organic polysiloxane is 0.05 to 0.05 part by mass, preferably 0.01 to 0.03 part by mass, based on 100 parts by mass of the rubber-modified styrene resin composition. Department. If the amount is less than 0.05 part by mass, the impact resistance of the thin-walled molded product is insufficient, and if the amount exceeds 0.05 part by mass, the transparency deteriorates, which is not preferable.
  • the preferred content of the ester-based lubricant is 0.1 to 2.5 parts by mass, and preferably 0.5 to 2 parts by mass, based on 100 parts by mass of the rubber-modified styrene resin composition.
  • the amount is less than 0.1 part by mass, the effect of using the organic polysiloxane and the ester-based lubricant in combination is small, and when the amount exceeds 2.5 parts by mass, the transparency is greatly reduced.
  • thermoplastic resin composition of the present invention contains known additives such as an antioxidant, a weathering agent, a lubricant, a plasticizer, a coloring agent, an antistatic agent, and a mineral oil, and the performance of the thermoplastic resin composition of the present invention. You may mix
  • thermoplastic resin composition of the present invention can be processed into various molded articles by a method such as injection molding, compression molding and extrusion molding, and can be put to practical use.
  • Mixing (mixing) in the case of producing various molded articles using the thermoplastic resin composition of the present invention the melt extrusion method is not particularly limited, and a known method can be employed.
  • each raw material is uniformly mixed in advance with a tumbler, Henschel mixer, or the like, and supplied to a single-screw extruder or a twin-screw extruder to melt and mix to prepare pellets for molding. As a result, various molded products are manufactured.
  • a styrene- (meth) acrylate copolymer A-5 was produced in the same manner as in Reference Example 5 except that the t-dodecylmer force was changed to 600 g.
  • (Meth) acrylic ester copolymer A-6 was obtained. (Mouth) Production of rubber-like elastic latex
  • the rubber-like elastic latex G-1 of Reference Example 7 was weighed at 30 kg in terms of solid content, transferred to a 200 L autoclave, added with 90 kg of pure water, and heated to a temperature of 5 Ot under a nitrogen stream while stirring. Warmed.
  • a powdery copolymer was prepared in the same manner as in the graft copolymer-containing polymer B-2 except that the rubber-like elastic latex was changed to the rubber-like elastic body G-3 in Reference Example 12. Containing polymer B-3 was obtained.
  • Styrene mono (meth) acrylate based copolymer produced in Reference Examples 1 to 6 graft copolymer-containing polymer produced in Reference Examples 11 to 14, polydimethylsiloxane (Shin-Etsu Chemical Co., Ltd.)
  • Table 1 and Table 2 show KF-966), hydrogenated castor oil (Kao Wax 85-P manufactured by Kao Corporation), and ethylene bisstearic acid amide (Kao Wax EB-P manufactured by Kao Corporation). Were blended at the ratios indicated by.
  • Example 1 Example 2
  • Example 3 'Example 4
  • Example 5 Example 6
  • Example 7 Example 8
  • Example 10 Example 11 Styrene mono (meth) A-1 (parts by mass) 70 70 70 ; 70 65 65 65 65
  • Copolymer A-5 (parts by mass) 65
  • Graft copolymer B-1 (parts by mass) 30 30 30 30: 30 35 35 40 40 35 35
  • Contained polymer B-2 (parts by mass)
  • Organic polysiloxane (parts by mass) 0.005 0.015 0.045: 0.015 0.015 0.015 0.015 0.015 0.015 0.015 U.U ⁇ ⁇ 0.015 0.015 hydrogenated castor oil (parts by mass); 0.5 1.52 3
  • Ethylenebisstearic acid amite (parts by mass) 1.5 parts by weight Mass ratio of continuous phase; mass% 73 68 64 70 68 MMA of constituent monomer units 72. 6 72. 7 72. 8 57. 5 72 7 series
  • the rubber-modified styrenic resin composition was analyzed using a rubber-modified styrene-based (meth) acrylic ester-based copolymer and a graft copolymer-containing polymer that were previously mixed at the compounding ratios shown in Tables 1 and 2. Pellets of the styrene-based resin composition were prepared, and each analytical value was measured using the pellets according to the following measurement method. The analytical values are shown in Tables 1 and 2.
  • the sample pellets (assuming mass A), whose mass has been measured in advance, are stirred in methyl ethyl ketone (MEK) at a temperature of 23 ° C. for 24 hours, and then the insoluble matter in MEK is separated by a centrifuge. After centrifugation operation, it was left still for 30 minutes.
  • MEK methyl ethyl ketone
  • the supernatant and the precipitate separated from the centrifuged solution are separated, and the precipitate is dried using a vacuum drier.
  • the mass is measured (assuming the mass is B), and the following formulas (3) and (4) are used.
  • the mass ratio between the continuous phase and the dispersed phase was determined.
  • the supernatant obtained by centrifuging the solution was fractionated, and methanol was added to precipitate a styrene- (meth) acrylate copolymer (continuous phase).
  • the precipitate was collected and measured under the following GPC measurement conditions.
  • Calibration curve Prepared using standard polystyrene (PS) (manufactured by PL), and the weight average molecular weight was expressed in terms of PS.
  • PS polystyrene
  • the continuous phase (MEK-soluble) consisting of the styrene- (meth) acrylate-based copolymer obtained in the pretreatment of the previous measurement was dissolved in heavy-duty-mouthed form, and FT-N MR (manufactured by JEOL Ltd.) FX_90Q) was used to determine the constituent monomer units.
  • sample pellet was stirred in 100 g of N, N-dimethylformamide (DMF) for 24 hours, diluted to an appropriate concentration with the addition of DMF, and measured by laser single-scattering scattering method. The measurement was carried out using a machine (Model No. 3230 of 111111).
  • DMF N, N-dimethylformamide
  • the ratio of the constituent monomer units of the styrene- (meth) acrylate-based copolymer grafted to the rubbery polymer was used. Since the ratio of the constituent monomer units of the ungrafted styrene- (meth) acrylate ester copolymer can be considered to be the same, The measured value was defined as the ratio of the monomer units constituting the styrene- (meth) acrylate-based copolymer grafted to the rubber-like polymer.
  • the precipitate of the centrifuged solution was collected by filtration, dried with a vacuum drier, and used as a measurement sample of the dispersed phase.
  • the obtained sample was swollen in a double-mouthed form, and the constituent monomer units were determined using FT-NMR (FX-90Q type manufactured by JEOL Ltd.).
  • the mass ratio of the constituent monomer units of the styrene- (meth) acrylate ester copolymer obtained by the measurement in the above (5) (where the ratio of the styrene monomer unit is a and the (meth) acrylic acid ester unit is The ratio of the monomer units is b.
  • the total amount of the constituent monomer units is 100.
  • the mass ratio of the constituent monomer units of the dispersed phase sample here, the The ratio of units is c, the ratio of styrene monomer units is d, and the ratio of (meth) acrylic acid ester monomer units is e, where the total amount of constituent monomer units is 100.
  • the amounts of the rubbery elastic body and the amount of the graft monomer were determined according to the following formulas (5) and (6).
  • thermoplastic resin composition of the present invention examples were all excellent in molding workability in thin-wall molding, impact resistance and transparency of a thin molded product, but a thermoplastic resin composition not meeting the conditions of the present invention.
  • the molding property in thin-wall molding, the impact resistance and the transparency of the thin-wall molded product were inferior in any one of physical properties.
  • thermoplastic resin composition having excellent transparency and exhibiting excellent impact resistance and moldability even in an extremely thin molded product.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne une composition de résine thermoplastique hautement transparente et permettant d'obtenir des articles moulés et présentant une excellente résistance aux chocs et une excellente qualité de fabrication, y compris lorsque leurs parois sont fines. La composition de résine thermoplastique est constituée d'une composition de résine de styrène modifiée au caoutchouc contenant de 60 à 80 % en masse d'une phase dispersée faite d'un copolymère de greffage obtenu par greffage d'un élastomère caoutchouteux avec un copolymère de styrène/(méth)acrylate, le diamètre de particule volumétrique moyen de la phase dispersée étant de 0,3 à 0,6 νm, et le poids moléculaire moyen (Mw) de la phase continue et de ses unités monomériques constitutives satisfaisant une relation spécifique, et se caractérisant par un contenu de 0,005 à 0,05 % en masse d'un organopolysiloxane et, si nécessaire, de 0,1 à 2,5 % en masse d'un lubrifiant à base d'esters pour 100 % en masse de la composition de résine de styrène modifiée au caoutchouc.
PCT/JP2003/007038 2002-06-04 2003-06-03 Composition de resine thermoplastique WO2003102076A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1020047019598A KR101050701B1 (ko) 2002-06-04 2003-06-03 열가소성 수지 조성물
AU2003241990A AU2003241990A1 (en) 2002-06-04 2003-06-03 Thermoplastic resin composition
JP2004510323A JP4534075B2 (ja) 2002-06-04 2003-06-03 熱可塑性樹脂組成物
HK05111790A HK1079807A1 (en) 2002-06-04 2005-12-21 Thermoplastic resin composition

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JP2002-162583 2002-06-04
JP2002162583 2002-06-04

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WO2003102076A1 true WO2003102076A1 (fr) 2003-12-11

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KR (1) KR101050701B1 (fr)
CN (1) CN1289593C (fr)
AU (1) AU2003241990A1 (fr)
HK (1) HK1079807A1 (fr)
WO (1) WO2003102076A1 (fr)

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WO2021014735A1 (fr) 2019-07-19 2021-01-28 東レ株式会社 Composition de résine thermoplastique transparente et article moulé à partir de cette dernière

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JP5687920B2 (ja) * 2010-03-03 2015-03-25 日本エイアンドエル株式会社 熱可塑性樹脂組成物
TWI465509B (zh) * 2012-12-28 2014-12-21 Chi Mei Corp 橡膠改質甲基丙烯酸酯系樹脂組成物
CN107250255B (zh) * 2015-02-12 2020-12-29 电化株式会社 光学用苯乙烯系树脂组合物
WO2020137843A1 (fr) * 2018-12-26 2020-07-02 東洋スチレン株式会社 Composition de résine, et corps moulé
US20220177628A1 (en) * 2019-03-15 2022-06-09 Toray Industries, Inc. Styrene-based thermoplastic resin composition, production method of styrene-based thermoplastic resin composition, molded article, and production method of molded article

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JP2001131368A (ja) * 1999-11-02 2001-05-15 Nippon A & L Kk 押出し成形用熱可塑性樹脂樹脂組成物
JP2001151974A (ja) * 1999-11-29 2001-06-05 Denki Kagaku Kogyo Kk 難燃性樹脂組成物
JP2001181470A (ja) * 1999-12-28 2001-07-03 Nippon A & L Kk 押出し成形用熱可塑性樹脂樹脂組成物
JP2001200134A (ja) * 2000-01-19 2001-07-24 Toray Ind Inc 透明性樹脂組成物およびそれからなる成形品
JP2001200131A (ja) * 2000-01-19 2001-07-24 Toray Ind Inc 難燃性樹脂組成物およびそれからなる成形品

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JP6801827B1 (ja) * 2019-07-19 2020-12-16 東レ株式会社 透明熱可塑性樹脂組成物およびその成形品
WO2021014735A1 (fr) 2019-07-19 2021-01-28 東レ株式会社 Composition de résine thermoplastique transparente et article moulé à partir de cette dernière
CN114127140A (zh) * 2019-07-19 2022-03-01 东丽株式会社 透明热塑性树脂组合物及其成型品
KR20220038283A (ko) 2019-07-19 2022-03-28 도레이 카부시키가이샤 투명 열가소성 수지 조성물 및 그 성형품
CN114127140B (zh) * 2019-07-19 2024-03-19 东丽株式会社 透明热塑性树脂组合物及其成型品

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CN1289593C (zh) 2006-12-13
KR20050024308A (ko) 2005-03-10
AU2003241990A1 (en) 2003-12-19
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