CN102190844B - Thermoplastic resin composition - Google Patents
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Abstract
The present invention provides a thermoplastic resin composition and a formed object thereof, wherein the thermoplastic resin composition has the following advantages: balanced physical property, excellent color emissivity, excellent damage resistance, and no inferior forming caused by mold pollution. The thermoplastic resin composition is characterized by comprising the following components relatively to 100 by weight parts of resin composition: (A) 20-80 by weight parts of acrylic resins; (B) 15-50 by weight parts of graft polymer which is obtained through graft copolymerization of at least one monomer selected from: aromatic vinyl monomer, vinyl cyanide monomer, (methyl)methyl acrylate monomer and other copolymerizable monomer; (C) 5-65 by weight parts of (co)polymer which is obtained through copolymerization of at least one monomer selected from: aromatic vinyl monomer, vinyl cyanide momomer, (methyl)methyl acrylate monomer and other copolymerizable monomer; and (D) 0.1-10 by weight parts of silicon-containing compound which is formed through carrying silicone compounds on silicon oxide powder.
Description
Technical field
The present invention relates to thermoplastic resin composition and molding thereof, the feature of described thermoplastic resin composition is, not only physical property balance, color emissivity are excellent but also the traumatic resistance also excellent and then cob webbing that do not produce because mold fouling causes.
Background technology
At present, phenylethylene resin series is owing to having good shaping processability and balanced mechanical characteristics, and electrical insulating property is excellent, so be widely used in electric/electronic field, OA apparatus field etc. widely in field.But in the goods stage, the molding obtained by ester moulding, when being such as delivered to assembling line, in order to prevent tiny scratch, sometimes being packed described molding one by one with soft non-woven fabrics, therefore, being needed a large amount of man-hours and cost.
In addition, the damage of goods during in order to give the various design of resin or prevent use, carries out whole application or part application to goods sometimes.But there is the problem easily producing the decrease in yield of the production caused because application is bad in application process.In addition, from the trend that suppression VOC in recent years discharges, in order to be colored as chromatic colour or dark color with unreally as far as possible can applying dress process or there is the outward appearance etc. of metal-like or pearly-lustre sample, preferably easily give designability and not easily damaged resin.
On the other hand, for phenylethylene resin series, by making vinylbenzene and the monomer copolymerization such as vinyl cyanide, methyl methacrylate, the consistency with the excellence of methyl methacrylate system resin can be obtained.Therefore, these mishmashes (Alloy) are proposed according to various object.Such as, there will be a known by the specific wax of appropriate combination, specifically fatty acid metal salt in these mishmashes thus maintain plasticity and the method that traumatic resistance is improved (patent documentation 1).But in recent years, for the purposes needing high-quality outward appearance, traumatic resistance is still low and be not suitable for.In addition, also disclose when using polysiloxane, produce polysiloxane and ooze out the problem of (bleed out), by adding the resin combination with ad hoc structure and traumatic resistance can not be improved method (patent documentation 2) with oozing out.But its color emissivity is insufficient and traumatic resistance is also insufficient.
Patent documentation 1: Japanese Unexamined Patent Publication 2006-2038 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2001-40160 publication
Summary of the invention
The object of the invention is to, there is provided a kind of thermoplastic resin composition and molding thereof, described thermoplastic resin composition not only has good physical property balance and color emissivity, and traumatic resistance is also excellent, and then, can also suppress and even prevent the cob webbing because mold fouling causes.
The present inventor etc. concentrate on studies to solve the problem of prior art, found that, by in the resin combination that makes to comprise the multipolymer of acrylic resin, specifically monomer-grafted graft copolymer and specific monomer polymerization containing the silicon-containing compound with ad hoc structure, can above-mentioned purpose be reached, this completes the present invention.
Namely, the molding that the present invention relates to thermoplastic resin composition and use this resin combination and obtain, the feature of described thermoplastic resin composition is, relative to comprising (A) acrylic resin 20 ~ 80 weight part, (B) make to be selected from aromatic vinyl base system monomer under the existence of rubbery polymer, vinyl cyanide base system monomer, (methyl) acrylic ester monomer and other can graft copolymer 15 ~ 50 weight part of the monomer-grafted copolymerization of at least one in the monomer of copolymerization, (C) make to be selected from aromatic vinyl base system monomer, vinyl cyanide base system monomer, (methyl) acrylic ester monomer and other can resin combination 100 weight part of (being total to) polymkeric substance 5 ~ 65 weight part of at least one monomer copolymerization in the monomer of copolymerization, comprise (D) and silicone compound is supported silicon-containing compound 0.1 ~ 10 weight part formed on SiO 2 powder.
According to the present invention, the excellent but also traumatic resistance of not only physical property balance, the color emissivity also excellent and then cacoplastic thermoplastic resin composition that do not produce because mold fouling causes and molding thereof can be provided.
Embodiment
Below, the present invention is described in detail.
The feature of thermoplastic resin composition used in the present invention is, relative to comprising (A) acrylic resin 20 ~ 80 weight part, (B) make to be selected from aromatic vinyl base system monomer under the existence of rubbery polymer, vinyl cyanide base system monomer, (methyl) acrylic ester monomer and other can graft copolymer 15 ~ 50 weight part of the monomer-grafted copolymerization of at least one in the monomer of copolymerization, (C) make to be selected from aromatic vinyl base system monomer, vinyl cyanide base system monomer, (methyl) acrylic ester monomer and other can resin combination 100 weight part of (being total to) polymkeric substance 5 ~ 65 weight part of at least one monomer copolymerization in the monomer of copolymerization, comprise (D) and silicone compound is supported silicon-containing compound 0.1 ~ 10 weight part formed on SiO 2 powder.
As acrylic resin used in the present invention (A), such as, can enumerate: the multipolymer etc. of polyalkyl methacrylate, alkyl methacrylate and alkyl acrylate.As alkyl methacrylate, such as, can enumerate: methyl methacrylate, β-dimethyl-aminoethylmethacrylate etc.As the alkyl in alkyl acrylate, the alkyl of preferred carbonatoms 2 ~ 10.As described alkyl acrylate, such as, can enumerate: acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, Ethyl acrylate, Octyl acrylate etc.
When using the multipolymer of alkyl methacrylate and alkyl acrylate as acrylic resin, alkylmethacrylate unit in this multipolymer is more than 50 % by weight, be preferably 50 ~ 99 % by weight, acrylate unit is less than 50 % by weight, is preferably 50 ~ 1 % by weight.
Need, containing acrylic resin used in the present invention (A) 20 ~ 80 weight part in resin combination 100 weight part, to be preferably 25 ~ 70 weight parts.During lower than 20 weight, traumatic resistance and color emissivity reduce, and during more than 80 weight part, shock-resistance reduces.
As the rubbery polymer for graft copolymer used in the present invention (B), there is no particular limitation, such as, can enumerate: the diene series rubbers such as polybutadiene rubber, styrene butadiene rubbers (SBR), styrene-butadiene-styrene (SBS) segmented copolymer, vinylbenzene-(ethylene-butylene)-vinylbenzene (SEBS) segmented copolymer, acrylonitrile-butadiene rubber (NBR), butyl acrylate-divinyl; The acrylic rubber such as butyl acrylate rubber, butadiene-propylene acid butyl ester rubber, 2-EHA-butyl acrylate rubber, 2-Ethylhexyl Methacrylate-butyl acrylate rubber, stearyl acrylate ester-butyl acrylate rubber, organopolysiloxane-butyl acrylate compounded rubber; The polyolefin rubber polymers such as ethylene-propylene rubber, Ethylene-Propylene-Diene rubber; The silicon system rubber polymers such as poly organo methane series rubber, these polymkeric substance can use one kind or two or more.Particularly preferably polybutadiene rubber, styrene butadiene rubbers, butyl acrylate rubber, Ethylene-Propylene-Diene rubber.
From the viewpoint of physical property balance, rubbery polymer 30 ~ 85 weight part preferably containing use in graft copolymer (B) in graft copolymer (B) 100 weight part, more preferably containing 40 ~ 75 weight parts.
From the viewpoint of physical property balance and color emissivity, the weight average particle diameter of the rubbery polymer used in graft copolymer (B) is preferably 0.05 ~ 2.0 μm, is more preferably 0.1 ~ 1.0 μm.
As the aromatic vinyl base system monomer for graft copolymer (B), can illustrate: vinylbenzene, alpha-methyl styrene, p-methylstyrene, t-butyl styrene and dimethyl styrene etc., can use more than a kind or a kind.As aromatic vinyl base system monomer, particularly preferably vinylbenzene.
As the vinyl cyanide base system monomer for graft copolymer (B), can illustrate: vinyl cyanide, methacrylonitrile, ethyl acrylonitrile, rich horse dintrile etc., can use more than a kind or a kind.As vinyl cyanide base system monomer, particularly preferably vinyl cyanide.
As (methyl) acrylic ester monomer for graft copolymer (B), can illustrate: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) phenyl acrylate, (methyl) vinylformic acid 4-tertiary butyl phenyl ester, (methyl) vinylformic acid bromobenzene ester, (methyl) vinylformic acid dibromo phenyl ester, (methyl) vinylformic acid 2, 4, 6-tribromophenyl, (methyl) vinylformic acid mono chloro benzene ester, (methyl) vinylformic acid Dichlorfop, (methyl) vinylformic acid trichlorine phenyl ester etc., more than a kind or a kind can be used.As (methyl) acrylic ester monomer, particularly preferably methyl methacrylate.
From the viewpoint of traumatic resistance and color emissivity, preferably in graft copolymer (B) 100 weight part, contain (methyl) acrylic ester monomer 13 ~ 68 weight part, more preferably containing 20 ~ 50 weight parts.
In addition, as for graft copolymer (B) other can the monomer of copolymerization, such as can use maleimide system monomer (such as, N-phenylmaleimide, N-N-cyclohexylmaleimide etc.), unsaturated carboxylic acid or its acid anhydrides (such as vinylformic acid, methacrylic acid and maleic anhydride etc.) and acid amides system monomer (such as acrylamide and Methacrylamide etc.) etc., these monomers can use a kind or combine two or more respectively.
Need in resin combination 100 weight part containing graft copolymer used in the present invention (B) 15 ~ 50 weight part.During lower than 15 weight part, shock-resistance reduces, and during more than 50 weight part, traumatic resistance and mobility reduce.Be preferably 20 ~ 45 weight parts.
For the polymerization process of graft copolymer (B), there is no particular limitation, such as, can utilize letex polymerization, suspension polymerization, mass polymerization, solution polymerization or these methods combination manufacture.
(being total to) used in the present invention polymkeric substance (C) for by make to be selected from comprise aromatic vinyl base system monomer, vinyl cyanide base system monomer, (methyl) acrylic ester monomer and other can more than one monomer polymerizations in the monomer of copolymerization and (being total to) polymkeric substance of obtaining, the monomer used can use the monomer identical with each monomer that the example used in graft copolymer (B) describes.
Need in resin combination 100 weight part containing (being total to) used in the present invention polymkeric substance (C) 5 ~ 65 weight part.During lower than 5 weight part, impact strength decreased, during more than 65 weight part, traumatic resistance reduces.Be preferably 10 ~ 45 weight parts.
For the polymerization process of (being total to) polymerization (C), there is no particular limitation, can utilize known letex polymerization, suspension polymerization, mass polymerization, solution polymerization or these methods combination manufacture.
The compound of silicon-containing compound (D) for making silicone compound support gained on SiO 2 powder used in the present invention.Specifically, for supporting the silicon-containing compound of silicone compound gained on the surface of SiO 2 powder.
As the silicone compound for silicon-containing compound (D), can illustrate: silicone oil, silicone rubber or its intermediate, silicone resin or its intermediate etc.
Silicone compound can use in the molecule further or molecular end comprises the compound of such as epoxy group(ing), acryloxy, methacryloxy, vinyl, phenyl, hydroxyl etc. as reactive functional groups.Wherein, the compound containing methacryloxy can preferably be used.
SiO 2 powder for silicon-containing compound (D) works in the mode supporting (absorption and sorption or maintenance) silicone compound, can use aerosil, precipitated silica or Crushing of Ultrafine silicon-dioxide etc.The surface-area of these silicon-dioxide is preferably at 50 ~ 400m
2the scope of/g.Surface-area, when this scope, is easy to support silicone compound.
There is no particular limitation for the content of the silicone compound of the silicon-containing compound (D) used in the present invention, from the viewpoint of traumatic resistance and color emissivity, preferably in silicon-containing compound (D) 100 weight part, contains 40 ~ 80 weight parts.In addition, from the viewpoint of the difficulty of the dispersion to resin combination, the volume average particle size of silicon-containing compound (D) is preferably the scope of 5 ~ 250 μm.In addition, the bulk specific gravity of silicon-containing compound (D) preferably 0.1 ~ 0.7 scope.
Relative to resin combination 100 weight part, the usage quantity of silicon-containing compound used in the present invention (D) is 0.1 ~ 10 weight part.During lower than 0.1 weight part, traumatic resistance is insufficient, and during more than 10 weight part, color emissivity is deteriorated.Be preferably 0.1 ~ 3 weight part.
Thermoplastic resin composition in the present invention can be suitable for adding various additive as required, such as known antioxidant, photostabilizer, lubricant, softening agent, static inhibitor, tinting material, fire retardant, matting agent, weighting agent etc.
Thermoplastic resin composition in the present invention can be used alone, also can be used in combination with other thermoplastic resin as required.As other described thermoplastic resin, such as, can use polycarbonate resin, polybutylene terephthalate resin, pet resin, polyamide resin, polylactic resin etc.
Thermoplastic resin composition in the present invention can be obtained by mixing mentioned component.Mixing can use the known devices that mix such as such as forcing machine, roller, Banbury, kneader.
And then the thermoplastic resin composition in the present invention can utilize known method such as extrusion molding, injection molding forming, blow molding and press molding etc. to form, and can manufacture various molding.
Embodiment
Below illustrate that embodiment carries out more specific description to the present invention, but the present invention is not limited to these embodiments.It should be noted that, " part " and " % " shown in embodiment is the unit based on weight.
< embodiment 1 ~ 11 and comparative example 1 ~ 6>
Relative to the acrylic resin (A) of the proportion of composing shown in table 1 and table 2, graft copolymer (B), multipolymer (C) and silicon-containing compound (D), mixing Sumiplast Black HB (Sumitomo Chemical Co's manufacture) 1.0 parts.Use the 50mm single axle extruding machine (onk-net machinofacture) of band ventilating pit, melting mixing under working cylinder temperature 210 DEG C of conditions, carries out granulating, obtains the particle being colored as black thus.It should be noted that, each composition that table 1 and table 2 represent is as follows.
acrylic resin (A)
Acrylic resin (A-1): Sumipex LG (Sumitomo Chemical Co's manufacture), the mobility measured under temperature 230 DEG C, load 37.3N according to test method(s) JIS K7210 are 10g/10 minute.
Acrylic resin (A-2): Sumipex LG2 (Sumitomo Chemical Co's manufacture), the mobility measured under temperature 230 DEG C, load 37.3N according to test method(s) JIS K7210 are 15g/10 minute.
Acrylic resin (A-3): Sumipex LG21 (Sumitomo Chemical Co's manufacture), the mobility measured under temperature 230 DEG C, load 37.3N according to test method(s) JIS K7210 are 21g/10 minute.
graftomer (B)
Graftomer (B-1): add styrene butadiene rubbers latex (vinylbenzene 5 % by weight, volume average particle size 0.25 μm) 50 parts of (solids component), 150 parts, water, disodium EDTA 0.1 part, 0.001 part, ferrous sulfate, rongalite 0.3 part in the reactor being full of nitrogen, after being heated to 60 DEG C, added the mixture comprising vinylbenzene 15 parts, methyl methacrylate 35 parts and hydrogen phosphide cumene 0.2 part through 3 hours continuously, and then be polymerized 2 hours under 60 DEG C of conditions.Then, saltout, dewater, after drying, obtain graft copolymer (B-1).The percentage of grafting of the graft copolymer obtained and the limiting viscosity (measuring temperature 30 DEG C) of acetone soluble ingredient are respectively 50% and 0.50dl/g.
Graftomer (B-2): add styrene butadiene rubbers latex (vinylbenzene 5 % by weight, volume average particle size 0.25 μm) 50 parts of (solids component), 150 parts, water, disodium EDTA 0.1 part, 0.001 part, ferrous sulfate, rongalite 0.3 part in the reactor being full of nitrogen, after being heated to 60 DEG C, added through 3 hours the mixture comprising vinylbenzene 35 parts, vinyl cyanide 15 parts and hydrogen phosphide cumene 0.2 part continuously, and then be polymerized 2 hours under 60 DEG C of conditions.Then, saltout, dewater, after drying, obtain graft copolymer (B-2).The percentage of grafting of the graft copolymer obtained and the limiting viscosity (measuring temperature 30 DEG C) of acetone soluble ingredient are respectively 50% and 0.53dl/g.
Graftomer (B-3): add styrene butadiene rubbers latex (vinylbenzene 5 % by weight, volume average particle size 0.25 μm) 50 parts of (solids component), 150 parts, water, disodium EDTA 0.1 part, 0.001 part, ferrous sulfate, rongalite 0.3 part in the reactor being full of nitrogen, after being heated to 60 DEG C, added through 3 hours the mixture comprising vinylbenzene 12 parts, vinyl cyanide 5 parts, methyl methacrylate 33 parts and hydrogen phosphide cumene 0.2 part continuously, and then be polymerized 2 hours under 60 DEG C of conditions.Then, saltout, dewater, after drying, obtain graft copolymer (B-3).The percentage of grafting of the graft copolymer obtained and the limiting viscosity (measuring temperature 30 DEG C) of acetone soluble ingredient are respectively 50% and 0.49dl/g.
multipolymer (C)
Multipolymer (C-1): utilize known mass polymerization, obtains the multipolymer (C-1) be made up of vinylbenzene 75 weight part, vinyl cyanide 25 weight part.
Multipolymer (C-2): utilize known mass polymerization, obtains the multipolymer (C-2) be made up of vinylbenzene 30 weight part, methyl methacrylate 70 weight part.
silicon-containing compound (D)
Silicon-containing compound (D-1): DC4-7081 (manufacture of Dong Li DOW CORNING Co., Ltd.) ... the silicone compound 60 parts containing methacryloxy functional groups is made to support the silicon-containing compound on SiO 2 powder 40 parts.Bulk specific gravity: 0.3 ~ 0.5, particle diameter: 10 ~ 200 μm
Silicon-containing compound (D-2): SH200-100CS (manufacture of Dong Li DOW CORNING Co., Ltd.) ... dimethyl silicone oil.Viscosity: 100mm
2/ s
Silicon-containing compound (D-3): BY27-007 (manufacture of Dong Li DOW CORNING Co., Ltd.) ... to be mixed ultra-high molecular weight dimethyl silicone polymers and ABS resin and the particle (silicone content 50%) made by melting.
< test example 1>
Be used in the colored particles obtained in each embodiment and comparative example, for following evaluation.Its result is shown in table 1 and table 2.
(1) color emissivity
By measuring according to the form and aspect of JIS-Z8729, yardstick as color emissivity is measured to the brightness (L*) of molding.As above-mentioned molding, be used in the colored particles obtained in embodiment and comparative example, use and to be shaped the molding (150mm × 120mm × 3mm) obtained by injection molding machine (J-150EP, working cylinder temperature manufactured by Japanese smart steel: 200 DEG C, die temperature: 80 DEG C).Spectrophotometer uses company of color institute in (strain) village to manufacture CMS-35SP.
(2) traumatic resistance
Use reciprocal wear testing machine (Xin Dong science Co., Ltd. manufactures, goods name: tribogear, TYPE:30S), at top ends diameter be 27mm pressure head on fix the cotton of No. 3, plain weave Kanakin, under the load of constant 1kg, carry out 50 times reciprocal (speed 600mm/ minute) friction on molding surface.As above-mentioned molding, use the molding identical with the molding used in described (1).After test, range estimation confirms the damage on the surface of molding, carries out the evaluation of traumatic resistance according to following judgement.
Do not damage completely: ◎
Almost do not find damage: zero
Find small damage: △
Find significantly damage: ×
(3) mold fouling
Be used in the colored particles obtained in embodiment and comparative example, use the J-150EP manufactured by Japanese smart steel, to be shaped dull and stereotyped test film (long 150mm, wide 150mm, thickness 3mm) at the condition hemostasis molding 100 times (shot) of working cylinder design temperature 240 DEG C, die temperature 50 DEG C, forming cycle 30 seconds, then, the evaluation of mold fouling is carried out according to following judgement.
Do not find change on the mold surface: zero
Find stain on the mold surface: △
Die surface is extremely dirty, the appearance poor of molding: ×
(4) shock-resistance
Be used in the colored particles obtained in each embodiment and comparative example, be shaped various test film according to ISO test method 294, measure shock-resistance.
Shock-resistance, according to ISO179, with 4mm thickness, measures band breach summer ratio (Charpy) impact value.Unit: kJ/m
2.
(5) mobility
Be used in the colored particles obtained in each embodiment and comparative example, measure melt volume-flow rate according to ISO1133.Unit: cm
3/ 10 minutes
[table 1]
[table 2]
As shown in Table 1, thermoplastic resin composition of the present invention not only physical property balance and color emissivity excellent, and traumatic resistance and mold fouling excellence.When particularly using acrylic ester monomer as graft copolymer (B), not only physical property balancing good, and also traumatic resistance is excellent.
As shown in Table 2, do not have to use the traumatic resistance with the comparative example 1 of the silicon-containing compound of ad hoc structure poor.In addition, in the comparative example employing silicone oil, traumatic resistance is good, but produces mold fouling when silicone oil oozes out and causes being shaped.Employing compounded silicone polymer and ABS and in the comparative example 6 of the particle obtained, traumatic resistance transitivity balancing good, but color emissivity and mold fouling poor.The color emissivity of the comparative example 2 that the usage quantity of acrylic resin (A) is few and traumatic resistance poor, the poor impact resistance of the comparative example 3 that usage quantity is many.The traumatic resistance of the comparative example 4 that the usage quantity of graft copolymer (B) is many and poor fluidity.
Industrial utilizability
Thermoplastic resin composition of the present invention has played the characteristic of above-mentioned excellence, can with electric/electronic field, OA apparatus field etc. for the field widely of representative in utilize.Be particularly preferred for combined with superior physical property balance and color emissivity, traumatic resistance purposes.
Claims (5)
1. a thermoplastic resin composition, it is characterized in that, relative to comprising (A) polyalkyl methacrylate as acrylic resin or multipolymer 20 ~ 80 weight part of alkyl methacrylate and alkyl acrylate, (B) make to be selected from aromatic vinyl base system monomer under the existence of rubbery polymer, vinyl cyanide base system monomer, (methyl) acrylic ester monomer and other can graft copolymer 15 ~ 50 weight part of the monomer-grafted copolymerization of at least one in the monomer of copolymerization, and (C) makes to be selected from aromatic vinyl base system monomer, vinyl cyanide base system monomer, (methyl) acrylic ester monomer and other can resin combination 100 weight part of multipolymer 5 ~ 65 weight part of at least two kinds of monomer copolymerizations in the monomer of copolymerization, comprising (D) makes silicone compound support silicon-containing compound 0.1 ~ 10 weight part formed on SiO 2 powder.
2. thermoplastic resin composition as claimed in claim 1, it is characterized in that, graft copolymer (B) for making aromatic vinyl base system monomer 2 ~ 30 % by weight, (methyl) acrylic ester monomer 13 ~ 68 % by weight, vinyl cyanide base system monomer 0 ~ 40 % by weight under the existence of rubbery polymer 30 ~ 85 % by weight, other other monomer 0 ~ 40 % by weight of copolymerization can carry out graft polymerization and the graft copolymer obtained, % by weight with graft copolymer (B) for benchmark, benchmark is set to 100 % by weight.
3. thermoplastic resin composition as claimed in claim 1, it is characterized in that, the volume average particle size of silicon-containing compound (D) is 5 ~ 250 μm, and bulk specific gravity is 0.1 ~ 0.7.
4. thermoplastic resin composition as claimed in claim 1, it is characterized in that, silicone compound contained by silicon-containing compound (D) in the molecule or molecular end contain methacryloxy, containing silicone compounds 40 ~ 80 weight part in 100 weight part silicon-containing compounds.
5. a resin forming product, is characterized in that, is obtained by thermoplastic resin composition according to claim 1.
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| JP5620835B2 (en) * | 2011-01-28 | 2014-11-05 | 日本エイアンドエル株式会社 | Thermoplastic resin composition |
| KR101531613B1 (en) * | 2011-11-24 | 2015-06-25 | 제일모직 주식회사 | Thermoplastic resin composition and molded product using the same |
| WO2013108719A1 (en) * | 2012-01-17 | 2013-07-25 | 日本エイアンドエル株式会社 | Rubber-reinforced styrene resin composition for resin foams, and resin foam |
| JP2019026716A (en) * | 2017-07-28 | 2019-02-21 | ユーエムジー・エービーエス株式会社 | Slidable resin composition and molded body of the same |
| CN115160604B (en) * | 2022-09-05 | 2022-11-18 | 成都思立可科技有限公司 | Ultrahigh molecular weight polysiloxane powder and preparation method thereof |
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| CN1659227A (en) * | 2002-06-04 | 2005-08-24 | 电气化学工业株式会社 | Thermoplastic resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102190844A (en) | 2011-09-21 |
| JP5687920B2 (en) | 2015-03-25 |
| JP2011202155A (en) | 2011-10-13 |
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