CN102190844A - 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, described thermoplastic resin composition is characterised in that, not only rerum natura balance, color emissivity excellence but also traumatic resistance are also excellent and then not produce the shaping that causes because of mold fouling bad.
Background technology
At present, phenylethylene resin series is owing to have good shaping processability and isostatic mechanical characteristics, and the electrical insulating property excellence, so be widely used in the extensive fields such as electric/electronic field, OA apparatus field.But at goods in the stage, the molding that ester moulding is obtained in order to prevent tiny scratch, is packed described molding with the softish non-woven fabrics sometimes one by one when for example being delivered to assembling line, therefore, need a large amount of man-hour and cost.
In addition, in order to give the various designs of resin or the damage of goods when preventing to use, sometimes goods are carried out whole applications or part application.But the problem that has the decrease in yield that is easy to generate the production that causes because of application is bad is handled in application.In addition, the trend of discharging from recent years inhibition VOC is colored as chromatic colour or dark color with handling or has metal-like or the outward appearance of pearly-lustre sample etc. in order unreally as far as possible to apply dress, preferably gives designability easily and is difficult for impaired resin.
On the other hand, for phenylethylene resin series, by making monomer copolymerizations such as vinylbenzene and vinyl cyanide, methyl methacrylate, can obtain with methyl methacrylate is the consistency of the excellence of resin.Therefore, according to various purposes these mishmashes (Alloy) have been proposed.For example, thus known have a method (patent documentation 1) of keeping plasticity and traumatic resistance being improved by specific wax, the specific fatty acid metal salt of an amount of combination in these mishmashes.But in recent years, for the purposes of the high-quality outward appearance of needs, traumatic resistance is still low and be not suitable for.In addition, also disclose, produce the problem that polysiloxane oozes out (bleed out), have the resin combination of ad hoc structure and can not improve the method (patent documentation 2) of traumatic resistance with oozing out by interpolation using under the situation of polysiloxane.But its color emissivity is insufficient and traumatic resistance is also insufficient.
Patent documentation 1: TOHKEMY 2006-2038 communique
Patent documentation 2: TOHKEMY 2001-40160 communique
Summary of the invention
The objective of the invention is to, a kind of thermoplastic resin composition and molding thereof are provided, and described thermoplastic resin composition not only has good rerum natura balance and color emissivity, and traumatic resistance is also excellent, and then, can also suppress and even prevent that the shaping that causes because of mold fouling is bad.
The inventor etc. concentrate on studies in order to solve prior art problems, found that, contain silicon-containing compound by making in the resin combination that comprises the multipolymer that graft copolymer that acrylic resin, certain monomers grafting form and certain monomers be polymerized with ad hoc structure, can reach above-mentioned purpose, finish the present invention thus.
Promptly, the present invention relates to the thermoplastic resin composition and use this resin combination and the molding that obtains, described thermoplastic resin composition is characterised in that, with respect to comprising (A) acrylic resin 20~80 weight parts, (B) in the presence of rubbery polymer, make and be selected from aromatic vinyl base system monomer, vinyl cyanide base system monomer, (methyl) but graft copolymer 15~50 weight parts that at least a monomer-grafted copolymerization in the monomer of acrylic ester monomer and other copolymerization forms, (C) make and be selected from aromatic vinyl base system monomer, vinyl cyanide base system monomer, (methyl) but resin combination 100 weight parts of (being total to) polymkeric substance 5~65 weight parts that at least a monomer copolymerization in the monomer of acrylic ester monomer and other copolymerization forms comprise (D) silicone compound supported on SiO 2 powder and silicon-containing compound 0.1~10 weight part that forms.
According to the present invention, can provide not only rerum natura balance, color emissivity excellence but also traumatic resistance also excellent and then do not produce cacoplastic thermoplastic resin composition and the molding thereof that causes because of mold fouling.
Embodiment
Below, the present invention is described in detail.
Thermoplastic resin composition used in the present invention is characterised in that, with respect to comprising (A) acrylic resin 20~80 weight parts, (B) in the presence of rubbery polymer, make and be selected from aromatic vinyl base system monomer, vinyl cyanide base system monomer, (methyl) but graft copolymer 15~50 weight parts that at least a monomer-grafted copolymerization in the monomer of acrylic ester monomer and other copolymerization forms, (C) make and be selected from aromatic vinyl base system monomer, vinyl cyanide base system monomer, (methyl) but resin combination 100 weight parts of (being total to) polymkeric substance 5~65 weight parts that at least a monomer copolymerization in the monomer of acrylic ester monomer and other copolymerization forms comprise (D) silicone compound supported on SiO 2 powder and silicon-containing compound 0.1~10 weight part that forms.
As acrylic resin used in the present invention (A), for example can enumerate: the multipolymer of polyalkyl methacrylate, alkyl methacrylate and alkyl acrylate etc.As alkyl methacrylate, for example can enumerate: methyl methacrylate, Jia Jibingxisuanyizhi etc.As the alkyl in the alkyl acrylate, the alkyl of preferred carbonatoms 2~10.As described alkyl acrylate, for example can enumerate: acrylate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, Ethyl acrylate, Octyl acrylate etc.
The multipolymer that uses alkyl methacrylate and alkyl acrylate is during as acrylic resin, alkyl methacrylate unit in this multipolymer is more than the 50 weight %, be preferably 50~99 weight %, the acrylic acid alkyl ester units is below the 50 weight %, is preferably 50~1 weight %.
Need in resin combination 100 weight parts, contain acrylic resin used in the present invention (A) 20~80 weight parts, be preferably 25~70 weight parts.When being lower than 20 weight, traumatic resistance and color emissivity reduce, and when surpassing 80 weight parts, shock-resistance reduces.
As the rubbery polymer that is used for graft copolymer used in the present invention (B), there is no particular limitation, for example can enumerate: diene series rubbers such as polybutadiene rubber, styrene butadiene rubbers (SBR), styrene-butadiene-styrene (SBS) segmented copolymer, vinylbenzene-(ethene-divinyl)-vinylbenzene (SEBS) segmented copolymer, acrylonitrile-butadiene rubber (NBR), butyl acrylate-divinyl; Butyl acrylate rubber, butadiene-acrylic acid butyl ester rubber, 2-EHA-butyl acrylate rubber, methacrylic acid 2-ethylhexyl-butyl acrylate rubber, stearyl acrylate ester-butyl acrylate rubber, organopolysiloxane-acrylic rubber such as butyl acrylate compounded rubber; Polyolefin rubber polymers such as ethylene-propylene rubber, ethylene-propylene-elastoprene; Silicon such as poly organo methane series rubber are rubber polymer, and these polymkeric substance can use more than a kind or 2 kinds.Preferred especially polybutadiene rubber, styrene butadiene rubbers, butyl acrylate rubber, ethylene-propylene-elastoprene.
Consider from rerum natura equilibrated viewpoint, preferably in graft copolymer (B) 100 weight parts, contain rubbery polymer 30~85 weight parts that use in the graft copolymer (B), more preferably contain 40~75 weight parts.
Consider that from the viewpoint of rerum natura balance and color emissivity the weight average particle diameter of the rubbery polymer that uses in the graft copolymer (B) is preferably 0.05~2.0 μ m, more preferably 0.1~1.0 μ m.
As the aromatic vinyl base system monomer that is used for graft copolymer (B), but illustration: 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, special optimization styrene.
As the vinyl cyanide base system monomer that is used for graft copolymer (B), but illustration: vinyl cyanide, methacrylonitrile, ethyl acrylonitrile, rich horse dintrile etc., can use more than a kind or a kind.As vinyl cyanide base system monomer, preferred especially vinyl cyanide.
As (methyl) acrylic ester monomer that is used for graft copolymer (B), but illustration: (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, the 6-tribromophenyl, (methyl) vinylformic acid mono chloro benzene ester, (methyl) vinylformic acid Dichlorfop, (methyl) vinylformic acid trichlorine phenyl esters etc. can use more than a kind or a kind.As (methyl) acrylic ester monomer, special preferable methyl methyl acrylate.
Consider from the viewpoint of traumatic resistance and color emissivity, preferably in graft copolymer (B) 100 weight parts, contain (methyl) acrylic ester monomer 13~68 weight parts, more preferably contain 20~50 weight parts.
In addition, as being used for graft copolymer (B) but other the monomer of copolymerization, for example can use maleimide be monomer (for example, N-phenylmaleimide, N-cyclohexyl maleimide etc.), unsaturated carboxylic acid or its acid anhydrides (for example vinylformic acid, methacrylic acid and maleic anhydride etc.), and acid amides be monomer (for example acrylamide and Methacrylamide etc.) etc., these monomers can use a kind or make up more than 2 kinds respectively.
In resin combination 100 weight parts, need to contain graft copolymer used in the present invention (B) 15~50 weight parts.When being lower than 15 weight parts, shock-resistance reduces, when surpassing 50 weight parts, and traumatic resistance and mobile the reduction.Be preferably 20~45 weight parts.
For the polymerization process of graft copolymer (B), there is no particular limitation, for example, can utilize the combination of letex polymerization, suspension polymerization, mass polymerization, solution polymerization or these methods to make.
(being total to) used in the present invention polymkeric substance (C) is for comprising aromatic vinyl base system monomer, vinyl cyanide base system monomer, (methyl) but (be total to) polymkeric substance that more than one monomer polymerizations in the monomer of acrylic ester monomer and other copolymerization obtain by making to be selected from, and employed monomer can use the identical monomer of narrating with the example of use in graft copolymer (B) of each monomer.
In resin combination 100 weight parts, need to contain (being total to) used in the present invention polymkeric substance (C) 5~65 weight parts.When being lower than 5 weight parts, impact strength decreased, when surpassing 65 weight parts, traumatic resistance reduces.Be preferably 10~45 weight parts.
There is no particular limitation for the polymerization process of (being total to) polymerization (C), can utilize the combination of known letex polymerization, suspension polymerization, mass polymerization, solution polymerization or these methods to make.
The silicon-containing compound that uses among the present invention (D) is for to make silicone compound support the compound of gained on SiO 2 powder.Specifically, on the surface of SiO 2 powder, supporting the silicon-containing compound of silicone compound gained.
As the silicone compound that is used for silicon-containing compound (D), but illustration: silicone oil, silicone rubber or its intermediate, silicone resin or its intermediate etc.
Silicone compound further can use in molecule or molecular end comprises the compound of for example epoxy group(ing) as reactive functional groups, acryloxy, methacryloxy, vinyl, phenyl, hydroxyl etc.Wherein, can preferably use the compound that contains methacryloxy.
The SiO 2 powder that is used for silicon-containing compound (D) works in the mode that supports (absorb, adsorb or keep) silicone compound, can use aerosil, precipitated silica or the broken silicon-dioxide of micro mist etc.The surface-area of these silicon-dioxide is preferably at 50~400m
2The scope of/g.Surface-area is easy to support silicone compound when this scope.
There is no particular limitation for the content of the silicone compound of the silicon-containing compound that uses among the present invention (D), considers from the viewpoint of traumatic resistance and color emissivity, preferably contains 40~80 weight parts in silicon-containing compound (D) 100 weight parts.In addition, consider that the volume average particle size of silicon-containing compound (D) is preferably in the scope of 5~250 μ m from viewpoint to the dispersive difficulty of resin combination.In addition, the bulk specific gravity of silicon-containing compound (D) is preferably in 0.1~0.7 scope.
With respect to resin combination 100 weight parts, the usage quantity of silicon-containing compound used in the present invention (D) is 0.1~10 weight part.When being lower than 0.1 weight part, traumatic resistance is insufficient, when surpassing 10 weight parts, and the color emissivity variation.Be preferably 0.1~3 weight part.
Thermoplastic resin composition among the present invention various additives that can suit as required to add, for example known antioxidant, photostabilizer, lubricant, softening agent, static inhibitor, tinting material, fire retardant, matting agent, weighting agent etc.
Thermoplastic resin composition among the present invention can use separately, also can mix use with other thermoplastic resin as required.As described other thermoplastic resin, for example can use polycarbonate resin, polybutylene terephthalate resin, pet resin, polyamide resin, polylactic resin etc.
Thermoplastic resin composition among the present invention can obtain by mixing mentioned component.Mixing can be used for example known devices that mix such as forcing machine, roller, Banbury, kneader.
And then, the thermoplastic resin composition among the present invention can utilize known method for example extrusion molding, injection molding forming, blow molding and press molding etc. form, can make various molding.
Embodiment
Embodiment below is shown the present invention is carried out more specific description, but the present invention is not limited to these embodiment.Need to prove that it is unit based on weight that " part " shown in the embodiment reaches " % ".
<embodiment 1~11 and comparative example 1~6 〉
With respect to the acrylic resin (A) of the proportion of composing shown in table 1 and the table 2, graft copolymer (B), multipolymer (C), and silicon-containing compound (D), mix Sumiplast Black HB (Sumitomo Chemical Co's manufacturing) 1.0 parts.Use the 50mm single shaft forcing machine (onk-net machinofacture) of band ventilating pit, melting mixing under 210 ℃ of conditions of working cylinder temperature is carried out granulating, obtains being colored as the particle of black thus.Need to prove that each composition of table 1 and table 2 expression is as follows.
Acrylic resin (A)
Acrylic resin (A-1): Sumipex LG (Sumitomo Chemical Co's manufacturing), the flowability of measuring under 230 ℃ of temperature, load 37.3N according to test method(s) JIS K7210 are 10g/10 minute.
Acrylic resin (A-2): Sumipex LG2 (Sumitomo Chemical Co's manufacturing), the flowability of measuring under 230 ℃ of temperature, load 37.3N according to test method(s) JIS K7210 are 15g/10 minute.
Acrylic resin (A-3): Sumipex LG21 (Sumitomo Chemical Co's manufacturing), the flowability of measuring under 230 ℃ of temperature, load 37.3N according to test method(s) JIS K7210 are 21g/10 minute.
Graftomer (B)
Graftomer (B-1): in being full of the reactor of nitrogen, add styrene butadiene rubbers latex (vinylbenzene 5 weight %, volume average particle size 0.25 μ m) 50 parts of (solids component), 150 parts in water, 0.1 part of disodium EDTA, 0.001 part in ferrous sulfate, 0.3 part of rongalite, after being heated to 60 ℃, added the mixture comprise 0.2 part of 15 parts of vinylbenzene, 35 parts of methyl methacrylates and hydrogen phosphide cumene continuously through 3 hours, and then polymerization 2 hours under 60 ℃ of conditions.Then, saltout, dewater, after the drying, obtain graft copolymer (B-1).The limiting viscosity of the percentage of grafting of the graft copolymer that obtains and the solvable composition of acetone (measure temperature 30 ℃) is respectively 50% and 0.50dl/g.
Graftomer (B-2): in being full of the reactor of nitrogen, add styrene butadiene rubbers latex (vinylbenzene 5 weight %, volume average particle size 0.25 μ m) 50 parts of (solids component), 150 parts in water, 0.1 part of disodium EDTA, 0.001 part in ferrous sulfate, 0.3 part of rongalite, after being heated to 60 ℃, added continuously the mixture that comprises 0.2 part of 35 parts of vinylbenzene, 15 parts of vinyl cyanide and hydrogen phosphide cumene through 3 hours, and then polymerization 2 hours under 60 ℃ of conditions.Then, saltout, dewater, after the drying, obtain graft copolymer (B-2).The limiting viscosity of the percentage of grafting of the graft copolymer that obtains and the solvable composition of acetone (measure temperature 30 ℃) is respectively 50% and 0.53dl/g.
Graftomer (B-3): in being full of the reactor of nitrogen, add styrene butadiene rubbers latex (vinylbenzene 5 weight %, volume average particle size 0.25 μ m) 50 parts of (solids component), 150 parts in water, 0.1 part of disodium EDTA, 0.001 part in ferrous sulfate, 0.3 part of rongalite, after being heated to 60 ℃, added continuously the mixture that comprises 0.2 part of 12 parts of vinylbenzene, 5 parts of vinyl cyanide, 33 parts of methyl methacrylates and hydrogen phosphide cumene through 3 hours, and then polymerization 2 hours under 60 ℃ of conditions.Then, saltout, dewater, after the drying, obtain graft copolymer (B-3).The limiting viscosity of the percentage of grafting of the graft copolymer that obtains and the solvable composition of acetone (measure temperature 30 ℃) is respectively 50% and 0.49dl/g.
Multipolymer (C)
Multipolymer (C-1): utilize known mass polymerization, obtain the multipolymer (C-1) that constitutes by vinylbenzene 75 weight parts, vinyl cyanide 25 weight parts.
Multipolymer (C-2): utilize known mass polymerization, obtain the multipolymer (C-2) that constitutes by vinylbenzene 30 weight parts, methyl methacrylate 70 weight parts.
Silicon-containing compound (D)
Silicon-containing compound (D-1): DC4-7081 (eastern beautiful DOW CORNING Co., Ltd. make) ... make 60 parts of silicone compounds that contain methacryloxy functional groups support the silicon-containing compound that on 40 parts of SiO 2 powders, forms.Bulk specific gravity: 0.3~0.5, particle diameter: 10~200 μ m
Silicon-containing compound (D-2): SH200-100CS (eastern beautiful DOW CORNING Co., Ltd. make) ... dimethyl silicone oil.Viscosity: 100mm
2/ s
Silicon-containing compound (D-3): BY27-007 (eastern beautiful DOW CORNING Co., Ltd. make) ... by the fusion particle (silicone content 50%) that ultra-high molecular weight dimethyl-silicon ketone polymer and ABS resin make that mixes.
<test example 1 〉
The colored particles that use obtains in each embodiment and comparative example is used for following evaluation.Its result is shown in table 1 and the table 2 respectively.
(1) color emissivity
Form and aspect by foundation JIS-Z8729 are measured yardstick as color emissivity are measured in the brightness (L*) of molding.As above-mentioned molding, the colored particles that use obtains in embodiment and comparative example, and the molding that use obtains by injection molding machine (Japanese smart steel manufacturing J-150EP, working cylinder temperature: 200 ℃, die temperature: 80 ℃) shaping (150mm * 120mm * 3mm).Spectrophotometer uses company of color institute manufacturing CMS-35SP in (strain) village.
(2) traumatic resistance
Use reciprocal wear testing machine (new eastern science Co., Ltd. makes, goods name: tribogear, TYPE:30S), it at the top ends diameter the fixing cotton of No. 3, plain weave Kanakin on the pressure head of 27mm, under the load of constant 1kg, carry out 50 times reciprocal (speed 600mm/ minute) friction on the molding surface.As above-mentioned molding, use and described (1) the middle identical molding of molding that uses.After the test, the damage on the surface of molding is confirmed in range estimation, carries out the evaluation of traumatic resistance according to following judgement.
Do not damage fully: ◎
Almost do not find damage: zero
Find small damage: △
Find obvious impairment: *
(3) mold fouling
The colored particles that use obtains in embodiment and comparative example, use the J-150EP of Japanese smart steel manufacturing, injection-molded 100 (shot) shaping treadmill test sheets (long 150mm, wide 150mm, thickness 3mm) under 240 ℃ of working cylinder design temperatures, 50 ℃ of die temperatures, 30 seconds the condition of circulation that is shaped, then, carry out the evaluation of mold fouling according to following judgement.
On die surface, do not find to change: zero
On die surface, find stain: △
Die surface is extremely dirty, the appearance poor of molding: *
(4) shock-resistance
The colored particles that use obtains in each embodiment and comparative example according to the various test films of ISO test method 294 shapings, is measured shock-resistance.
Shock-resistance with 4mm thickness, is measured the band breach summer than (Charpy) impact value according to ISO179.Unit: kJ/m
2
(5) flowability
The colored particles that use obtains in each embodiment and comparative example is measured 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 is rerum natura balance and color emissivity excellence not only, and traumatic resistance and mold fouling excellence.When particularly using the acrylic ester monomer as graft copolymer (B), rerum natura balance excellence not only, and, the traumatic resistance excellence.
As shown in Table 2, there is not to use the traumatic resistance of comparative example 1 of silicon-containing compound poor with ad hoc structure.In addition, traumatic resistance is good in the comparative example that has used silicone oil, produces mold fouling when causing being shaped but silicone oil oozes out.In the particulate comparative example 6 that has obtained having used compounded silicone polymer and ABS, traumatic resistance transitivity balance excellence, but color emissivity and mold fouling are poor.The color emissivity and the traumatic resistance of the comparative example 2 that the usage quantity of acrylic resin (A) is few are 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 mobile poor.
Industrial utilizability
Thermoplastic resin composition of the present invention has brought into play the characteristic of above-mentioned excellence, can utilize in the widely field of representative take electric/electronic field, OA apparatus field etc. Be particularly preferred for having both the purposes of excellent rerum natura balance and color emissivity, traumatic resistance.
Claims (5)
1. thermoplastic resin composition, it is characterized in that, with respect to comprising (A) acrylic resin 20~80 weight parts, (B) in the presence of rubbery polymer, make and be selected from aromatic vinyl base system monomer, vinyl cyanide base system monomer, (methyl) but graft copolymer 15~50 weight parts that at least a monomer-grafted copolymerization in the monomer of acrylic ester monomer and other copolymerization forms, and (C) make and be selected from aromatic vinyl base system monomer, vinyl cyanide base system monomer, (methyl) but resin combination 100 weight parts of (being total to) polymkeric substance 5~65 weight parts that at least a monomer copolymerization in the monomer of acrylic ester monomer and other copolymerization forms comprise (D) and silicone compound supported on SiO 2 powder and silicon-containing compound 0.1~10 weight part that forms.
2. thermoplastic resin composition as claimed in claim 1, it is characterized in that, graft copolymer (B) in the presence of rubbery polymer 30~85 weight %, making aromatic vinyl base system monomer 2~30 weight %, (methyl) but other monomer 0~40 weight % of acrylic ester monomer 13~68 weight %, vinyl cyanide base system monomer 0~40 weight %, other copolymerization carries out the graft copolymer that graft polymerization obtains, weight % is a benchmark with graft copolymer (B), and benchmark is made as 100 weight %.
3. thermoplastic resin composition as claimed in claim 1 is characterized in that, the volume average particle size of silicon-containing compound (D) is 5~250 μ m, and bulk specific gravity is 0.1~0.7.
4. thermoplastic resin composition as claimed in claim 1, it is characterized in that, the contained silicone compound of silicon-containing compound (D) in molecule or molecular end contain methacryloxy, in 100 weight part silicon-containing compounds, contain silicone compounds 40~80 weight parts.
5. a resin forming product is characterized in that, described thermoplastic resin composition obtains by claim 1.
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- 2011-03-02 CN CN201110051709.0A patent/CN102190844B/en active Active
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JP2003020378A (en) * | 2001-07-06 | 2003-01-24 | Nippon A & L Kk | Transparent sliding thermoplastic resin composition |
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CN104080846A (en) * | 2012-01-17 | 2014-10-01 | 日本A&L株式会社 | Rubber-reinforced styrene resin composition for resin foams, and resin foam |
CN115160604A (en) * | 2022-09-05 | 2022-10-11 | 成都思立可科技有限公司 | Ultrahigh molecular weight polysiloxane powder and preparation method thereof |
Also Published As
Publication number | Publication date |
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CN102190844B (en) | 2015-06-10 |
JP5687920B2 (en) | 2015-03-25 |
JP2011202155A (en) | 2011-10-13 |
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