KR102022998B1 - In situ trimodal abs based graft resin and preparation method thereof - Google Patents
In situ trimodal abs based graft resin and preparation method thereof Download PDFInfo
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- KR102022998B1 KR102022998B1 KR1020150144252A KR20150144252A KR102022998B1 KR 102022998 B1 KR102022998 B1 KR 102022998B1 KR 1020150144252 A KR1020150144252 A KR 1020150144252A KR 20150144252 A KR20150144252 A KR 20150144252A KR 102022998 B1 KR102022998 B1 KR 102022998B1
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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
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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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/05—Bimodal or multimodal molecular weight distribution
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Abstract
The present disclosure relates to an in situ trimodal ABS-based graft resin composition and a method of manufacturing the same. More specifically, (a) 100 wt% of an aromatic vinyl compound-conjugated diene-based rubber-vinyl cyan compound graft resin And (b) 2.5 to 4.5 parts by weight of the polymer aggregate having an average particle diameter of 800 to 3000 mm, wherein the graft resin is 40 to 70 parts by weight of the conjugated diene rubber, 20 to 40 parts by weight of the aromatic vinyl compound, and vinyl cyan compound 1 To 20 parts by weight of a polymerized graft copolymer, wherein the conjugated diene rubber is 30 to 45 wt% of the conjugated diene rubber having an average particle diameter of 500 to 2000 Pa, and 45 to 55 wt% of the conjugated diene rubber having an average particle diameter of 2500 to 4500 Pa %, And in situ trimodal ABS graft resin comprising 5 to 15% by weight of conjugated diene-based rubber having an average particle diameter of 4500 to 6000 kPa and its preparation It relates to the law.
According to the present invention, there is an effect to provide an ABS resin composition and a method of manufacturing the impact strength, particularly low temperature impact strength, fluidity and surface properties significantly improved in the in situ tri-modal system.
Description
The present disclosure relates to an in situ trimodal ABS graft resin and a method for preparing the same, and more specifically, (a) 100 parts by weight of an aromatic vinyl compound-conjugated diene rubber-vinylcyan compound graft resin. And (b) 2.5 to 4.5 parts by weight of the polymer aggregate having an average particle diameter of 800 to 3000 mm, wherein the graft resin is 40 to 70 parts by weight of the conjugated diene rubber, 20 to 40 parts by weight of the aromatic vinyl compound, and 1 to 1 vinyl cyan compound. It is a graft copolymer polymerized including 20 parts by weight, wherein the conjugated diene rubber is 30 to 45% by weight of the conjugated diene rubber having an average particle diameter of 500 to 2000Å, 45 to 55% by weight of the conjugated diene rubber of the average particle diameter of 2500 to 4500Å And an in situ trimodal ABS graft resin comprising 5 to 15 wt% of a conjugated diene rubber having an average particle diameter of 4500 to 6000 mm 3 and a method for manufacturing the same.
For ABS-based graft resins, the most commonly used general purpose resins in TVs, refrigerators, and automobiles, surface glossiness improvement is a potential property of the consumer because the higher the gloss, the higher the quality of the product.
For this purpose, a large-diameter rubber latex was used for the ABS-based graft resin, but there was a limit in surface gloss increase, and the reflection haze was lowered, and in particular, the impact strength was severely lowered. In addition, the use of small-diameter rubber latex has the opposite effect to that of large-diameter rubber latex, so to improve this, the large-diameter and the small-diameter are used in the latex state or by polymerizing the dried particles, respectively, but impact strength, surface gloss And the reflection haze was not satisfactory, the problem that the physical properties vary greatly depending on the injection conditions.
In order to solve this problem, three kinds of particles having average particle size, small diameter, large diameter and super-large diameter were introduced to ABS graft resin, and mainly after polymerizing ABS resin with two kinds of latex having different average particle diameters, Extrusion latex may be mixed during extrusion, or three latexes having different average particle diameters may be prepared first and then mixed during extrusion. However, this method has a disadvantage in that the economic and time loss is large because each particle must be prepared separately.
In order to solve the problems of the prior art as described above, an object of the present invention is to provide an ABS resin and a method of manufacturing the same as an in situ trimodal system.
The above and other objects of the present disclosure can be achieved by the present disclosure described below.
In order to achieve the above object, the present substrate is (a) 100 parts by weight of aromatic vinyl compound-conjugated diene-based rubber-vinyl cyan compound graft resin, and (b) 2.5 to 4.5 parts by weight of a polymer aggregate having an average particle size of 800 to 3000 Pa. Including, but the graft resin is a graft copolymer polymerized 40 to 70 parts by weight of conjugated diene rubber, 20 to 40 parts by weight of aromatic vinyl compound and 1 to 20 parts by weight of vinyl cyan compound, the conjugated diene rubber 30 to 45% by weight of the conjugated diene rubber having an average particle diameter of 500 to 2000Å, 45 to 55% by weight of the conjugated diene rubber having an average particle diameter of 2500 to 4500Å, and 5 to 15% by weight of the conjugated diene rubber having an average particle size of 4500 to 6000Å It provides an in situ tri-modal ABS-based graft resin comprising.
In addition, the present description is based on (i) 100 parts by weight of the total conjugated diene rubber, aromatic vinyl compound and vinyl cyan compound in total, 5 to 40 parts by weight of the conjugated diene rubber latex having an average particle diameter of 500 to 2000 mm (based on solid content). 5 to 40 parts by weight of the conjugated diene rubber latex having an average particle diameter of 2500 to 4500 mm (based on solids), 20 to 40 parts by weight of the aromatic vinyl compound, 1 to 20 parts by weight of the vinyl cyan compound, and 2.5 to 2.5 parts by weight of the polymer aggregate having an average particle size of 800 to 3000 mm. Polymerizing the solution having a mixture of 4.5 parts by weight, 0.01 to 3 parts by weight of an initiator, and 0.01 to 5 parts by weight of an emulsifier while heating the temperature from 45 to 55 ° C. to 70 to 80 ° C. for 80 to 100 minutes; And (ii) adding 0.01 to 3 parts by weight of an initiator after the polymerization reaction, raising the temperature to 75 to 85 ° C. (higher than the temperature rising temperature in step (i)), and then ripening for 30 to 80 minutes and terminating the reaction. It provides a method for producing an in situ tri-modal ABS-based graft resin comprising.
According to the present invention is an in situ trimodal system (in situ trimodal system) has an effect of providing an ABS-based resin and a method of manufacturing the improved impact strength, particularly low temperature impact strength, flowability and surface properties significantly.
Hereinafter, the in situ trimodal ABS resin of the present disclosure and a method of manufacturing the same will be described in detail.
The in situ trimodal ABS resin of the present invention comprises (a) 100 parts by weight of an aromatic vinyl compound-conjugated diene rubber-vinyl cyan compound graft resin, and (b) 2.5 to 4.5 parts by weight of a polymer aggregate having an average particle size of 800 to 3000 Pa. Including, but the graft resin is a graft copolymer polymerized 40 to 70 parts by weight of conjugated diene rubber, 20 to 40 parts by weight of aromatic vinyl compound and 1 to 20 parts by weight of vinyl cyan compound, the conjugated diene rubber 30 to 45% by weight of the conjugated diene rubber having an average particle diameter of 500 to 2000Å, 45 to 55% by weight of the conjugated diene rubber having an average particle diameter of 2500 to 4500Å, and 5 to 15% by weight of the conjugated diene rubber having an average particle size of 4500 to 6000Å Within this range, impact strength and surface properties are excellent.
As another example, the in situ trimodal ABS resin may include (a) 100 parts by weight of an aromatic vinyl compound-conjugated diene rubber-vinyl cyan compound graft resin, and (b) 2.5 to 4.5 parts by weight of a polymer aggregate having an average particle diameter of 800 to 3000 Pa. Wherein, the graft resin is a graft copolymer polymerized including 50 to 60 parts by weight of conjugated diene rubber, 25 to 35 parts by weight of aromatic vinyl compound and 5 to 15 parts by weight of vinyl cyan compound, the conjugated diene-based The rubber is 35 to 45% by weight of the conjugated diene rubber having an average particle diameter of 500 to 2000Å, 47 to 53% by weight of the conjugated diene rubber having an average particle size of 2500 to 4500Å, and 7 to 13% by weight of the conjugated diene rubber having an average particle size of 4500 to 6000Å It includes and has an excellent effect of impact strength and surface properties within this range.
The in situ trimodal system of the present disclosure refers to an in situ method in which three kinds of particles are generated in a reaction process, rather than mixing rubber latexes having different average particle diameters.
As another example, the average particle diameter of the polymer aggregate may be 1000 to 2700 mm 3, or 1500 to 2500 mm 3, and the rubber latex is excellent in this range.
As another example, the polymer aggregate may include 3.0 to 4.0 parts by weight, and in this case, the ratio of generating three kinds of rubber latex having different average particle diameters is appropriate, so that the surface gloss is improved in the ABS graft resin. Do.
The polymer aggregates are, for example, unsaturated carboxylic acid polymers or unsaturated carboxylic acid ester polymers, and specific examples thereof include carboxylic acid or ester monomers thereof; And a comonomer having a functional group; and may be a polymerized copolymer.
The unsaturated carboxylic acid or ester monomers thereof may be, for example, at least one selected from the group consisting of ethylenically unsaturated carboxylic acids, ester monomers thereof, and acrylate monomers.
The unsaturated carboxylic acid polymer may further include, for example, at least one comonomer selected from the group consisting of C 4-6 conjugated double bond monomers, monovinyl aromatic hydrocarbon monomers and vinyl cyan monomers, in which case the surface The characteristic is excellent effect.
The functional group may be at least one selected from the group consisting of an amide group, an alcohol group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a boric acid group.
The comonomer having the functional group may be at least one selected from the group consisting of methacrylic amide, acrylamide, methacrylic acid, and acrylic acid.
The conjugated diene rubber may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, and pyrrylene.
The vinyl cyan compound may be at least one selected from the group consisting of, for example, acrylonitrile, methacrylonitrile, and ethacrylonitrile.
The vinylaromatic compound may be at least one selected from the group consisting of styrene, α-methylstyrene, o-ethylstyrene, p-ethylstyrene, and vinyltoluene.
The in situ trimodal ABS graft resin may further include at least one selected from the group consisting of antistatic agents, flame retardants, ultraviolet stabilizers, lubricants, heat stabilizers, colorants and antioxidants.
The in situ trimodal ABS-based graft resin may be, for example, a gloss of 100 or more, or 100 to 120, measured according to ASTM D528.
For example, the in situ trimodal ABS graft resin may have an image sharpness (DOI) of 99 or more, or 99 to 110, measured by a Rhopoint IQ.
For example, the in situ trimodal ABS graft resin may have a reflection image quality (RIQ) of 94 or more, or 94 to 110, measured by a Rhopoint IQ.
The in situ trimodal ABS graft resin composition of the present disclosure may include, for example, 45 to 70 wt% of the in situ trimodal ABS graft resin and 30 to 55 wt% of the vinylaromatic compound-vinylcyan compound polymer. In this range, both the surface characteristics and the impact strength are excellent.
The method for preparing an in situ trimodal ABS graft resin according to the present disclosure is based on (i) 100 parts by weight of a total of the following conjugated diene-based rubber, aromatic vinyl compound, and vinyl cyan compound, and has an average particle diameter of 500 to 2000 Pa. 5 to 40 parts by weight of rubber latex (based on solids), 5 to 40 parts by weight of conjugated diene rubber latex (based on solids) with an average particle diameter of 2500 to 4500 mm, 20 to 40 parts by weight of aromatic vinyl compound, and 1 to 20 parts by weight of vinyl cyan compound , The mixture of 2.5 to 4.5 parts by weight of the polymer aggregate having an average particle diameter of 800 to 3000 Pa, 0.01 to 3 parts by weight of the initiator, and 0.01 to 5 parts by weight of the emulsifier was uniformly mixed at 45 to 55 ℃, then 80 to 80 to 70 to 80 ℃ Polymerizing while heating for 100 minutes; And (ii) adding 0.01 to 3 parts by weight of an initiator after the polymerization reaction, raising the temperature to 75 to 85 ° C. (higher than the temperature rising temperature in step (i)), and then ripening for 30 to 80 minutes and terminating the reaction. It may include.
For example, the polymer aggregate may include: (a) polymerizing 10 to 20 parts by weight of an unsaturated carboxylic acid or an ester monomer thereof; (b) polymerizing by introducing an emulsion form of 75 to 85 parts by weight of unsaturated carboxylic acid or its ester monomer and 5 to 10 parts by weight of a comonomer having a functional group in an emulsion form at 80 to 95% of the polymerization conversion rate; And (c) terminating the polymerization at a polymerization conversion rate of 98% or more during the polymerization.
The step (a) may be an emulsion polymerization at 75 to 85 ° C. using 0.1 to 0.5 parts by weight of an emulsifier, 0.05 to 0.02 parts by weight of an initiator and 60 to 70 parts by weight of ion-exchanged water.
The (a) unsaturated carboxylic acid or ester monomer thereof may be, for example, an ethylenic carboxylic acid, an ester thereof, an acrylate monomer, or a mixture thereof.
The unsaturated carboxylic acid polymer may further include one or more comonomers selected from the group consisting of C 4-6 conjugated double bond monomers, monovinyl aromatic hydrocarbon monomers and vinyl cyan monomers, for example, various rubbers. It is applicable to latex and has the effect of improving mechanical properties and surface properties.
The ethylenically unsaturated carboxylic acid may be at least one selected from the group consisting of acrylic acid, methacrylic acid, methyl acrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic acid.
The unsaturated carboxylic ester monomer may be, for example, an alkyl ester of the unsaturated carboxylic acid, ie an alkyl unsaturated carboxylic ester.
The functional group may be at least one selected from the group consisting of, for example, an amide group, an alcohol group, a carboxylic acid group, a sulfonic acid group, a phosphate group, and a boric acid group, and in this case, deteriorates the role of an emulsifier in the rubber latex or prevents ionic bonding. It is effective in causing the particles to collide effectively and make the particles grow larger.
The comonomer having the functional group may be at least one selected from the group consisting of methacrylic amide, acrylamide, methacrylic acid and acrylic acid.
Step (b) may be polymerized using, for example, 1 to 5 parts by weight of an emulsifier, 30 to 40 parts by weight of ion-exchanged water, and 0.5 to 2 parts by weight of an initiator.
The emulsifier may be at least one selected from the group consisting of, for example, allyl aryl sulfonate, alkali methyl alkyl sulfate, sulfonated alkyl esters, fatty acid soaps, and rosin acid alkali salts.
The initiator may be, for example, a water-soluble polymerization initiator, a fat-soluble polymerization initiator or a mixture thereof.
For example, the water-soluble polymerization initiator may be a persulfate salt, and the persulfate salt may be, for example, one or more selected from the group consisting of potassium persulfate, sodium persulfate, and ammonium persulfate.
The fat-soluble polymerization initiator may be a peroxy compound, for example, the peroxy compound may be, for example, cumene hydro peroxide, diisopropyl benzene hydroperoxide, azobis isobutylonitrile, tertiary butyl hydroperoxide, para It may be at least one selected from the group consisting of methane hydroperoxide, and benzoyl peroxide.
Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.
EXAMPLE
Example One
<Polymer Aggregate Preparation>
After filling the reactor with nitrogen or argon gas, 15 parts by weight of ethyl acrylate, 0.3 parts by weight of fatty acid soap (oleic acid potassium salt) as an emulsifier, 0.01 parts by weight of initiator potassium persulfate, and 65 parts by weight of ion-exchanged water were added at a temperature of 80 ° C. Emulsion polymerization was carried out at. In the emulsion polymerization, the polymerization conversion rate of 90% (based on the batch monomer conversion) 80% by weight of ethyl acrylate and 5 parts by weight of methacrylamide, 3 parts by weight of fatty acid soap (oleic acid potassium salt) as an emulsifier, 35 parts by weight of ion-exchanged water It was made in the form of 3 hours, and on the other side, 1 part by weight of initiator potassium persulfate and 165 parts by weight of ion-exchanged water were added for 3 hours, followed by emulsion polymerization at 80 ° C. The polymerization was terminated at the polymerization conversion rate of 98% or more during the emulsion polymerization, and the obtained polymer aggregate had an average particle diameter of 1970 mm 3.
In-situ trimodal ABS resin manufacturing
25 parts by weight of butadiene rubber latex with an average particle diameter of 1000 kPa and 35 parts by weight of butadiene rubber latex with 3000 kPa, 3 parts by weight of polymer aggregates with an average particle diameter of 2000 kPa, 0.07 part by weight of tertiary butyl hydroperoxide as an initiator in a nitrogen-substituted polymerization reactor. A solution containing 0.4 parts by weight of tertiary dodecyl mercaptan as a molecular weight regulator, 30 parts by weight of styrene, 10 parts by weight of acrylonitrile, and 0.5 parts by weight of potassium rosinate as an emulsifier was mixed at 50 ° C, and then heated up to 76 ° C for 90 minutes. After the reaction, 0.23 parts by weight of cumene hydroperoxide was added as an initiator, the temperature was raised to 80 ° C., and aged for 1 hour, after which the reaction was completed to prepare ABS latex. At this time, the polymerization conversion rate was 98%. Three rubber latexes having different average particle diameters and their contents in the ABS latex were identified through Capillary Hydrodynamic Fractionation (CHDF, Matec Applied Science, Model 1100).
The prepared ABS latex was aggregated with sulfuric acid, and dehydrated and dried to prepare ABS powder.
<Preparation of ABS Graft Resin Composition>
The prepared in-situ trimodal ABS resin powder and SAN resin was mixed in a weight ratio of 26:74 (ABS: SAN) to produce a specimen for measuring physical properties by injection molding.
Example 2
Except that 4 parts by weight of the polymer aggregate in Example 1 was the same as in Example 1.
Comparative example One
The same experiment as in Example 1 except that the polymer aggregate was not administered in Example 1.
Comparative example 2
The same experiment as in Example 1 was carried out except that the polymer aggregate was added in an amount of 1 part by weight.
Comparative example 3
Except that 5 parts by weight of the polymer aggregate in Example 1 was the same experiment as in Example 1.
[Test Example]
The characteristics of the specimens prepared in Examples 1 to 2 and Comparative Examples 1 to 3 were measured by the following method, and the results are shown in Table 1 below.
How to measure
* Average particle diameter (Å) and its content (% by weight): measured using Capillary Hydrodynamic Fractionation (CHDF, Matec Applied Science, Model 1100).
* Polymerization Conversion Rate (%): 1.5 g of the prepared latex was dried in a 150 ° C. hot air dryer for 15 minutes, and then weighed to obtain a total solids content (TSC). The polymerization conversion rate was calculated by Equation 1 below, and the average particle size The measurement was carried out by diluting the prepared latex 1g in distilled water 100g, using a light scattering measuring device (Nicomp), and recorded the number average particle diameter of the measuring device.
[Equation 1]
* Izod impact strength (1/4 ″, 1/8 ″; kgf · cm / cm): Measured according to ASTM 256.
* Glossiness: measured according to ASTM D528 at 45 ° angle.
Reflection haze: Measurements were made using 512 diodes arranged in a straight line to profile reflected light in large arcs from 14 ° to 27 ° using a Rhopoint IQ device. It was calculated by the following Equation 2 at a 20 ° angle.
[Equation 2]
DOI (Distinctness of Image): Rhopoint IQ measures how clear the reflected image is on the reflective surface. The higher the DOI, the clearer the image. Low DOI is caused by the distortion of reflected light in large surface structures and the surface looks like an orange peel (Orange Peel).
Reflected Image Quality (RIQ): The quality of the image reflected by Rhopoint IQ (RIQ) is measured by the phenomenon of orange peel and surface wave. The higher the value of the RIQ, the better the quality of the reflected image.
As shown in Table 1, Examples 1 and 2 of the present substrate not only had excellent impact strength but also excellent surface properties of gloss, DOI, reflective haze, and RIQ.
On the other hand, Comparative Examples 1 to 3, which do not contain polymer aggregates or contain small amounts or excessive amounts, have both reduced impact strength and surface properties.
Claims (13)
(ii) adding 0.01 to 3 parts by weight of an initiator after the polymerization reaction, raising the temperature to 75 to 85 ° C. (higher than the temperature rising temperature in step (i)), and then ripening for 30 to 80 minutes and terminating the reaction;
Including,
The polymer aggregate is (a) polymerizing 10 to 20 parts by weight of an unsaturated carboxylic acid or ester monomer thereof; (b) polymerizing by introducing an emulsion form of 75 to 85 parts by weight of unsaturated carboxylic acid or its ester monomer and 5 to 10 parts by weight of a comonomer having a functional group in an emulsion form at 80 to 95% of the polymerization conversion rate; And (c) terminating the polymerization at a polymerization conversion rate of 98% or more during the polymerization.
Step (a) is an in situ trimodal ABS graft, characterized in that the emulsion polymerization at 75 to 85 ℃ using 0.1 to 0.5 parts by weight of emulsifier, 0.05 to 0.02 parts by weight of initiator and 60 to 70 parts by weight of ion-exchanged water. Method for producing a resin.
The step (b) is a method for producing an in situ trimodal ABS graft resin, characterized in that the polymerization using 1 to 5 parts by weight of emulsifier, 30 to 40 parts by weight of ion-exchanged water and 0.5 to 2 parts by weight of initiator.
The emulsifier is at least one selected from the group consisting of allyl aryl sulfonate, alkali methyl alkyl sulfate, sulfonated alkyl ester, fatty acid soap, and rosin acid alkali salt. Way.
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| KR102468058B1 (en) * | 2018-09-28 | 2022-11-17 | 주식회사 엘지화학 | In-situ bimodal acrylonitrile-conjugated diene rubber-aromatic vinyl copolymer, method for preparing thereof and thermoplastic resin composition comprising thereof |
| KR20200077384A (en) | 2018-12-20 | 2020-06-30 | 주식회사 엘지화학 | Diene based rubber latex, preparation method thereof and core-shell structured graft copolymer comprising the same |
| WO2020130569A1 (en) * | 2018-12-20 | 2020-06-25 | 주식회사 엘지화학 | Diene-based rubber latex, manufacturing method thereof, and core-shell structured graft copolymer comprising same |
| KR102489409B1 (en) * | 2019-08-16 | 2023-01-17 | 주식회사 엘지화학 | Method for preparing vinylcyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer and thermoplastic resin composition contatining the same |
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| JP2896331B2 (en) * | 1995-08-30 | 1999-05-31 | 奇美実業股▲分▼有限公司 | Rubber modified styrenic resin composition |
| JP3350423B2 (en) * | 1997-11-26 | 2002-11-25 | 信越ポリマー株式会社 | ABS resin sheet |
| KR100585942B1 (en) * | 1999-06-24 | 2006-06-01 | 제일모직주식회사 | Thermoplastic resin composition with good heat resistance and elongation property |
| KR100564816B1 (en) | 2003-12-29 | 2006-03-27 | 제일모직주식회사 | Method of Preparing ABS Resin Composition with Good Heat Resistance, Transparence and Natural Color |
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