KR20170025722A - Thermoplastic resin composition and molded article comprising the same - Google Patents
Thermoplastic resin composition and molded article comprising the same Download PDFInfo
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- KR20170025722A KR20170025722A KR1020150122581A KR20150122581A KR20170025722A KR 20170025722 A KR20170025722 A KR 20170025722A KR 1020150122581 A KR1020150122581 A KR 1020150122581A KR 20150122581 A KR20150122581 A KR 20150122581A KR 20170025722 A KR20170025722 A KR 20170025722A
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- 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
- C08L25/10—Copolymers of styrene with conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
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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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
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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
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
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Abstract
More particularly, the present invention relates to a thermoplastic resin composition comprising (a) an aromatic vinyl compound-conjugated diene compound-vinyl cyanide copolymer; And (b) an aromatic vinyl compound-vinyl cyanide copolymer; and a polyol-based heat stabilizer. The present invention also relates to a molded article comprising the thermoplastic resin composition.
According to the present invention, it is possible to provide a flame retardant resin composition which is excellent in discoloration resistance, reduced silver generation and excellent in appearance characteristics while providing mechanical properties equal to or higher than that of the flame retardant resin composition, The present invention provides an excellent thermoplastic resin composition and a molded article containing the same.
Description
The present invention relates to a thermoplastic resin composition, and more particularly, to a thermoplastic resin composition which is excellent in discoloration resistance, silver reduction amount, and excellent in appearance characteristics while providing mechanical properties equal to or higher than that of the thermoplastic resin composition. To a thermoplastic resin composition having excellent flame retardancy by reducing the content of a flammable substance in the resin composition.
Acrylonitrile-butadiene-styrene (ABS) resins are widely used in automotive products, electrical and electronic products, automobiles, and automobiles due to the stiffness and chemical resistance of acrylonitrile, butadiene and styrene processability, mechanical strength, Office equipment, etc., but there are drawbacks unstable to heat.
In order to improve the thermal stability of the ABS resin, a combination of metal soap and diketone metal salt; combination of? -diketone metal salt and zinc organic acid salt; A combination of an alkali or alkaline earth metal and a basic organic sulfonate or phenate complex; a combination of? -diketone metal salt and hydrotalcite; And a combination of calcium acetylacetonate and a zinc organic acid salt, a hydrocarbon wax, an ester of a polyol, a phosphorous acid ester, a zeolite or an epoxy compound; And the like. Currently, the most commonly used heat stabilizers are zinc salts or calcium salts of acetylacetone based on organotin-containing sulfur compounds; Or a calcium salt, a magnesium salt or a barium salt of an organic carboxylic acid are used in combination, but a satisfactory stabilizing effect on heat and light has not yet been exhibited.
The present invention provides a resin composition which is excellent in discoloration resistance, reduced in silver generation amount and excellent in appearance characteristics while providing mechanical properties equal to or greater than that of the resin composition, And an object of the present invention is to provide an excellent thermoplastic resin composition.
Another object of the present invention is to provide a molded article comprising the thermoplastic resin composition.
These and other objects of the present invention can be achieved by the present invention described below.
In order to achieve the above object, the present invention provides a thermoplastic resin composition comprising (a) an aromatic vinyl compound-conjugated diene compound-vinyl cyanide copolymer; And (b) an aromatic vinyl compound-vinyl cyanide copolymer; and a thermoplastic resin composition comprising a flame retardant and a polyol-based heat stabilizer.
The present invention also provides a molded article comprising the thermoplastic resin composition.
According to the present invention, it is possible to provide a flame retardant resin composition which is excellent in discoloration resistance, reduced silver generation and excellent in appearance characteristics while providing mechanical properties equal to or higher than that of the flame retardant resin composition, The present invention provides an excellent thermoplastic resin composition and a molded article containing the same.
1 is a photograph of the surface of the thermoplastic resin composition according to Example 1. Fig.
Fig. 2 is a photograph of the surface of the thermoplastic resin composition according to Comparative Example 4. Fig.
Hereinafter, the present invention will be described in detail.
The present inventors have found that when a thermoplastic resin composition comprising an aromatic vinyl compound-conjugated diene compound-vinyl cyan compound copolymer and an aromatic vinyl compound-vinyl cyan compound copolymer together with a flame retardant contains a polyol-based heat stabilizer, It is possible to improve the thermal stability.
The thermoplastic resin composition according to the present invention will be described in detail as follows.
The thermoplastic resin composition comprises (a) an aromatic vinyl compound-conjugated diene compound-vinyl cyanide copolymer; And (b) an aromatic vinyl compound-vinyl cyan compound copolymer; and a polyol-based heat stabilizer.
The conjugated diene compound of (a) is not particularly limited as long as it can be used for the copolymerization. Examples of the conjugated diene compound include 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, Butadiene, 1,3-pentadiene, isoprene, and derivatives thereof, and 1,3-butadiene can be preferably used. In this case, an excellent balance of mechanical strength and physical properties is obtained .
The conjugated diene compound (a) may be contained in an amount of 30 to 80% by weight, or 30 to 70% by weight, based on the copolymer (a), and has excellent mechanical properties within this range.
The aromatic vinyl compounds of (a) and (b) include, for example, one kind selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, vinyltoluene, Or more.
The aromatic vinyl compound contained in the (a) aromatic vinyl compound-conjugated diene compound-vinyl cyanide copolymer may be contained in an amount of 10 to 40% by weight or 10 to 30% by weight based on the copolymer (a) And an excellent balance of mechanical properties and physical properties within this range.
The aromatic vinyl compound contained in the aromatic vinyl compound-vinyl cyanide copolymer (b) is contained in an amount of 10 to 90% by weight, 30 to 90% by weight, or 70 to 90% by weight based on the copolymer (b) And has an excellent balance of mechanical properties and physical properties within this range.
The vinyl cyan compounds (a) and (b) may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile and derivatives thereof.
The vinyl cyan compound contained in the aromatic vinyl compound-conjugated diene compound-vinyl cyan compound copolymer (a) may be included in an amount of 1 to 30% by weight or 10 to 30% by weight based on the copolymer (a) , There is an effect of excellent flame retardancy and thermal stability within this range.
The vinyl cyan compound contained in the aromatic vinyl compound-vinyl cyan compound copolymer (b) may be contained in an amount of 10 to 90% by weight, 10 to 70% by weight, or 10 to 30% by weight based on the copolymer (b) And has an excellent mechanical property and flame retardancy within this range.
The aromatic vinyl compound-conjugated diene compound-vinyl cyanide copolymer (a) may be one obtained by emulsion polymerization, bulk polymerization, solution polymerization or suspension polymerization, and preferably emulsion polymerization. In this case, Compared to a resin produced by polymerization, it has an excellent impact resistance and gloss and an excellent balance of physical properties such as fluidity.
The aromatic vinyl compound-conjugated diene compound-vinyl cyan compound copolymer (a) may be obtained by copolymerizing an aromatic vinyl compound and a vinyl cyan compound grafted with a conjugated diene-based rubber polymer containing the conjugated diene compound And in this case, it is excellent in impact resistance and gloss, and has an excellent balance of physical properties such as fluidity.
The aromatic vinyl compound-conjugated diene compound-vinyl cyanide copolymer (a) may be included in an amount of 10 to 50% by weight, 20 to 45% by weight, or 25 to 40% by weight based on the base resin, The impact strength and the tensile strength are excellent within the range.
The aromatic vinyl compound-vinyl cyanide copolymer (b) may be contained in an amount of 50 to 90% by weight, 55 to 80% by weight, or 60 to 75% by weight based on the base resin. Within this range, And an excellent balance of physical properties.
The flame retardant is not particularly limited as long as it can be used in the thermoplastic resin composition, and may be, for example, a halogen flame retardant, preferably an aromatic bromine flame retardant.
Examples of the flame retardant include 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine, hexabromocyclododecane, tetrabromoxyclooctane, monochloro Tetrabromobisphenol A, brominated epoxy oligomer, bis (triphenylphosphine) pentoxide, tetrabromobisphenol A, tetrabromobisphenol A, brominated diphenylmethane, bis (Tribromophenoxy) ethane, tetrabromobisphenol A bis (allyl ether) and derivatives thereof, and in this case, there are effects of excellent mechanical properties and flame retardancy.
The flame retardant may be included in an amount of 10 to 30 parts by weight, 15 to 30 parts by weight, or 15 to 25 parts by weight based on 100 parts by weight of the base resin, and the flame retardancy is excellent within this range.
The polyol refers to a compound having two or more hydroxyl groups (-OH). Examples of the polyol-based heat stabilizer include a primary to tertiary alkyl group having 1 to 50 carbon atoms, a hydroxy group having 2 to 20 carbon atoms, and an ether And another example may include a primary to a tertiary alkyl group having 1 to 30 carbon atoms, a hydroxy group having 2 to 20 carbon atoms, and an ether group having 1 to 10 carbon atoms. Within this range, a compound having excellent thermal stability and compatibility It is effective.
Examples of the polyol type heat stabilizer include trimethylol propane, pentaerythritol, tripentaerythritol, xylitol, mannitol, sorbitol, glycerin, a mixture of glycerin oligomers having a degree of polymerization of 2 to 10, and a group consisting of hydroxystearyl alcohol . In this case, the heat stabilizer is easily dispersed in the matrix resin, and there is an effect of excellent compatibility between the polymer and the heat stabilizer.
The polyol type heat stabilizer may be contained in an amount of 0.01 to 1 part by weight, 0.1 to 1 part by weight, or 0.1 to 0.5 part by weight based on 100 parts by weight of the base resin. Within this range, excellent heat stability and mechanical properties There is no deterioration effect.
The thermoplastic resin composition may further include a heat stabilizer containing an organic tin together with the polyol heat stabilizer.
The organotin-containing heat stabilizer may be, for example, a derivative of di-n-methyltin, di-n-butyltin or di-n-octyltin, and specific examples thereof include dibutyltin dilaurate, dibutyltin maleate , Dibutyltin laurate-maleate, dibutyltin bis (mono-C 4 to C 8 alkyl malate), dibutyltin bis (lauroylmercaptide), dibutyltin S-S ' And the like), and the like.
The organotin-containing heat stabilizer may be included in an amount of 0.01 to 1 part by weight, 0.1 to 1 part by weight, or 0.1 to 0.5 part by weight based on 100 parts by weight of the base resin, The mechanical properties are not deteriorated.
The total content of the polyol series heat stabilizer and the organotin-containing heat stabilizer may be 0.01 to 1 part by weight, 0.1 to 1 part by weight, or 0.1 to 0.5 part by weight based on 100 parts by weight of the base resin, There is an effect that the thermal stability is excellent and the mechanical properties are not deteriorated.
The thermoplastic resin composition may include a pigment, and the pigment is not particularly limited as long as it is usable in a thermoplastic resin composition such as carbon black or titanium dioxide (TiO 2 ).
The pigment may be included in an amount of 1 to 10 parts by weight, or 1 to 5 parts by weight, based on 100 parts by weight of the base resin. Within this range, the pigment is excellent in coloring property and low in discoloration degree while maintaining mechanical properties .
The thermoplastic resin composition may be, for example, a tin-free thermoplastic resin composition. In this case, the thermoplastic resin composition is excellent in thermal stability and does not deteriorate mechanical properties.
For example, the thermoplastic resin composition may have a gas generation time of 20 minutes or more, 20 to 30 minutes, or 20 to 25 minutes, and the content of the combustible material in the resin composition is reduced within this range to provide an excellent flame retardancy.
The thermoplastic resin composition may have a discoloration degree (L) of 5.1 or less, 1 to 5, or 3 to 4.8.
The thermoplastic resin composition may optionally include additives such as a light stabilizer, an antioxidant, an antistatic agent, an antimicrobial agent or a lubricant within a range not affecting the physical properties.
The molded article according to the present invention is characterized by comprising the thermoplastic resin composition.
The molded article may be, for example, an injection molded article.
It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory only and are not to be taken by way of illustration in the practice of the practice of this invention. And it is natural that such variations and modifications are included in the appended claims.
[Example]
Example 1
33% by weight of a SAN resin having an acrylonitrile content of 25% by weight and a weight average molecular weight of 120,000 g / mol, 33% by weight of an ABS copolymer (product name: DP270 manufactured by LG Chemical Co., Ltd., 55% by weight of butadiene rubber) 21 parts by weight of 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine (product name: SR 245), 0.3 parts by weight of pentaerythritol , 3.5 parts by weight of carbon black (manufactured by Polyplus Co., Ltd., product name: BK50) as a pigment, 2 parts by weight of stearamide-based lubricant ethylenebisstearamide (EBA) as an additive, 0.5 part by weight of dimethylpolysiloxane, And 0.75 parts by weight of polytetrafluoroethylene were uniformly mixed through a Henschel mixer, and the mixture was introduced into a twin-screw extruder. The mixture was melted and kneaded at 190 to 230 ° C to prepare a resin composition in the form of pellets. The resin composition of It was prepared as specimens for measuring the resistance and flame retardancy.
Example 2
The procedure of Example 1 was repeated, except that 0.15 part by weight of pentaerythritol was added instead of 0.3 part by weight and 0.15 part by weight of di-n-butyltin maleate was added.
Comparative Example 1
The procedure of Example 1 was repeated, except that di-n-butyltin maleate was added in the same amount in place of pentaerythritol.
Comparative Example 2
Example 1 was carried out in the same manner as in Example 1, except that the same amount of zinc salt of acetylacetone was added in place of pentaerythritol.
Comparative Example 3
In Example 1, the same procedure as in Example 1 was carried out except that pentaerythritol was replaced with calcium salt of stearic acid in the same amount.
Comparative Example 4
In Example 1, the same procedure as in Example 1 was carried out except that pentaerythritol was not added.
[Test Example]
The properties of the thermoplastic resin composition specimens obtained in Examples 1 and 2 and Comparative Examples 1 to 4 were measured by the following methods, and the results are shown in Table 1 below.
How to measure
* Vertical Flammability (UL-94): A specimen with a thickness of 1/12 "was manufactured and evaluated according to the UL-94 test standard. Respectively.
The flame retardancy is divided into V-0, V-1, V-2 and burning, and the flame retardancy decreases with increasing V-0, V-1, V-2 and burning. Generally, The backing time is shortened and the flame retardancy tends to decrease as the thickness of the specimen becomes thinner. Therefore, even in the case of the same composition, the flame retardancy grade may vary depending on the thickness.
* Notched Izod Impact Strength (kgf · cm / cm): Measured according to standard measurement ASTM D256 using 1/8 "specimen.
Tensile Strength (TS, kgf / cm 2 ): Measured according to standard measurement ASTM D638 using specimens.
The degree of discoloration (DELTA E): The pellets obtained in the extruder were placed in an extruder and held for 15 minutes under the conditions of 230 to 250 DEG C to obtain specimens for thermal discoloration measurement. The specimens were extruded at the respective retention temperatures A, b 'and L', a ', and b' for the specimens before and after the retention were obtained using a color meter (Suga color computer) and the degree of discoloration was calculated by the following equation (1).
* Silver amount: Silver is a phenomenon that occurs during continuous injection molding, and refers to a phenomenon in which fine lines of silver are formed along the direction of flow of a raw material on the surface of a resin composition. This means that before the molded article is solidified, , Volatile components in raw materials, etc.). Therefore, the more the amount of silver on the surface of the molded article which is injected under the same conditions, the better the appearance of the molded article. The silver amount was evaluated by observing the surface of the specimen with the degree of discoloration by visual observation, and when the silver was hardly visible, when silver was present over the entire specimen, .
* Gas generation time (minute): The time during which the organic gas (hydrocarbon, bromine, etc.) in the resin composition generated during the compression / injection processing of the resin composition was generated was measured. The measurement was carried out at the set temperature (250 ° C), starting from the end of the measurement of the resin composition in the cylinder, and ending when the initial gas appeared at the inlet of the cylinder.
The organic gas is a combustible material that remains in the resin composition to decompose the resin composition. The longer the gas generation time is, the less organic material is generated in the resin composition. In this case, the residual amount of the organic material in the resin composition is reduced Therefore, the resin composition is excellent in thermal stability.
Flammability
(Erase time)
(3s)
(5 s)
(7 s)
(8 s)
(7 s)
(9 h)
As shown in Table 1, in Examples 1 to 3 prepared according to the present invention, the amount of silver was reduced while having an impact strength and a tensile strength equal to or higher than those of Examples 1 to 3, the discoloration degree and gas generation were remarkably improved, It was confirmed that the time for which the fire was erased was significantly reduced. 1, it was confirmed that almost no silver appeared on the surface of the thermoplastic resin composition prepared according to Example 1.
On the other hand, in the case of Comparative Example 4 which did not contain a heat stabilizer, it was found that the discoloration degree was very high, the gas generation time was remarkably low, and the heat stability was poor after 9 seconds passed until the flame was erased. I can confirm that a lot of silver appeared.
In addition, in Comparative Example 1 using the conventional organic tin-containing compound, it was confirmed that the discoloration degree, the gas generation time, and the time for which the flame was erased were not improved as compared with Comparative Example 4.
Further, in the case of Comparative Example 2 using a zinc salt of acetylacetone, neither the gas generation time nor the burn-out time was improved. In Comparative Example 3 using the calcium salt of the organic carboxylic acid, the degree of discoloration was also large, And the time for which the fire was erased was not improved.
As a result, when the thermoplastic resin composition of the present invention contains the polyol type heat stabilizer in a specific range together with the flame retardant in the thermoplastic resin composition, the content of the flammable material in the resin composition due to the increase in gas generation time during processing is reduced, It was confirmed that the thermoplastic resin composition having excellent color resistance and reduced silver generation due to the above characteristics and having excellent appearance characteristics can be realized.
Claims (18)
The conjugated diene compound of (a) is at least one compound selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, Wherein the thermoplastic resin composition is at least one selected from the group consisting of a thermoplastic resin and a thermoplastic resin.
The aromatic vinyl compound of (a) and (b) is at least one selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, vinyltoluene and derivatives thereof Wherein the thermoplastic resin composition is a thermoplastic resin composition.
Wherein the vinyl cyan compound of (a) and (b) is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile and derivatives thereof.
Wherein the aromatic vinyl compound-conjugated diene compound-vinyl cyanide copolymer (a) is contained in an amount of 10 to 50% by weight based on the base resin.
Wherein the aromatic vinyl compound-vinyl cyanide copolymer (b) is contained in an amount of 50 to 90% by weight based on the base resin.
Wherein the flame retardant is a halogen-based flame retardant.
Wherein the flame retardant is included in an amount of 10 to 30 parts by weight based on 100 parts by weight of the base resin.
Wherein the polyol-based heat stabilizer is a polyol comprising a primary to a tertiary alkyl group having 1 to 50 carbon atoms, a hydroxyl group having 2 to 20 carbon atoms, and an ether group having 1 to 20 carbon atoms.
Wherein the polyol type heat stabilizer is selected from the group consisting of trimethylol propane, pentaerythritol, tripentaerythritol, xylitol, mannitol, sorbitol, glycerin, a mixture of glycerol oligomers having a degree of polymerization of 2 to 10, and hydroxystearyl alcohol And at least one thermoplastic resin composition.
Wherein the polyol type heat stabilizer is contained in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the base resin.
Wherein the thermoplastic resin composition further comprises a thermostable agent containing organotin.
Wherein the organotin-containing heat stabilizer is contained in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the base resin.
Wherein the total content of the polyol series heat stabilizer and the organotin-containing heat stabilizer is 0.01 to 1 part by weight based on 100 parts by weight of the base resin.
Wherein the thermoplastic resin composition is a tin-free thermoplastic resin composition.
Wherein the thermoplastic resin composition comprises 1 to 10 parts by weight of pigment relative to 100 parts by weight of the base resin.
Wherein the thermoplastic resin composition has a gas generation time of 20 minutes or more.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190083850A (en) * | 2018-01-05 | 2019-07-15 | 주식회사 엘지화학 | Thermoplastic resin composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07188513A (en) | 1993-12-27 | 1995-07-25 | Sumitomo Dow Ltd | Antistatic resin composition |
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- 2015-08-31 KR KR1020150122581A patent/KR20170025722A/en not_active Application Discontinuation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07188513A (en) | 1993-12-27 | 1995-07-25 | Sumitomo Dow Ltd | Antistatic resin composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190083850A (en) * | 2018-01-05 | 2019-07-15 | 주식회사 엘지화학 | Thermoplastic resin composition |
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