KR20160057601A - Thermoplastic resin composition - Google Patents
Thermoplastic resin composition Download PDFInfo
- Publication number
- KR20160057601A KR20160057601A KR1020140158400A KR20140158400A KR20160057601A KR 20160057601 A KR20160057601 A KR 20160057601A KR 1020140158400 A KR1020140158400 A KR 1020140158400A KR 20140158400 A KR20140158400 A KR 20140158400A KR 20160057601 A KR20160057601 A KR 20160057601A
- Authority
- KR
- South Korea
- Prior art keywords
- weight
- styrene
- thermoplastic resin
- acrylate rubber
- resin composition
- Prior art date
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Classifications
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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
-
- 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
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
Abstract
More particularly, the present invention relates to a thermoplastic resin composition comprising i) 25 to 50% by weight of a first graft copolymer comprising an acrylate rubber having an average particle diameter of 50 nm or more and 150 nm or less as a core, ii) 1 to 10% by weight of a second graft copolymer having an acrylate-based rubber as a core having a weight-average molecular weight of 150 to 200,000 g / mol, and 45 to 70% by weight of a high molecular weight styrene- 100 parts by weight of a base resin; And iv) 20 to 30 parts by weight of syndiotactic polystyrene, a derivative thereof, or a mixture thereof, as a quenching agent.
The present invention also provides a sheet for furniture produced by incorporating the thermoplastic resin composition.
According to the present invention, it is effective to provide a thermoplastic resin composition suitable for a sheet for furniture which has low gloss, coloring property and pencil hardness.
Description
The present invention relates to a thermoplastic resin composition, and more particularly to a thermoplastic resin composition suitable for a sheet for furniture because of its low gloss, coloring property and pencil hardness.
An acrylonitrile-styrene-acrylate copolymer using a crosslinked alkyl acrylate rubber polymer is a representative example of a thermoplastic resin having excellent weather resistance and aging resistance. The resin having excellent weatherability and aging resistance is used in various fields such as automobiles, ships, leisure goods, building materials, gardening, etc., and its usage is rapidly increasing. The products made from ASA resin are mostly shiny and the ASA resin extruded products exhibit surface gloss within the range of high gloss (90 gloss at 75 °) or intermediate gloss (60 gloss at 75 °).
In recent years, however, as the level of emotional quality of users has increased, there has been an increasing demand for low-gloss resin in order to produce a more refined atmosphere. In addition, as environmental problems have arisen, a matte resin or a pad- It is a trend to use directly.
In order to manufacture such a low-gloss resin, a method of increasing the low-gloss property by injecting large-diameter rubber particles or a light-quenching agent has been disclosed. However, when a small amount is injected, low- have.
Also, when used as a sheet, it is required to have excellent colorability and scratch resistance for aesthetic appearance, and it is necessary to adjust the gloss so as not to be conspicuous even if scratches occur.
In order to solve the problems of the related art as described above, the present invention aims at providing a thermoplastic resin composition which is excellent in low gloss, coloring property and pencil hardness and is suitable as a sheet for furniture.
It is another object of the present invention to provide a furniture sheet comprising the above thermoplastic resin composition.
These and other objects of the present disclosure can be achieved by all of the present invention described below.
In order to achieve the above object, the present invention provides a rubber composition comprising i) 25 to 50% by weight of a first graft copolymer having an acrylate rubber core having an average particle diameter of 50 nm or more and 150 nm or less as the core, ii) 1 to 10% by weight of a second graft copolymer having an acrylate rubber as a core, and iii) 45 to 70% by weight of a high molecular weight styrene resin having a weight average molecular weight of 150,000 to 200,000 g / mol. 100 parts by weight of a resin; And iv) 20 to 30 parts by weight of syndiotactic polystyrene, derivatives thereof, or mixtures thereof as a quenching agent.
Further, the present invention provides a sheet produced by including the above-mentioned thermoplastic resin composition.
As described above, according to the present invention, there is an effect of providing a thermoplastic resin composition suitable as a sheet for furniture having low gloss, coloring property and pencil hardness.
Hereinafter, the present invention will be described in detail.
The thermoplastic resin composition according to the present invention comprises i) 25 to 50% by weight of a first graft copolymer comprising an acrylate rubber having an average particle diameter of 50 nm or more and 150 nm or less as a core, ii) an acrylate based resin having an average particle diameter of 150 nm to 800 nm 1 to 10% by weight of a second graft copolymer having rubber as a core, and iii) 45 to 70% by weight of a high molecular weight styrene resin having a weight average molecular weight of 150,000 to 200,000 g / mol, ; And iv) 20 to 30 parts by weight of syndiotactic polystyrene, derivatives thereof, or mixtures thereof as a quenching agent.
The acrylate rubber of the first graft copolymer may have an average particle size of 50 nm to 150 nm, 60 nm to 140 nm, or 70 nm to 130 nm, for example, and has an excellent glossiness and colorability within the above range.
The acrylate rubber of the second graft copolymer may have an average particle size of more than 150 nm and less than 800 nm, 200 nm to 750 nm, or 250 nm to 700 nm, for example. Within this range, the impact resistance and flexural strength are excellent.
The first graft copolymer and the second graft copolymer may be obtained by graft-polymerizing an aromatic vinyl compound and a vinyl cyan compound on each acrylate rubber core.
As another example, the first graft copolymer and the second graft copolymer each contain 20 to 60% by weight of an aromatic vinyl compound and 5 to 40% by weight of a vinyl cyan compound in 30 to 70% by weight of each acrylate rubber Or graft-polymerized from 40 to 60% by weight of each acrylate-based rubber, 30 to 50% by weight of an aromatic vinyl compound and 10 to 30% by weight of a vinyl cyanide compound. Within the above range, the impact resistance and appearance characteristics are excellent.
The acrylate-based rubber may be, for example, an alkyl acrylate rubber.
The alkyl acrylate rubber may be at least one selected from the group consisting of methyl acrylate rubber, ethyl acrylate rubber, butyl acrylate rubber and ethylhexyl acrylate rubber.
The aromatic vinyl compound is at least one selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, 2,4-dimethylstyrene and vinyltoluene.
The vinyl cyan compound is, for example, acrylonitrile, methacrylonitrile, or a mixture thereof.
The total content of rubber in the entire first graft copolymer and the second graft copolymer may be, for example, 12 to 24% by weight, 14 to 22% by weight or 16 to 20% by weight, This has an excellent effect.
Examples of the high molecular weight styrene resin include styrene / acrylonitrile copolymer,? -Methylstyrene / acrylonitrile copolymer, styrene / methyl methacrylate copolymer, styrene / maleic anhydride copolymer,? -Styrene / Acrylonitrile copolymer, or an? -Styrene / acrylonitrile copolymer.
The high molecular weight styrenic resin has a weight average molecular weight of 150,000 to 200,000 g / mol, 160,000 to 190,000 g / mol or 170,000 to 180,000 g / mol, for example, and has an excellent pencil hardness and a matting effect within the above range .
The base resin may be, for example, i) 25 to 50% by weight of the first graft copolymer, ii) 1 to 10% by weight of the second graft copolymer, and iii) a high molecular weight polymer having a weight average molecular weight of 150,000 to 200,000 g / 45 to 70% by weight of a styrenic resin, i) 30 to 40% by weight of a first graft copolymer, ii) 3 to 7% by weight of a second graft copolymer, and iii) a weight average molecular weight of 150,000 to 200,000 g / mol, and 50 to 65% by weight of a high molecular weight styrene resin. Within this range, there is an effect of excellent impact resistance, pencil hardness and coloring property.
Examples of the syndiotactic polystyrenes include, but are not limited to, diene polystyrenes having a stereoregularity of 85% or more, pentad (racemic pentad) polystyrenes having a stereoregularity of 35% or more, polyhalogenated styrene, polyalkoxystyrene, polyalkylstyrene, Modified ester styrene, and copolymers based on at least one of them.
Examples of the syndiotactic polystyrene derivatives include polyhalogenated styrene, polyalkoxystyrene, polyalkylstyrene, polybenzoic ester styrene, syndiotactic polystyrene maleic anhydride (sPS-MAH), carboxyl terminal-syndiotactic polystyrene (sPS-COOH ), Maleic anhydride-syndiotactic polystyrene (sPS-MAH), maleic acid-syndiotactic polystyrene (sPS-MA), fumaric acid-syndiotactic polystyrene (sPS-FA), glycidyl methacrylate- (SPS-GMA), and copolymers composed mainly of them, and is preferably syndiotactic polystyrene maleic anhydride.
The thermoplastic resin composition has a glossiness of, for example, 45 to 72.5, 60 to 72.5 or 60 to 70, and the visual exposure to scratches generated within the above range is reduced.
The thermoplastic resin composition may contain at least one additive selected from the group consisting of a dropping inhibitor, a flame retardant, an antibacterial agent, an antistatic agent, a stabilizer, a releasing agent, a heat stabilizer, an inorganic additive, a lubricant, an antioxidant, a UV stabilizer, a pigment, .
There is provided a sheet comprising the composition of the present invention.
The seat may be, for example, for furniture.
The furniture can be, for example, a built-in kitchen, a living room, or a bathroom furniture for offices and kitchens.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.
[Example]
Example 1
The first graft copolymer was prepared by mixing 35 wt% of a copolymer comprising 50 wt% of butylacrylate rubber having an average particle size of 130 nm as a core and graft-polymerizing 30 wt% of styrene and 20 wt% of acrylonitrile, The copolymer contained 5% by weight of a copolymer obtained by graft-polymerizing 30% by weight of styrene and 20% by weight of acrylonitrile with 50% by weight of butyl acrylate rubber having an average particle diameter of 500 nm as a core and a copolymer having a weight average molecular weight of 200,000 g / mol 20 parts by weight of syndiotactic polystyrene (99% by weight) as a quencher was mixed with 100 parts by weight of a base resin containing 60% by weight of high molecular weight SAN resin, and then 1 part by weight of the lubricant, 0.5 part by weight of antioxidant, And 0.5 part by weight of a stabilizer were added thereto, and this was made into a pellet form at a cylinder temperature of 220 DEG C by using an extrusion kneader, and the thermoplastic resin composition specimen Joe was.
Example 2
A thermoplastic resin composition specimen was prepared in the same manner as in Example 1, except that 25 parts by weight of syndiotactic polystyrene was added as a quencher in Example 1.
Example 3
A thermoplastic resin composition specimen was prepared in the same manner as in Example 1, except that 30 parts by weight of syndiotactic polystyrene was added as a quencher in Example 1.
Comparative Example 1
A thermoplastic resin composition specimen was prepared in the same manner as in Example 1 except that syndiotactic polystyrene was not added as a quencher in Example 1.
Comparative Example 2
A thermoplastic resin composition specimen was prepared in the same manner as in Example 1 except that 60 wt% of a low molecular weight SAN resin having a weight average molecular weight of 120,000 g / mol was used in Example 1 and a quenching agent was not used .
Comparative Example 3
A thermoplastic resin specimen was prepared in the same manner as in Example 1, except that 5 wt% of the first graft copolymer and 35 wt% of the second graft copolymer were used in Example 1.
[Test Example]
The properties of the physical specimens prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were measured by the following methods, and the results are shown in Table 1 below.
* Average particle size: measured by Particle Size Analyzer (NICOM TM 80).
* Stereochemistry diagram: Measured quantitatively based on 13 C-NMR.
Impact strength (kgf · cm / cm): measured according to ASTM D256 at 1/4 "Notched.
* Pencil hardness: measured according to ASTM D2197.
Flexural Strength (kgf / cm 2 ): Measured according to ASTM D790.
Tensile strength (kgf / cm 2 ): Measured according to ASTM D638.
* Polishing degree: Measured according to ASTM D528 at an angle of 45 °.
* Appearance: The L value of the colorimetric specimen was measured using a colorimeter. At this time, the lower the L value, the lower the brightness and the darker the black color.
Copolymer
Copolymer
SAN resin
SAN resin
As shown in Table 1, it was confirmed that Examples 1 to 3 of the present invention had an impact strength, a pencil hardness, a flexural strength, a tensile strength, a gloss, and a coloring property superior to those of Comparative Examples 1 and 2.
In addition, Example 1 and Comparative Example 1, which differed only in the use of a polish agent, had an effect that the mechanical properties of Example 1 were superior to that of Comparative Example 1, and the gloss was lowered.
Also, in Comparative Example 2 using a low molecular weight SAN resin having a weight average molecular weight of 120,000 g / mol, pencil hardness, flexural strength and tensile strength were poor.
Claims (15)
Ii) 1 to 10% by weight of a second graft copolymer having an acrylate rubber having an average particle diameter of more than 150 nm and not more than 800 nm as a core, and
Iii) 100 parts by weight of a base resin comprising 45 to 70% by weight of a high molecular weight styrene resin having a weight average molecular weight of 150,000 to 200,000 g / mol; And
(Iv) 20 to 30 parts by weight of syndiotactic polystyrene, derivatives thereof, or mixtures thereof, as a quenching agent.
The thermoplastic resin composition according to claim 1, wherein the acrylate rubber is an alkyl acrylate rubber.
Wherein the alkyl acrylate rubber is at least one selected from the group consisting of methyl acrylate rubber, ethyl acrylate rubber, butyl acrylate rubber and ethylhexyl acrylate rubber.
Wherein the first graft copolymer and the second graft copolymer are graft-polymerized with an aromatic vinyl compound and a vinyl cyan compound, respectively, on an acrylate rubber core.
The first graft copolymer and the second graft copolymer are obtained by graft-polymerizing 20 to 60% by weight of an aromatic vinyl compound and 5 to 40% by weight of a vinyl cyan compound in 30 to 70% by weight of an acrylate rubber Wherein the thermoplastic resin composition is a thermoplastic resin composition.
Wherein the aromatic vinyl compound is at least one selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, 2,4-dimethylstyrene and vinyltoluene.
Wherein the vinyl cyan compound is acrylonitrile, methacrylonitrile or a mixture thereof.
Wherein the total content of the rubber in the first graft copolymer and the second graft copolymer is from 12 to 24% by weight.
The high molecular weight styrenic resin having a weight average molecular weight of 150,000 to 200,000 g / mol may be a styrene / acrylonitrile copolymer, an? -Methylstyrene / acrylonitrile copolymer, a styrene / methyl methacrylate copolymer, a styrene / Styrene / maleic anhydride copolymer,? -Styrene / acrylonitrile copolymer, or? -Styrene / acrylonitrile copolymer.
The syndiotactic polystyrene derivative may be at least one selected from the group consisting of polyhalogenated styrene, polyalkoxystyrene, polyalkylstyrene, polybenzoic acid ester styrene, syndiotactic polystyrene maleic anhydride (sPS-MAH), carboxyl terminal-syndiotactic polystyrene ), Maleic anhydride-syndiotactic polystyrene (sPS-MAH), maleic acid-syndiotactic polystyrene (sPS-MA), fumaric acid-syndiotactic polystyrene (sPS-FA), glycidyl methacrylate- (SPS-GMA), and a copolymer mainly composed of the thermoplastic resin and the thermoplastic resin composition.
The syndiotactic polystyrene may be selected from the group consisting of a diene polystyrene having a stereoregularity of 85% or more, a pentad (racemic pentad) polystyrene having a stereoregularity of 35% or more, a polyhalogenated styrene, a polyalkoxystyrene, a polyalkylstyrene, Styrene, styrene, styrene, styrene, styrene, and styrene, and a copolymer mainly composed of these.
Wherein the thermoplastic resin composition has a gloss of 45 to 72.5.
The thermoplastic resin composition may contain at least one additive selected from the group consisting of a dropping inhibitor, a flame retardant, an antibacterial agent, an antistatic agent, a stabilizer, a releasing agent, a heat stabilizer, an inorganic additive, a lubricant, an antioxidant, a UV stabilizer, a pigment, The thermoplastic resin composition according to claim 1,
Wherein the sheet is for furniture.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140158400A KR20160057601A (en) | 2014-11-14 | 2014-11-14 | Thermoplastic resin composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140158400A KR20160057601A (en) | 2014-11-14 | 2014-11-14 | Thermoplastic resin composition |
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| KR20160057601A true KR20160057601A (en) | 2016-05-24 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180052333A (en) * | 2016-11-10 | 2018-05-18 | 주식회사 엘지화학 | Thermoplstic resin composition with good low gloss, weather resistant property and mechanical properties, and extruded articles produced from the same |
| CN109071912A (en) * | 2016-11-04 | 2018-12-21 | 株式会社Lg化学 | Thermoplastic resin composition, preparation method and the mechanograph comprising it |
| WO2019112239A1 (en) * | 2017-12-04 | 2019-06-13 | 주식회사 엘지화학 | Thermoplastic resin composition |
| US10351699B2 (en) | 2015-11-10 | 2019-07-16 | Lg Chem, Ltd. | Thermoplastic resin composition providing superior low-gloss characteristic, weather resistance, and mechanical properties and extruded article manufactured from the same |
| KR20200046696A (en) | 2018-10-25 | 2020-05-07 | 주식회사 엘지화학 | Thermoplastic resin composition |
| CN111386309A (en) * | 2017-12-04 | 2020-07-07 | 株式会社Lg化学 | Thermoplastic resin composition |
| WO2022065625A1 (en) * | 2020-09-22 | 2022-03-31 | (주) 엘지화학 | Thermoplastic resin composition and molded product thereof |
| US11401409B2 (en) | 2017-11-09 | 2022-08-02 | Lg Chem, Ltd. | Thermoplastic resin composition |
| WO2022186484A1 (en) * | 2021-03-02 | 2022-09-09 | (주) 엘지화학 | Thermoplastic resin composition, and exterior material formed therefrom |
| EP4011972A4 (en) * | 2020-07-23 | 2022-11-30 | LG Chem, Ltd. | Thermoplastic resin composition and molded product thereof |
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2014
- 2014-11-14 KR KR1020140158400A patent/KR20160057601A/en active Search and Examination
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10351699B2 (en) | 2015-11-10 | 2019-07-16 | Lg Chem, Ltd. | Thermoplastic resin composition providing superior low-gloss characteristic, weather resistance, and mechanical properties and extruded article manufactured from the same |
| CN109071912B (en) * | 2016-11-04 | 2021-04-02 | 株式会社Lg化学 | Thermoplastic resin composition, method for preparing the same, and molded article comprising the same |
| EP3438198A4 (en) * | 2016-11-04 | 2019-07-17 | LG Chem, Ltd. | Thermoplastic resin composition, method for preparing same, and molded product comprising same |
| CN109071912A (en) * | 2016-11-04 | 2018-12-21 | 株式会社Lg化学 | Thermoplastic resin composition, preparation method and the mechanograph comprising it |
| US10640638B2 (en) | 2016-11-04 | 2020-05-05 | Lg Chem, Ltd. | Thermoplastic resin composition, method of preparing the same, and molded part including the same |
| KR20180052333A (en) * | 2016-11-10 | 2018-05-18 | 주식회사 엘지화학 | Thermoplstic resin composition with good low gloss, weather resistant property and mechanical properties, and extruded articles produced from the same |
| US11401409B2 (en) | 2017-11-09 | 2022-08-02 | Lg Chem, Ltd. | Thermoplastic resin composition |
| CN111386309B (en) * | 2017-12-04 | 2022-05-03 | 株式会社Lg化学 | Thermoplastic resin composition |
| WO2019112239A1 (en) * | 2017-12-04 | 2019-06-13 | 주식회사 엘지화학 | Thermoplastic resin composition |
| CN111386309A (en) * | 2017-12-04 | 2020-07-07 | 株式会社Lg化学 | Thermoplastic resin composition |
| US11359086B2 (en) | 2017-12-04 | 2022-06-14 | Lg Chem, Ltd. | Thermoplastic resin composition |
| KR20200046696A (en) | 2018-10-25 | 2020-05-07 | 주식회사 엘지화학 | Thermoplastic resin composition |
| EP4011972A4 (en) * | 2020-07-23 | 2022-11-30 | LG Chem, Ltd. | Thermoplastic resin composition and molded product thereof |
| CN114555695A (en) * | 2020-09-22 | 2022-05-27 | 株式会社Lg化学 | Thermoplastic resin composition and molded article comprising same |
| WO2022065625A1 (en) * | 2020-09-22 | 2022-03-31 | (주) 엘지화학 | Thermoplastic resin composition and molded product thereof |
| CN114555695B (en) * | 2020-09-22 | 2024-04-19 | 株式会社Lg化学 | Thermoplastic resin composition and molded article comprising same |
| WO2022186484A1 (en) * | 2021-03-02 | 2022-09-09 | (주) 엘지화학 | Thermoplastic resin composition, and exterior material formed therefrom |
| CN115427500A (en) * | 2021-03-02 | 2022-12-02 | 株式会社Lg化学 | Thermoplastic resin composition and exterior material comprising the same |
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