KR20160127397A - Thermoplstic resin composition with low gloss and impact strength and construction meterials produced from the same - Google Patents

Thermoplstic resin composition with low gloss and impact strength and construction meterials produced from the same Download PDF

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Publication number
KR20160127397A
KR20160127397A KR1020150058739A KR20150058739A KR20160127397A KR 20160127397 A KR20160127397 A KR 20160127397A KR 1020150058739 A KR1020150058739 A KR 1020150058739A KR 20150058739 A KR20150058739 A KR 20150058739A KR 20160127397 A KR20160127397 A KR 20160127397A
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South Korea
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weight
resin composition
thermoplastic resin
gloss
acrylate rubber
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KR1020150058739A
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Korean (ko)
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KR101791736B1 (en
Inventor
강은수
황용연
김민정
박춘호
이상미
이영민
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주식회사 엘지화학
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/62—Mechanical aspects
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE

Abstract

The present invention relates to a thermoplastic resin composition having excellent low gloss and impact resistance and building exterior materials produced from the thermoplastic resin composition, and more specifically, to a thermoplastic resin composition having excellent low gloss and impact resistance comprising: 30 to 50 wt% of an ASA resin in which an aromatic vinyl compound and a vinyl cyan compound are graft polymerized to an acrylate-based rubber core; 45 to 65 wt% of an SAN resin in which the aromatic vinyl compound and the vinyl cyan compound are polymerized; and 3 to 10 wt% of a high density polyethylene resin having a weight average molecular weight of 150,000 g/mol or more, and building exterior materials produced from the thermoplastic resin composition. The present invention has effects of providing a thermoplastic resin composition having excellent weatherability, low gloss and impact resistance, and building exterior materials produced from the thermoplastic resin composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermoplastic resin composition excellent in low glossiness and impact resistance, and a building exterior material made therefrom. BACKGROUND OF THE INVENTION 1. Field of the Invention [0002]

More particularly, the present invention relates to a thermoplastic resin composition having excellent weatherability, low gloss, and impact resistance, and a constructional exterior material manufactured therefrom. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having low gloss and excellent impact resistance, .

Acrylonitrile-butadiene-styrene (ABS) resin, which is a styrene copolymer used widely in industry, has excellent properties such as impact resistance, chemical resistance and molding processability, It is widely used for interior and exterior materials for automobiles. However, since weatherability is not good, there is a problem in using it as an exterior material, especially a building exterior material, which receives a lot of sunlight. In order to solve this problem, ABS resin is plated or painted in order to reinforce weatherability and to add luxury. In this case, the cost is increased due to the additional process and environmental problems are caused, which is not a desirable solution.

Therefore, an acrylate-styrene-acrylonitrile (ASA) resin has emerged as an alternative to a building material having excellent weather resistance. ASA resin has excellent weather resistance, chemical resistance and thermal stability, and is mainly used for external use. It is used as an end product itself without any treatment such as coating, painting and plating on the surface. It is mainly used for outdoor electric / electronic parts, building materials, sporting goods, automobile parts and so on. Mainly applied products are satellite antenna, kayak paddle, chassis joiner and profile, door panel, automobile radiator grill, side mirror housing .

In addition, the ASA resin has the advantage of saving manufacturing cost and owing to environmental friendliness since the post-process such as plating and coating is omitted, but has a high gloss which is not good because of lack of impact strength and coating There is a problem in that the appearance of the appearance is off.

Korean Published Patent Application No. 2009-0095764 (Published September 10, 2009)

In order to solve the problems of the prior art as described above, the present invention aims to provide a thermoplastic resin composition excellent in weatherability, low gloss and impact resistance.

It is another object of the present invention to provide a building exterior material made of the above-mentioned 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 relates to a rubber composition comprising 30 to 50% by weight of an ASA resin obtained by graft-polymerizing an aromatic vinyl compound and a vinyl cyan compound onto an acrylate rubber core; 45 to 65 wt% of SAN resin in which an aromatic vinyl compound and a vinyl cyan compound are polymerized; And 3 to 10% by weight of a high-density polyethylene resin having a weight average molecular weight of 150,000 g / mol or more; and a low-gloss and impact-resistant thermoplastic resin composition.

The present invention also provides a building exterior material made from the above thermoplastic resin composition.

According to the present invention, there is provided an effect of providing a thermoplastic resin composition which is excellent in weatherability, low gloss and impact resistance without using a quenching agent or an impact modifier, and a building exterior material manufactured therefrom.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition of the present invention comprises 30 to 50% by weight of an ASA resin obtained by graft-polymerizing an aromatic vinyl compound and a vinyl cyan compound onto an acrylate-based rubber core; 45 to 65 wt% of SAN resin in which an aromatic vinyl compound and a vinyl cyan compound are polymerized; And 3 to 10% by weight of a high-density polyethylene resin having a weight average molecular weight of 150,000 g / mol or more. Within this range, there is an effect of excellent weather resistance, low gloss and impact resistance.

As another example, the ASA resin in which the aromatic vinyl compound and the vinyl cyan compound are graft-polymerized in the acrylate rubber core may be 35 to 45 wt% (the SAN resin is 45 to 62 wt%), and within this range, This has an excellent effect.

Wherein the ASA resin comprises 20 to 60% by weight of an acrylate rubbery polymer, 25 to 45% by weight of an aromatic vinyl compound and 5 to 35% by weight of a vinyl cyan compound, 30 to 50% by weight of an acrylate rubbery polymer, 40% by weight and a vinyl cyanide compound in an amount of 10% by weight to 30% by weight, and an excellent balance of weatherability and physical properties within this range.

The ASA resin in which the aromatic vinyl compound and the vinyl cyan compound are graft-polymerized to the acrylate-based rubber core includes a core-shell acrylate-styrene-acrylonitrile copolymer having an average particle diameter of 500 to 2,000 Å Styrene-acrylonitrile copolymer (hereinafter referred to as a large-diameter ASA copolymer) having a core-shell structure having an average particle diameter of 2,500 to 6,000 angstrom, The impact strength is improved.

The ASA resin may be, for example, 10 to 90% by weight of a small diameter ASA copolymer and 10 to 90% by weight of a large diameter ASA copolymer.

The small diameter ASA copolymer may contain 15 to 55% by weight of an acrylate rubber, 20 to 55% by weight of an aromatic vinyl compound and 10 to 30% by weight of a vinyl cyanide compound.

The large diameter ASA copolymer may contain 20 to 60 wt% of an acrylate rubber, 25 to 55 wt% of an aromatic vinyl compound, and 5 to 25 wt% of a vinyl cyan compound.

The acrylate-styrene-acrylonitrile-based copolymer of the core-shell structure may be prepared by emulsion polymerization including an emulsifier, an initiator, a grafting agent, a crosslinking agent and an electrolyte in an acrylate rubber.

The acrylate-based rubber may be, for example, an alkyl acrylate rubber.

The alkyl acrylate rubber is at least one selected from the group consisting of methyl acrylate rubber, ethyl acrylate rubber, butyl acrylate rubber, hexyl acrylate rubber, octyl acrylate rubber and 2-ethylhexyl acrylate rubber.

As another example, the SAN resin in which the aromatic vinyl compound and the vinyl cyan compound are polymerized can be 50 to 60 wt% (the ASA resin is 30 to 47 wt%), and the impact strength is excellent within this range.

The SAN resin may be 20 to 40% by weight of a vinyl cyan compound and 60 to 80% by weight of an aromatic vinyl compound, 25 to 35% by weight of a vinyl cyan compound, and 65 to 75% by weight of an aromatic vinyl compound, And an excellent balance of physical properties.

The aromatic vinyl compound is at least one selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, vinyltoluene, and t-butylstyrene.

The vinyl cyan compound is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile.

As another example, the high-density polyethylene resin may be 4 to 8% by weight, and the low-gloss and impact strength are all excellent within this range.

The high-density polyethylene resin is the case of conventional HDPE is not particularly limited and may be a polyethylene resin density of 0.93 to 0.97 g / cm 3, 0.95 to 0.97 g / cm 3, or 0.955 to 0.965 g / cm 3 as an example, Within this range, the balance of physical properties is excellent.

As another example of the high-density polyethylene resin, the weight average molecular weight may be 150,000 to 550,000 g / mol, and the low-gloss and impact strength are excellent within this range.

As another example of the high-density polyethylene resin, the weight average molecular weight may be 150,000 g / mol to 390,000 g / mol, or 390,000 g / mol to 550,000 g / mol. In this case, low-gloss and impact strength are excellent.

The high-density polyethylene resin may be a mixture of two or more high-density polyethylene resins having different weight average molecular weights, for example. In this case, the balance of physical properties is excellent.

The mixing of the high-density polyethylene resin is, for example, a mixture of a high-density polyethylene resin having a weight average molecular weight of 150,000 to 390,000 g / mol and a high-density polyethylene resin having a weight average molecular weight of more than 390,000 g / mol and not more than 550,000 g / mol, Has an excellent effect.

As another example of the mixing of the high-density polyethylene resin, a high-density polyethylene resin having a weight-average molecular weight of 350,000 to 450,000 g / mol and a high-density polyethylene resin having a weight-average molecular weight of 450,000 g / mol to 550,000 g / mol An excellent balance of physical properties is obtained.

The thermoplastic resin composition may further include at least one selected from the group consisting of a lubricant, an antioxidant, and a light stabilizer.

The exterior material for construction of the present invention is characterized by being produced from a thermoplastic resin composition having excellent low-gloss and impact resistance.

The building exterior material may be, for example, a wall or a decorative material for an exterior of a building.

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]

The compounds used in the following Table 1 are as follows.

* ASA Resin: A resin having an average particle diameter of 3500 Å and containing 40% by weight of acrylate as a core and 35% by weight of styrene and 25% by weight of acrylonitrile

* SAN resin: Polymerized resin containing 75% by weight of styrene and 25% by weight of acrylonitrile

* HDPE 1: High density polyethylene resin having a density of 0.96 g / cm 3 and a weight average molecular weight of 100,000 g / mol

* HDPE 2: High density polyethylene resin having a density of 0.96 g / cm 3 and a weight average molecular weight of 350,000 g / mol

HDPE 3: High density polyethylene resin having a density of 0.96 g / cm 3 and a weight average molecular weight of 500,000 g / mol

Examples 1 to 3 and Comparative Examples 1 to 4

The components were added in the respective amounts as shown in Table 1 below, mixed and extruded using a twin-screw extruder under the condition of 220 DEG C, and then prepared into pellets, dried and extruded at an injection temperature of 200 to 250 DEG C, A resin composition specimen was prepared.

[Test Example]

The properties of the specimens prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were measured by the following methods, and the results are shown in Table 1 below.

* Average Particle Diameter (Å): Measured using an intensity Gaussian distribution (Nicomp 380) by a dynamic laser light scattering method.

* Gloss (60 °): Measured at 60 ° with a gloss meter. The higher the gloss value, the better the gloss of the surface.

* Impact strength (1/4 "; kgf · cm / cm): Measured according to ASTM D256.

* Weight average molecular weight (g / mol): Measured by HT-GPC (High Temperature-Gel Permeation Chromatography).

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 ASA (% by weight) 40 40 40 40 40 40 40 SAN (wt%) 56 56 56 58 58 58 60 HDPE 1 (% by weight) 0 0 0 2 0 0 0 HDPE 2 (% by weight) 4 0 2 0 2 0 0 HDPE 3 (% by weight) 0 4 2 0 0 2 0 Gloss 48.7 44.7 45.2 75.2 70.5 68.8 87.4 Impact strength
(1/4 ") 23.89 25.55 24.22 15.15 17.55 18.72 11.58

As shown in Table 1, the thermoplastic resin composition of the present invention was excellent in low-gloss effect without using a quencher, and the impact strength was improved. The higher the weight average molecular weight of the high-density polyethylene resin, the lower the gloss and the higher the impact strength.

Claims (12)

30 to 50% by weight of an ASA resin obtained by graft-polymerizing an aromatic vinyl compound and a vinyl cyan compound in an acrylate rubber core; 45 to 65 wt% of SAN resin in which an aromatic vinyl compound and a vinyl cyan compound are polymerized; And 3 to 10% by weight of a high-density polyethylene resin having a weight average molecular weight of 150,000 g / mol or more; and a low-gloss and impact-resistant thermoplastic resin composition.
The method according to claim 1,
The high-density polyethylene resin has a weight average molecular weight of 150,000 to 550,000 g / mol. The thermoplastic resin composition is excellent in low-gloss and impact resistance.
3. The method of claim 2,
The high-density polyethylene resin is a high-density polyethylene resin having a weight-average molecular weight of 150,000 g / mol to 390,000 g / mol, and a high-density polyethylene resin having a weight-average molecular weight of more than 390,000 g / mol and less than 550,000 g / mol. Thermoplastic resin composition.
The method according to claim 1,
Wherein the ASA resin comprises 20 to 60% by weight of an acrylate-based rubbery polymer, 25 to 45% by weight of an aromatic vinyl compound and 5 to 35% by weight of a vinyl cyan compound, wherein the thermoplastic resin composition is excellent in low- .
The method according to claim 1,
The SAN resin comprises 20 to 40% by weight of a vinyl cyan compound and 60 to 80% by weight of an aromatic vinyl compound, wherein the SAN resin is excellent in low-gloss and impact resistance.
The method according to claim 1,
Wherein the acrylate rubber is an alkyl acrylate rubber. The thermoplastic resin composition is excellent in low-gloss and impact resistance.
The method according to claim 6,
The alkyl acrylate rubber is at least one selected from the group consisting of methyl acrylate rubber, ethyl acrylate rubber, butyl acrylate rubber, hexyl acrylate rubber, octyl acrylate rubber and 2-ethylhexyl acrylate rubber. Which is excellent in low-gloss and impact resistance.
The method according to claim 1,
Wherein the aromatic vinyl compound is at least one selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, vinyltoluene, and t-butylstyrene.
The method according to claim 1,
Wherein the vinyl cyan compound is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile. The thermoplastic resin composition is excellent in low-gloss and impact resistance.
The method according to claim 1,
The thermoplastic resin composition excellent in low-gloss and impact resistance further comprises at least one member selected from the group consisting of a lubricant, an antioxidant, and a light stabilizer.
A building exterior material characterized by being produced from a thermoplastic resin composition having excellent low-gloss and impact resistance according to any one of claims 1 to 10.
12. The method of claim 11,
Wherein the building exterior material is a wall or building exterior material.
KR1020150058739A 2015-04-27 2015-04-27 Thermoplstic resin composition with low gloss and impact strength and construction meterials produced from the same KR101791736B1 (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114685909A (en) * 2020-12-30 2022-07-01 上海汽车集团股份有限公司 Resin composition and method for producing the same
EP4011974A4 (en) * 2020-09-24 2022-11-09 Lg Chem, Ltd. Thermoplastic resin composition, preparation method therefor, and molded product manufactured therefrom
WO2024090995A1 (en) * 2022-10-25 2024-05-02 주식회사 엘지화학 Thermoplastic resin composition

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090095764A (en) 2008-03-06 2009-09-10 주식회사 엘지화학 Termoplastic Resin Composition Having A Good Weather Resistance And Low Gloss

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090095764A (en) 2008-03-06 2009-09-10 주식회사 엘지화학 Termoplastic Resin Composition Having A Good Weather Resistance And Low Gloss

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4011974A4 (en) * 2020-09-24 2022-11-09 Lg Chem, Ltd. Thermoplastic resin composition, preparation method therefor, and molded product manufactured therefrom
CN114685909A (en) * 2020-12-30 2022-07-01 上海汽车集团股份有限公司 Resin composition and method for producing the same
WO2024090995A1 (en) * 2022-10-25 2024-05-02 주식회사 엘지화학 Thermoplastic resin composition

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