KR101961866B1 - Weatherproof two-layer resin sheet - Google Patents

Weatherproof two-layer resin sheet Download PDF

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KR101961866B1
KR101961866B1 KR1020150189580A KR20150189580A KR101961866B1 KR 101961866 B1 KR101961866 B1 KR 101961866B1 KR 1020150189580 A KR1020150189580 A KR 1020150189580A KR 20150189580 A KR20150189580 A KR 20150189580A KR 101961866 B1 KR101961866 B1 KR 101961866B1
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South Korea
Prior art keywords
resin
layer
resin sheet
weight
asa
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KR1020150189580A
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Korean (ko)
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KR20170079231A (en
Inventor
하현대
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세원정공 주식회사
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2355/00—Specific polymers obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of index codes B32B2323/00 - B32B2333/00
    • B32B2355/02—ABS polymers, i.e. acrylonitrile-butadiene-styrene polymers

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  • Laminated Bodies (AREA)

Abstract

The present invention relates to: I) a base layer of an ABS resin; And II) a two-layer structure resin sheet excellent in weather resistance laminated with a skin layer of a matt-free ASA resin on the base layer.
The resin sheet having a two-layer structure including the skin layer of the mattless ASA resin produced according to the present invention is excellent in moldability, chemical resistance, impact resistance and the like in a simple manufacturing process, It can be applied to mass production, which can increase the value of the product.

Description

A weather-resistant two-layer resin sheet (weatherproof two-layer resin sheet)

The present invention relates to a resin sheet having a two-layer structure excellent in weatherability, and more particularly, to a resin sheet comprising: I) a base layer of an ABS resin; And II) a two-layer structure resin sheet excellent in weather resistance laminated with a skin layer of a matt-free ASA resin on the base layer.

Resin products based on plastic materials are used in many fields of daily life in modern life, and properties and physical properties required for resin products vary according to their use fields. In particular, ABS (acrylonitrile-butadiene-styrene) resin is widely used as a resin for extrusion and injection molding for home appliances, office automation equipment, general goods, and the like because of excellent molding processability, chemical resistance and impact resistance. A variety of prior art are known.

Among these prior arts, a multilayer extruded sheet composed of a surface layer comprising a graft ABS copolymer, an acrylic rubber modified copolymer and a styrene acrylate copolymer and an inner layer comprising a graft ABS copolymer has excellent gloss (Such as scratch resistance), chemical resistance, and impact strength (Patent Document 1).

Further, a multilayer extrusion sheet comprising an ABS layer, a surface layer comprising an ABS graft copolymer, a silicone rubber-modified copolymer and a styrene acrylonitrile copolymer, and an inner layer comprising an ABS graft copolymer and a styrene acrylonitrile copolymer Has excellent impact strength and stability at low temperatures, and is also excellent in chemical resistance and hygroscopicity (Patent Document 2).

However, the ABS-based multilayer extruded sheets disclosed in Patent Documents 1 and 2 are unsatisfactory in weatherability and are therefore difficult to apply to outdoor or outdoor resin products.

On the other hand, the inventors of the present invention have found that when the ABS resin is used as a base layer, a core layer containing PMMA and metal powder, and a skin layer containing a MMA-acrylate copolymer resin or a skin layer containing an impact- Are all registered as patents. However, these resin sheets have a three-layered resin sheet, which is relatively complicated in the manufacturing process, and is mainly limited to kitchen furniture, interior decoration, and the like (Patent Documents 3 and 4).

Therefore, the inventors of the present invention have repeatedly studied resin sheets suitable for outdoor or outdoor products. As a result, they have found that an ABS resin excellent in molding processability, chemical resistance and impact resistance is used as a base layer, and matt ASA (acrylate- Acrylonitrile-styrene) resin layer laminated thereon, it is possible to mass-produce an outdoor or outdoor resin product having excellent weather resistance by a simple manufacturing process even if only a two-layered resin sheet is laminated.

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Patent Document 1: Korean Patent Registration No. 10-0843604 Patent Document 2: Korean Patent Publication No. 10-0998377 Patent Document 3: Korean Patent Publication No. 10-1414058 Patent Document 4: Korean Patent Publication No. 10-1420288

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and it is an object of the present invention to provide a resin composition for outdoor or outdoor use which is excellent in moldability, chemical resistance, impact resistance, A resin sheet having a two-layer structure.

In order to achieve the above-mentioned object, the present invention provides a laminate comprising: I) a base layer of an ABS resin; And II) a two-layer structure resin sheet excellent in weather resistance laminated with a skin layer of a matt-free ASA resin on the base layer.

The ABS resin comprises 15 to 35% by weight of an acrylonitrile monomer, 5 to 30% by weight of a butadiene rubber, and 40 to 60% by weight of a styrene monomer.

The butadiene rubber has an average particle diameter of 0.05 to 0.5 탆.

The matte ASA resin is characterized by comprising 90 to 95% by weight of an ASA resin and 5 to 10% by weight of a quencher.

The ASA resin is characterized by containing 10 to 30% by weight of an acrylate-based rubber.

The thickness of the skin layer is 10 to 15% of the total thickness of the resin sheet.

The resin sheet is characterized by being an outdoor or outdoor exterior material.

The resin sheet having a two-layer structure including the skin layer of the mattless ASA resin produced according to the present invention is excellent in moldability, chemical resistance, impact resistance and the like in a simple manufacturing process, It can be applied to mass production, which can increase the value of the product.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a resin sheet construction view showing a two-layer structure including a skin layer of matte ASA resin according to the present invention. Fig.

Hereinafter, a resin sheet having a two-layer structure having excellent weather resistance according to the present invention will be described in detail with reference to the accompanying drawings.

In the present invention, I) a base layer of an ABS resin; And II) a two-layer structure resin sheet excellent in weather resistance laminated with a skin layer of a matt-free ASA resin on the base layer.

1, an ABS (acrylonitrile-butadiene-styrene) resin is used as the polymer material constituting the base layer 10 of the resin sheet 100 of the two-layer structure according to the present invention. ABS resin is a copolymer having acrylonitrile chemical resistance, butadiene impact resistance and styrene excellent processability and is widely used as a material for furniture or bathtubs.

The ABS resin has a structure of a copolymer in which an acrylonitrile monomer and a styrene monomer are grafted to a butadiene rubber polymer. When the copolymer is used in consideration of the use of the copolymer, the acrylonitrile, butadiene and styrene monomer However, in the present invention, ABS resin preferably contains 15 to 35% by weight of acrylonitrile monomer, 5 to 30% by weight of butadiene rubber and 40 to 60% by weight of styrene monomer.

If the content of the acrylonitrile monomer constituting the ABS resin is less than 15% by weight, the chemical resistance may be deteriorated. If the content exceeds 35% by weight, heat discoloration may occur during molding. If the content of the butadiene rubber is less than 5% by weight, the impact strength is lowered. If the content is more than 30% by weight, the thermal stability may be deteriorated. If the content of the styrene monomer is less than 40% by weight, the processability is deteriorated. If the content of the styrene monomer exceeds 60% by weight, the chemical resistance is deteriorated.

The butadiene rubber preferably has an average particle diameter of 0.05 to 0.5 占 퐉. When the average particle diameter of the butadiene rubber is less than 0.05 占 퐉, the impact resistance may be deteriorated. When the average particle diameter of the butadiene rubber exceeds 0.5 占 퐉, the acrylonitrile monomer and styrene The degree to which the monomer is grafted is lowered and the molecular weight of the copolymer may be reduced.

In general, ABS resins are widely used for home appliances, office automation equipment, and general merchandise since they are excellent in molding processability, chemical resistance, and impact resistance. However, when they come in contact with oxygen, ozone, ultraviolet rays, etc. in the air, There is a limit to use in an electronic product or an outdoor or outdoor resin product which requires a weather resistance. Conventionally, there has been a method of coating a paint having excellent weather resistance on the surface of a molded article or blending an additive such as a light stabilizer in order to solve such a problem. However, this is not preferable because it causes a limit of long-term weatherability and a cost increase due to secondary processing .

Therefore, in the present invention, by using ASA (acrylate-acrylonitrile-styrene) resin having various physical properties of general ABS resin level and having excellent weatherability and securing long-term stable physical properties, The disadvantage of the ABS resin sheet is solved by producing a two-layered sheet in which the skin layer of the ASA resin is laminated on the base material layer of the ABS resin by a simple process by molding.

As the ASA resin of the present invention, mattless ASA resin having no gloss is used in consideration of its application as an exterior material for outdoor or outdoor use. The matte ASA resin is formulated with a quencher in the molding process of the ASA resin to remove the gloss. As a general light-quenching agent, it is known that the gloss of the thermoplastic resin can be removed by adding a fine filler such as silica, silicate or aluminate, but the mechanical properties of the thermoplastic resin are lowered. Therefore, in the present invention, it is preferable to use a styrene-acrylonitrile copolymer resin (SAN) blended with a matting property as a quencher which does not cause deterioration of the physical properties of the ASA resin.

It is more preferable that the matte ASA resin contains 90 to 95% by weight of the ASA resin and 5 to 10% by weight of the quencher. When the content of the quencher in the matte ASA resin is less than 5% by weight, On the other hand, when the amount exceeds the above range, the workability is deteriorated.

The acrylate-based rubber constituting the matte ASA resin may be one obtained by polymerizing ethyl acrylate, butyl acrylate, hexyl acrylate or 2-ethylhexyl acrylate monomers, or copolymerizing these monomers. The content of the rubber is preferably 10 to 30% by weight. When the content of the acrylate rubber is less than 10% by weight, the impact resistance is poor. When the content is more than 30% by weight, the thermal stability may be deteriorated.

The skin layer 20 of the matte ASA resin is laminated on the base layer 10 to form a uniform skin layer so that the thickness of the skin layer 20 is 10 to 15% of the total thickness of the resin sheet, And particularly, the weather resistance can be remarkably improved.

The resin sheet having a two-layer structure excellent in weather resistance according to the present invention is produced into a two-layer structure sheet composed of the skin layer 20 and the base layer 10 by coextrusion molding. ABS resin which is the base material of the base layer 10 and mattless ASA resin which is the base material of the skin layer 20 use the pelletized commercialized raw material as it is. The components of each layer are fed into the feed block by a double co-extruder maintained at the melting temperature of each resin or more and laminated with the base layer 10 of the ABS resin / the skin layer 20 of the non-light ASA resin. The laminated resin layer is processed into a sheet form from a die to produce a two-layer structure sheet 100.

In addition, the thickness of the resin sheet 100 produced in the present invention can obtain a uniform thickness by accurately controlling the extrusion amount of each resin introduced into the feed block from the double co-extruder.

The resin sheet having a two-layer structure excellent in weather resistance according to the present invention can be produced by the simple process as described above, and can be applied to mass production of outdoor or outdoor resin products.

Hereinafter, specific examples will be described in detail.

(Example)

ABS resin pellets and matt ASA resin pellets were respectively prepared. The pellets were put into a feed block through a twin co-extruder set at different temperatures of 260 [deg.] C and 250 [deg.] C, respectively, to form a skin layer / substrate layer. The laminated resin was passed through a die and processed into a sheet to obtain a resin sheet having a two-layer structure. At this time, the thickness of the skin layer was adjusted to 0.1 mm to finally prepare a resin sheet having a thickness of 1 mm.

(Comparative Example)

A single-layer resin sheet having a thickness of 1 mm was produced by extrusion molding using ABS resin pellets according to a known method.

(Test Example)

The properties of a two-layered resin sheet including the ASA skin layer prepared in the above example and a single-layer resin sheet without the ASA skin layer prepared from the comparative example were measured by the following method.

(1) Weatherability: Measurement according to SAE J 1960 (3000 hours, ΔE)

(2) Impact resistance: Izod impact strength measurement according to ASTM D256 method

(3) Pencil Hardness: The hardness value when no scratch is found by pushing a pencil 5 times at a speed of 10 mm / s by raising a weight of 500 g with a pencil according to hardness

Sample Weatherability
(? E) Izod impact strength
(kg.cm/cm) Pencil hardness Example 2.5 13.5 H Comparative Example 10.2 14.0 2B

As shown in Table 1, the resin sheet having the two-layer structure including the ASA skin layer manufactured from the embodiment of the present invention is not less susceptible to impact resistance than the ABS resin sheet having a single layer structure manufactured from the comparative example, It was found that the scratch resistance was excellent, and in particular, the weather resistance was excellent.

Therefore, the resin sheet having a two-layer structure including the skin layer of the matt light ASA resin produced according to the present invention is excellent in molding processability, chemical resistance, impact resistance and the like in a simple manufacturing process, To increase the value of the product.

100. Two-layer resin sheet
10. Base layer
20. Skin layer

Claims (8)

I) a base layer of an ABS resin; And
II) A resin sheet having a two-layer structure in which a skin layer of a non-light ASA resin is laminated on the base layer,
The matte ASA resin comprises 90 to 95% by weight of an ASA resin having an acrylate rubber content of 10 to 30% by weight and 5 to 10% by weight of a styrene-acrylonitrile copolymer resin (SAN) as a light extinguishing agent A resin sheet having a two-layer structure for an outdoor or outdoor exterior material. The ABS resin according to claim 1, wherein the ABS resin comprises 15 to 35% by weight of an acrylonitrile monomer, 5 to 30% by weight of a butadiene rubber, and 40 to 60% by weight of a styrene monomer. Resin sheet of structure. delete delete delete delete The resin sheet according to claim 1, wherein the skin layer has a thickness of 10 to 15% of the total thickness of the resin sheet. delete
KR1020150189580A 2015-12-30 2015-12-30 Weatherproof two-layer resin sheet KR101961866B1 (en)

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Application Number Priority Date Filing Date Title
KR1020150189580A KR101961866B1 (en) 2015-12-30 2015-12-30 Weatherproof two-layer resin sheet

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KR101961866B1 true KR101961866B1 (en) 2019-03-26

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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101977793B1 (en) 2017-09-20 2019-05-13 하현대 Non-glossy two-layer sheet comprising embossed PMMA skin layer
KR102179950B1 (en) * 2018-09-03 2020-11-17 하현대 Weatherproof two-layer resin sheet
KR102160162B1 (en) * 2018-09-03 2020-09-25 하현대 Weatherproof two-layer resin sheet
KR102169234B1 (en) * 2019-03-19 2020-10-23 심영수 Method for manufacturing a building interior materials and a building interior materials manufactured by the same
CN110435195A (en) * 2019-09-06 2019-11-12 广东共力建材有限公司 A kind of ASA/PVC multilayer watt co-extrusion production line and production method
KR102117524B1 (en) 2020-05-06 2020-06-02 하현대 Sheet comprising inline-laminated plastic film and manufacturing method thereof
CN117651644A (en) * 2021-08-13 2024-03-05 株式会社Lg化学 Method for manufacturing transparent sheet and transparent sheet
KR20230120324A (en) 2022-02-09 2023-08-17 하현대 Non-glossy acrylic multi-layer sheet for processing air conditioner cover or bathtub
KR20230120688A (en) 2022-02-09 2023-08-17 하현대 Non-glossy acrylic multi-layer sheet for processing air conditioner cover or bathtub

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Publication number Priority date Publication date Assignee Title
US5522196A (en) * 1994-04-25 1996-06-04 General Electric Company Thin wall profile having outer weather band ultra violet light resistant layer
KR100843604B1 (en) 2006-01-19 2008-07-03 주식회사 엘지화학 Multilayer extruded sheet
KR100998377B1 (en) 2006-09-11 2010-12-03 주식회사 엘지화학 Multilayer extruded sheet
KR101056314B1 (en) * 2006-10-24 2011-08-11 주식회사 엘지화학 Low gloss thermoplastic resin composition having excellent impact resistance and heat resistance
KR100915409B1 (en) * 2006-11-21 2009-09-03 주식회사 삼양사 Polycarbonate resin composition with low gloss and excellent light stability
KR100988999B1 (en) * 2007-10-19 2010-10-20 주식회사 엘지화학 Acrylate-styrene-acrylonitrile polymer, method of preparing the same and thermoplastic resin composition containing the same
KR101322102B1 (en) * 2009-10-12 2013-10-25 주식회사 엘지화학 Thermoplastic resin composition applicable to two cavities blow molding
KR101420288B1 (en) 2013-09-27 2014-07-17 세원정공 주식회사 Resin sheet having pearl-like luster or pattern
KR101414058B1 (en) 2014-01-24 2014-07-02 세원정공 주식회사 Resin sheet having pearl-like luster or pattern and bathtubs using the same

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