KR20120009860A - Asa resin composition for PPC co-extrusion, film, extruded sheet and architectural exterior material manufactured therefrom - Google Patents

Abstract

The present invention relates to an ASA resin composition for PVC coextrusion, a film prepared therefrom, an extruded sheet, and a building exterior material. More specifically, the present invention relates to a bimodal alkyl acrylate-styrene-acrylonitrile-based graft aerial. And ii) an alkyl methacrylate-styrene-acrylonitrile-based copolymer melt-kneaded, wherein iv) the bimodal alkyl acrylate-styrene-acrylonitrile-based graft copolymer has an average particle diameter of 180 ASA resin for PVC co-extrusion, characterized in that the graft polymerized, including the alkyl acrylate rubber having an average particle diameter of 80 to 130 nm and the vinyl cyan monomer in an amount of 35 to 45 wt% Composition, a film produced therefrom, an extruded sheet produced by co-extrusion of the film and a PVC resin film, and a building exterior material manufactured from the extruded sheet It is about.
According to the present invention, there is an effect of providing an ASA resin composition for co-extrusion of PVC having excellent adhesion, impact strength, weather resistance, scratch resistance, and chemical resistance with a PVC resin film, a film prepared therefrom, an extruded sheet, and a building exterior material. .

Description

ASA resin composition for PPC coextrusion, film, extruded sheet and architectural exterior material produced therefrom {ASA Resin Composite For Preparing PVC-ASA Co-extruded Sheet, Film Therefrom, Co-extruded Sheet And Exterior Sheet For Architecture}

The present invention relates to an ASA resin composition for PVC coextrusion, a film prepared therefrom, an extruded sheet, and a building exterior material, and more particularly, excellent adhesion, impact strength, weather resistance, scratch resistance and chemical resistance with a PVC resin film. The present invention relates to an ASA resin composition for PVC coextrusion, a film prepared therefrom, an extruded sheet, and a building exterior material.

Polyvinyl chloride (PVC) is a general-purpose resin, which is inexpensive, and has been applied to building exterior materials, especially window profiles, because it is easy to control flame resistance, chemical resistance, and product hardness, but has poor weather resistance, colorability, and weather resistance. There is.

Therefore, the PVC resin is used when applied to the building exterior coating or laminated with a resin film excellent in weather resistance and the like.

US Patent Publication No. 2008/0281023 discloses a sheet made by laminating a polymethyl (meth) acrylate (PMMA) foil having excellent weather resistance to a colored PVC foil, but the mechanical strength, adhesive strength, etc. of the PMMA foil protecting the PVC foil is poor. there is a problem.

The acrylate-styrene-acrylonitrile-based (ASA) thermoplastic resin, which is widely used in electrical and electronic parts, building materials, sporting goods, automobile parts, etc., is excellent in weathering resistance to discoloration, chemical resistance, and thermal stability, and thus is insufficient in PVC resin. Although much research has been conducted into resins for coextrusion that can fill physical properties, there is still a problem that scratch resistance, adhesive strength, and colorability are not sufficient.

In order to solve the problems of the prior art as described above, the present invention is a PVC co-extrusion ASA resin composition excellent in adhesive strength, impact strength, weather resistance, scratch resistance and chemical resistance with a PVC resin film, a film prepared therefrom, an extruded sheet And to provide a building exterior material.

The above 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 method for producing a bimodal alkyl acrylate-styrene-acrylonitrile-based graft copolymer and ii) alkyl methacrylate-styrene-acrylonitrile-based copolymer. It is kneaded, but iii) the bimodal alkyl acrylate-styrene-acrylonitrile-based graft copolymer is an alkyl acrylate rubber having an average particle size of 180 to 230 nm and alkyl acrylate having an average particle size of 80 to 130 nm ASA resin composition for PVC coextrusion comprising graft polymerized rubber and containing 35 to 45% by weight of vinyl monomer, a film prepared therefrom, an extruded sheet prepared by coextrusion of this film and a PVC resin film, and Provided is a building exterior material manufactured from this extruded sheet.

As described above, according to the present invention, the ASA resin composition for co-extrusion of PVC having excellent adhesion, impact strength, weather resistance, scratch resistance, and chemical resistance with a PVC resin film, a film prepared therefrom, an extruded sheet, and a building exterior material It is effective to provide.

1 is a schematic diagram schematically showing a method of measuring the adhesion of PVC-PMMA or PVC-ASA extruded sheet.
Figure 2 is a graph showing the comparison between the adhesive force of the PVC-ASA extruded sheet according to the present invention and the conventional PVC-PMMA extruded sheet.
Figure 3 is a graph showing the impact strength of the PVC co-extrusion ASA resin composition according to the present invention and the conventional PMMA.
Figure 4 is a photograph showing the thermal stability measurement method and results of the PVC film, ASA film and PMMA film.

Hereinafter, the present invention will be described in detail.

ASA resin composition for PVC co-extrusion of the present invention is ⅰ) bimodal alkyl acrylate-styrene-acrylonitrile graft copolymer and ii) alkyl methacrylate-styrene-acrylonitrile copolymer melt It is kneaded, but iii) the bimodal alkyl acrylate-styrene-acrylonitrile-based graft copolymer is an alkyl acrylate rubber having an average particle size of 180 to 230 nm and alkyl acrylate having an average particle size of 80 to 130 nm Graft polymerization including rubber, characterized in that the vinyl cyan monomer is contained in 35 to 45% by weight.

In the present invention, the alkyl acrylate-styrene-acrylonitrile-based graft copolymer refers to a copolymer in which an aromatic vinyl monomer and a vinyl cyan monomer are graft polymerized on an alkyl acrylate rubber.

The alkyl acrylate rubber of i) may be a rubber polymer prepared from an alkyl acrylate monomer, wherein the alkyl group (meaning 'alkyl' portion in the alkyl acrylate monomer) is preferably composed of 2 to 8 carbons, More preferably, it consists of 4-8 carbons.

The aromatic vinyl monomer is preferably at least one selected from the group consisting of styrene or derivatives thereof, more preferably at least one selected from the group consisting of styrene, alphamethylstyrene, paramethylstyrene, vinyl toluene and the like.

(Iii) The bimodal alkyl acrylate-styrene-acrylonitrile-based graft copolymer (hereinafter referred to as 'bimodal ASA graft copolymer') is preferably prepared by emulsion graft polymerization. If the particles of a certain size is produced stably, the graft efficiency is improved.

The emulsion polymerization may be used by appropriately selecting an emulsifier, an initiator, a grafting agent, a crosslinking agent, a molecular weight modifier, an electrolyte, and the like, which can be commonly used in preparing the ASA copolymer.

Iii) Bimodal ASA graft copolymer prepared by the emulsion polymerization is preferably agglomerated and dried to be recovered in the form of a dry powder to be applied to the PVC co-extrusion ASA resin composition.

Iii) the bimodal ASA graft copolymer is an alkyl acrylate rubber having an average particle diameter of 180 to 230 nm, preferably an alkyl acrylate rubber having an average particle diameter of 180 to 210 nm; Alkyl acrylate rubber having an average particle diameter of 80 to 130 nm, preferably an alkyl acrylate rubber having an average particle diameter of 90 to 120 nm; and is graft polymerized, including appearance characteristics such as gloss and colorability within the average particle diameter range. At the same time excellent mechanical strength is excellent.

The content ratio (large diameter / small diameter) of the alkyl acrylate rubber having an average particle diameter of 180 to 230 nm and the alkyl acrylate rubber having an average particle diameter of 80 to 130 nm is preferably 3/4 to 4/3, within this range. There is an effect that both excellent mechanical strength and appearance characteristics are expressed.

Iii) the bimodal ASA graft copolymer is 35 to 45% by weight of acrylonitrile-based monomer, preferably contained in 37 to 42% by weight, ASA for PVC coextrusion prepared within this range Adhesion and chemical resistance of the film with PVC is greatly improved.

The vinyl cyan monomer is preferably one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile and the like.

(Iii) The bimodal ASA graft copolymer may include 25 to 45 wt% of an alkyl acrylate rubber and 20 to 40 wt% of a vinyl aromatic monomer.

(Iii) The bimodal ASA graft copolymer preferably has a weight average molecular weight of 150,000 to 200,000, and has an excellent impact strength within this range.

The ii) alkyl methacrylate-styrene-acrylonitrile copolymer is a methyl methacrylate-styrene-acrylonitrile copolymer, ethyl methacrylate-styrene-acrylonitrile copolymer, or a mixture thereof. Preferably, it is a methyl methacrylate-styrene-acrylonitrile copolymer, and in this case, there exists an effect that the scratch resistance of the ASA resin composition for PVC coextrusion manufactured is greatly improved.

The ii) alkyl methacrylate-styrene-acrylonitrile copolymer has 50 to 80% by weight of alkyl methacrylate, 20 to 40% by weight of vinyl aromatic monomer, and 10 to 40% by weight of vinyl cyan monomer. It is preferable to include, it has an effect that the appearance properties such as scratch resistance and complexing and gloss of the PVC co-extrusion ASA resin composition prepared within this range is greatly improved.

The ii) alkyl methacrylate-styrene-acrylonitrile-based copolymer is preferably a weight average molecular weight of 80,000 to 150,000, scratch resistance and impact resistance of the ASA resin composition for PVC co-extrusion prepared within this range The effect is greatly improved.

The ii) alkyl methacrylate-styrene-acrylonitrile-based copolymer is preferably a ternary copolymer prepared by bulk polymerization.

The terpolymer is preferably a glass transition temperature of 80 to 120 ℃, more preferably 90 to 110 ℃.

The ASA resin composition for co-extrusion of the PVC comprises 20 to 50% by weight of the bimodal ASA graft copolymer, and ii) 50 to 80% by weight of the alkyl methacrylate-styrene-acrylonitrile copolymer. Although it is preferable to make it, it is excellent in the adhesive force with a PVC resin, impact strength, scratch resistance, etc. within this range.

The ASA resin composition for PVC coextrusion is selected from the group consisting of plasticizers, coupling agents, fluorescent brighteners, metal deactivators, blooming agents, antistatic agents, lubricants, antioxidants, UV stabilizers, dyes, pigments, flame retardants and inorganic fillers. It may further comprise one or more.

The ASA resin composition for co-extrusion of PVC is a specific example, the graft copolymer in the form of a dry powder and the copolymer of ii) in the form of pellets can be prepared by injecting into the extruder, followed by melt kneading.

PVC co-extrusion ASA film of the present invention is characterized in that made of the PVC co-extrusion ASA resin composition.

The method of making the ASA resin composition for PVC coextrusion into a film is not particularly limited in the case of the method of making the ASA resin composition into a film.

Extrusion sheet of the present invention is characterized in that the ASA film for PVC co-extrusion, and PVC resin film is produced by co-extrusion.

The co-extrusion is usually not particularly limited in the case of a method of laminating the PVC film and the ASA film.

Building exterior material of the present invention is characterized in that it is produced from the extruded sheet.

The building exterior material may be a window profile or the like.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.

[Example]

Example 1

<Preparation of alkyl acrylate rubber polymer with average particle diameter of 180 to 230 nm>

10 parts by weight of butyl acrylate, 0.03 parts by weight of sodium dodecyl sulfate, 0.05 parts by weight of ethylene glycol dimethacrylate, 0.02 parts by weight of allyl methacrylate, 0.1 parts by weight of sodium hydrogencarbonate, and 60 parts by weight of distilled water After heating up to 70 degreeC, 0.05 weight part of potassium persulfates were put and the reaction was started. After the reaction for 1 hour to prepare a butyl acrylate rubber polymer having an average particle diameter of 200 nm.

<Preparation of alkyl acrylate rubber polymer having an average particle diameter of 80 to 130 nm>

10 parts by weight of butyl acrylate, 0.06 parts by weight of sodium dodecyl sulfate, 0.05 parts by weight of ethylene glycol dimethacrylate, 0.02 parts by weight of allyl methacrylate, 0.1 parts by weight of sodium bicarbonate, and 60 parts by weight of distilled water After heating up to 70 degreeC, 0.05 weight part of potassium persulfates were put and the reaction was started. After the reaction for 1 hour to prepare a butyl acrylate rubber polymer having an average particle diameter of 100 nm.

<Production of Bimodal ASA Graft Copolymer>

36 parts by weight of styrene, 14 parts by weight of acrylonitrile, 1.5 parts by weight of potassium rosinate, and 0.1 weight of potassium persulfate in a mixture of the above average particle diameter 200 nm butyl acrylate rubber polymer and butyl acrylate rubber polymer having an average particle diameter of 100 nm The polymerization reaction was carried out while continuously adding a mixture of 0.1 parts by weight of tertiary dodecyl mercaptan and 60 parts by weight of distilled water at 70 ° C. for 3 hours. After the completion of the addition, in order to increase the polymerization conversion rate, the temperature was raised to 75 ° C., followed by further reaction for 1 hour, and the reaction was completed by cooling to 60 ° C. to prepare a bimodal butyl acrylate-styrene-acrylonitrile graft copolymer. .

<Preparation of Bimodal ASA Graft Copolymer Powder>

The prepared bimodal butyl acrylate-styrene-acrylonitrile graft copolymer was agglomerated at 80 ° C. using an aqueous calcium chloride solution, and then aged at 95 ° C., washed and dehydrated, followed by 30 minutes of hot air at 90 ° C. Drying to give a final bimodal butyl acrylate-styrene-acrylonitrile graft copolymer powder having a moisture content of less than 0.5% and a density of 0.4 g / cm 3.

<Preparation of ASA resin composition for PVC coextrusion>

40 parts by weight of the bimodal butyl acrylate-styrene-acrylonitrile graft copolymer powder, 60 parts by weight of methyl methacrylate-styrene-acrylonitrile terpolymer (XT-500, LG Chemical), lubricant 1 part by weight of EBS (precursor chemicals), 0.5 part by weight of Irganox 1076 (product of Ciba-Geigy) as an antioxidant, and 0.5 part by weight of Tinuvin 327 (product of Ciba-Geigy) as a UV stabilizer at 220 ° C. By kneading (or simply mixing without melt kneading?), ASA resin composition for PVC coextrusion was finally prepared.

Comparative Example 1

Except for using the butyl acrylate-styrene-acrylonitrile graft copolymer having an acrylonitrile content of 20% by weight (less than 35% by weight) in Example 1 was carried out in the same manner as in Example 1.

Comparative Example 2

Example 1 does not include a butyl acrylate rubber polymer having an average particle diameter of 200 nm (large diameter), except that a butyl acrylate rubber polymer having an average particle diameter of 100 nm (small diameter) is added in an amount not included It carried out in the same manner as in Example 1.

Comparative Example 3

Example 1 does not include a butyl acrylate rubber polymer having an average particle diameter of 100 nm (small diameter), except that a butyl acrylate rubber polymer having an average particle diameter of 200 nm (large diameter) is added in an amount not included. It carried out in the same manner as in Example 1.

[Test Example]

The ASA resin composition for PVC coextrusion prepared in Example 1 and Comparative Examples 1 to 4 was prepared in pellet form using a 40 pie extrusion kneader at a cylinder temperature of 200 ° C., respectively, and then injected to prepare a specimen. The properties of the specimens were measured by the following method, and the results are shown in Table 1 below.

A) Impact strength (Izod impact strength, 1/4 "notched at 23 ℃, kg ㎝ / cm): measured according to ASTM D256.

B) Scratch resistance: measured by pencil hardness.

C) Weather resistance: After 2,000 hours test using Atlas Ci35A W-O-M (Xenon Lamp, Energy 0.35 w / ㎡ at 340nm), the degree of discoloration was measured by ΔE.

D) Average particle size: measured using a particle size analyzer NICOMP 380.

ㅁ) Weight average molecular weight: The sample was dissolved in THF (tetrahydrofuran) and measured using GPC.

I) Glass transition temperature: measured using DSC Q100 (TA Instruments).

S) adhesive strength: by the method disclosed in Figure 1, it was measured using the following equation (1).

[Equation 1]

division Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Impact strength 12 10 4 14 Scratch resistance HB B HB B Weatherability 0.2 0.4 0.3 0.2 Adhesion 38 31 35 36

As shown in Table 1, the ASA resin composition for PVC coextrusion (Example 1) of the present invention is the case of acrylonitrile content outside the scope of the present invention (Comparative Example 1) and monomodal (monomodal) ASA graft Compared to the case of including the copolymer (Comparative Examples 2 and 3), it was confirmed that the weather resistance, scratch resistance, adhesion, impact strength and chemical resistance were all excellent.

For reference, the thermal stability of the ASA film, PMMA film and PVC film in the thermal stability test of Figure 4 was found to be similar, but this result is separate from the workability during co-extrusion.

Claims (17)

Iii) bimodal alkyl acrylate-styrene-acrylonitrile-based graft copolymers and ii) alkyl methacrylate-styrene-acrylonitrile-based copolymers by melt kneading,
(Iii) The bimodal alkyl acrylate-styrene-acrylonitrile graft copolymer includes an alkyl acrylate rubber having an average particle size of 180 to 230 nm and an alkyl acrylate rubber having an average particle size of 80 to 130 nm. Graft polymerization, characterized in that containing 35 to 45% by weight of vinyl cyan monomer
ASA resin composition for PVC coextrusion. The method of claim 1,
The content ratio (large diameter / small diameter) of the alkyl acrylate rubber having an average particle diameter of 180 to 230 nm and the alkyl acrylate rubber having an average particle diameter of 80 to 130 nm is 3/4 to 4/3.
ASA resin composition for PVC coextrusion. The method of claim 1,
(Iii) The bimodal alkyl acrylate-styrene-acrylonitrile graft copolymer is a vinyl aromatic monomer and a vinyl cyan monomer graft polymerized on a bimodal alkyl acrylate rubber.
ASA resin composition for PVC coextrusion. The method of claim 1,
The alkyl acrylate rubber, characterized in that the alkyl group is composed of an alkyl acrylate monomer consisting of 2 to 8 carbons
ASA resin composition for PVC coextrusion. The method of claim 3, wherein
The vinyl aromatic monomer is characterized in that at least one member selected from the group consisting of styrene and derivatives thereof.
ASA resin composition for PVC coextrusion. The method of claim 1,
(Iii) the bimodal alkyl acrylate-styrene-acrylonitrile-based graft copolymer is prepared by emulsion graft polymerization.
ASA resin composition for PVC coextrusion. The method of claim 1,
(Iii) The bimodal alkyl acrylate-styrene-acrylonitrile graft copolymer includes 25 to 45 wt% of an alkyl acrylate rubber, 20 to 40 wt% of a vinyl aromatic monomer, and 35 to 45 vinyl cyan monomer. Characterized by weight percent
ASA resin composition for PVC coextrusion. The method of claim 1,
(Iii) the bimodal alkyl acrylate-styrene-acrylonitrile graft copolymer has a weight average molecular weight of 150,000 to 200,000.
ASA resin composition for PVC coextrusion. The method of claim 1,
Ii) The alkyl methacrylate-styrene-acrylonitrile-based copolymer is a methyl methacrylate-styrene-acrylonitrile-based copolymer, an ethyl methacrylate-styrene-acrylonitrile-based copolymer, or a mixture thereof. Characterized by
ASA resin composition for PVC coextrusion. The method of claim 1,
Ii) Alkyl methacrylate-styrene-acrylonitrile copolymers are produced by bulk polymerization
ASA resin composition for PVC coextrusion. The method of claim 1,
The ii) alkyl methacrylate-styrene-acrylonitrile-based copolymer has a weight average molecular weight of 80,000 to 150,000.
ASA resin composition for PVC coextrusion. The method of claim 1,
Wherein the ii) alkyl methacrylate-styrene-acrylonitrile copolymer, the glass transition temperature is 80 to 120 ℃
ASA resin composition for PVC coextrusion. The method of claim 1,
The ASA resin composition for PVC co-extrusion, 20 to 50% by weight of the bimodal alkyl acrylate-styrene-acrylonitrile graft copolymer; And ii) 50 to 80% by weight of an alkyl methacrylate-styrene-acrylonitrile copolymer.
ASA resin composition for PVC coextrusion. The method of claim 1,
The ASA resin composition for PVC coextrusion, characterized in that it further comprises one or more selected from the group consisting of lubricants, antioxidants, ultraviolet stabilizers, dyes, pigments, flame retardants and inorganic fillers.
ASA resin composition for PVC coextrusion. The PVC co-extrusion ASA film of any one of claims 1 to 14 PVC co-extrusion ASA resin composition. The extruded sheet prepared by co-extrusion of the ASA film for PVC co-extrusion, and PVC resin film of claim 15. A building exterior material manufactured from the extruded sheet of claim 16.

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