KR20090029539A - Low surface gloss styrene resin composition, and low surface gloss sheet and composite article therefrom - Google Patents

Abstract

A low surface gloss styrene resin composition is provided to ensure excellent weather resistance, impact resistance, and low gloss, thereby being suitable for the exteriors of structures including lining board and window frame. A low surface gloss styrene resin composition comprises (A) base resin 80-99.9 weight% including a rubber-modified styrene polymer; (B) low gloss styrene resin containing syndiotatic polystyrene 0.1-20 weight% as a matting agent; and (C) hydrogenated styrene block copolymer 0.1-20 weight% including a styrene block and a butadiene rubber block as a compatibilizer, based on the total weight of the base resin(A) and the low gloss styrene resin containing a matting agent.

Description

LOW SURFACE GLOSS STYRENE RESIN COMPOSITION, AND LOW SURFACE GLOSS SHEET AND COMPOSITE ARTICLE THEREFROM

The present invention relates to a low gloss styrene resin composition, a sheet and a composite prepared therefrom, and more particularly, to excellent weather resistance and impact resistance, and to reduce surface gloss to use in exterior applications of structures such as walls and window frames. In particular, it relates to a low gloss styrenic resin composition, a sheet and a composite produced therefrom.

Styrene copolymers composed of a resin matrix and an elastomer or rubber component include acrylate-styrene-acrylonitrile (ASA), olefin-styrene-acrylonitrile (OSA), acrylonitrile-ethylenepropylenediene rubber (EPDM) -styrene ( AES) or acrylonitrile-butadiene-styrene (ABS) and the like are known. These resins are capable of various performance characteristics depending on the elastic component, in particular, ASA resin is known to be excellent in impact strength, workability and weather resistance, and ABS resin low temperature impact and processability.

In general, the use of thermoplastic resins such as ABS and ASA resins is rapidly increasing in a wide range of parts, such as automobile interior materials, office equipment, building materials, etc. from everyday life products. Products made from these thermoplastic resin compositions are mostly glossy, and extruded products of ABS, AES and ASA resins are in the high gloss (90 gloss at 75 °) or intermediate gloss (60 gloss at 75 °) ranges. It shows surface gloss.

However, in recent years, the demand for low-gloss resins has been increasing to create a more elegant atmosphere as users' emotional quality demands have risen. Also, due to environmental problems, the use of matte coatings or pads is omitted and the matte resins have been omitted. The trend is to use it directly. In particular, there is a great demand for low-gloss resin compositions in applications such as building wallboards, computer housings, keyboards, electrical appliances and automotive parts. Therefore, the provision of ABS, AES, ASA resin, especially ASA resin with reduced surface gloss while having excellent physical properties in the prior art would be more advantageous in the use of the construction industry, particularly in the field of exteriors for structures such as wallboard.

In order to manufacture such a low gloss resin, a method of controlling the flatness of the surface of the resin to be larger than the visible light region to scatter incident light to exert a matt effect is mainly used.

In the prior art, a method of adding or modifying a specific rubber or elastomer component is used. Specifically, the following three methods may be mentioned. First, there is a method of improving the ABS resin using large diameter rubber particles having an average particle diameter of 2 μm or more obtained by bulk polymerization. However, the resin produced by the above method has a low gloss effect and has a problem in that impact strength and heat resistance are lowered. Second, there is a method of injecting a matte filler having an average particle diameter of 5 μm or more into the resin. While the resin produced by the above method exhibits excellent moldability, the low glossiness is insufficient, and in particular, the drop in impact strength is severe. Third, there is a method of producing by graft polymerization of a monomer such as ethylene-unsaturated carboxylic acid with a modifier to the ABS polymer produced by the emulsion polymerization method. The resin produced by the above method is a method widely used due to its excellent impact strength and general physical properties and excellent low gloss effect, but has a limitation in that the heat resistance is lowered and the weather resistance is lowered when applied to the weathering resin (ASA).

U.S. Pat.No. 5,081,193 discloses a low gloss agent for thermoplastic resins comprising graft copolymers containing rubber as a rubber component, in particular low-cis polybutadiene, and U.S. Pat. No. 5,237,004 describes specific core / shells. A method of reducing surface gloss by adding polymer particles of 2 to 15 μm to a thermoplastic polymer composition of structure is disclosed. US Pat. No. 5,475,053 discloses a molding composition of a matte surface comprising impact modified thermoplastics such as ABS or ASA and matting agents. US Pat. No. 4,652,614 is based on neutral and acidic graft polymers. A matting surface molding material is disclosed. US Patent No. 4,169,869 discloses an ABS compound with a low gloss or matt finish, US Patent No. 4,668,737 has a total rubber content of 5 to 80% by weight, an average particle diameter of 0.05 to 20.0 μm, and a glass transition temperature. 20 to 0.1 parts by weight of heterocyclic nitrogen substrate, 40 to 99.8 parts by weight of aromatic vinyl monomer, 20 to 0.1 parts by weight of monoacid or diacid containing polymerizable double bond, and acrylonitrile on a particulate rubber of 10 ° C. or less. A graft polymer having a matte surface including from 40 parts by weight is disclosed.

However, the above-mentioned prior arts have limitations that exhibit one or more disadvantages without even satisfying features such as weather resistance, impact resistance, appropriate reduction of surface gloss, quality of surface appearance, manufacturing cost and processability of the resin.

In order to solve the problems of the prior art as described above, the present invention is excellent in weatherability and impact resistance, and the surface gloss is reduced to provide a low-gloss styrene resin composition particularly suitable for use in the field of exterior construction, such as wall panels, window frames, etc. For the purpose of

In addition, an object of the present invention is to provide a low-gloss styrene resin composition with improved workability and impact resistance.

It is another object of the present invention to provide a sheet and a composite suitable for external siding for a structure, and a method for producing the same, which are prepared from the low-gloss styrene resin composition having improved processability.

The above and other objects of the present invention can be achieved by the present invention described below.

The present invention provides a low gloss styrene resin composition. The composition of the present invention comprises (A) 80 to 99.9% by weight of a basic resin containing a rubber-modified styrene-based polymer, and (B) a low-gloss styrene resin composed of 0.1 to 20% by weight of syndiotactic polystyrene as a matte agent, (C) 0.1 to 20 hydrogenated styrene block copolymer comprising styrene block and butadiene rubber block as a compatibilizer based on the total weight of the low gloss styrene resin comprising (C) the base resin and the (B) matte agent. weight%

It further includes. The rubber modified styrene-based polymer is formed by copolymerizing a styrene-based monomer and optionally an unsaturated ethylene compound in the presence of rubber.

Here, the base resin (A) preferably further includes a non-rubber modified styrene copolymer in which a styrene monomer and an unsaturated ethylene compound are copolymerized. In particular, the non-rubber modified styrene copolymer is preferably a mixture of a styrene-acrylonitrile copolymer and a styrene-acrylonitrile- (meth) acrylate copolymer.

The low gloss styrene resin composition of the present invention also preferably further comprises 0.1 to 30% by weight of (D) plasticizer, based on the total weight of the low gloss styrene resin comprising (A) the base resin and (B) the matte agent. Do.

The low gloss styrene resin composition of the present invention has a low gloss of 1 to 50 glossiness at 75 °.

In another aspect, the present invention is a method for producing a sheet comprising the step of forming a sheet by extruding by a extruder at a temperature of at least 180 ℃ the low-gloss styrene-based resin composition and 20 ℃ or more lower than the melting temperature of the syndiotactic polystyrene matte The sheet manufactured by the manufacturing method is provided.

The present invention also provides a composite comprising an inner layer and an outer layer coupled to at least one surface of the inner layer to prevent the inner layer from being exposed to the external environment. At this time, the inner layer is formed of a thermoplastic resin material having better weather resistance than the outer layer, and the outer layer is formed by the low-gloss styrene resin composition described above.

The present invention can further improve impact resistance by adding a compatibilizer to a composition which does not deteriorate weather resistance and impact resistance of the base resin by the matte agent by combining syndiotactic polystyrene, which is a matte, with a base resin having excellent weatherability and impact resistance. have.

In addition, the present invention can further improve the workability and impact resistance by further adding a plasticizer to the composition in which the base resin and the matting agent are combined.

The present invention also provides a rubber-modified styrene-based polymer by adding a non-rubber-modified styrene-based copolymer, in particular a mixture of styrene-acrylonitrile copolymer and styrene-acrylonitrile- (meth) acrylate copolymer to form a basic resin. Weather resistance can be further improved.

In addition, the present invention can reduce the degradation of physical properties, in particular weatherability and impact resistance by producing a sheet by processing the low-gloss styrene resin composition described above at a lower temperature than the melting point of the syndiotactic polystyrene used as a matting agent.

Therefore, the sheet and composite prepared by the low-gloss styrene-based resin composition of the present invention can be applied to a variety of products because it has excellent weather resistance and impact resistance and low gloss, in particular for use in the exterior field of structures such as wall panels, window frames It can be applied suitably.

The present inventors include weather resistant styrene-based resin and syndiotactic polystyrene (sPS) as a matting agent, and further include a plasticizer as a compatibilizer and a processability improving additive, and adjust the rubber content and the content of the matting agent of the styrene-based resin. The thermoplastic resin composition was confirmed that the fall impact strength, weather resistance and low gloss effect is excellent, to complete the present invention based on this.

The low gloss styrene resin composition of the present invention is a low gloss styrene resin comprising (A) 80 to 99.9% by weight of a basic resin containing a rubber-modified styrene polymer, and (B) 0.1 to 20% by weight of syndiotactic polystyrene as a matte agent. And further comprising (C) a styrene block and a butadiene rubber block as compatibilizers based on the total weight of the low gloss styrene resin comprising (C) the base resin and (B) matte It further comprises 0.1 to 20% by weight of coalescing. In addition, the low-gloss styrene resin composition of the present invention, based on the total weight of the low-gloss styrene resin of the (A) base resin and the (B) matte agent, (D) plasticizer 0.1 to 30% by weight as a workability improving additive further It may include. Such a low gloss styrene resin composition of the present invention has a low gloss of 1 to 50 gloss at 75 ° as measured by a TOYOSEIKI (GLOSS METER UD) gloss meter.

Hereinafter, the components of the composition of the present invention will be described.

In the present specification, for convenience, the (a) rubber-modified styrene polymer and the (b) non-rubber-modified styrene copolymer described below are referred to as (A) styrene resin and this is referred to as the basic resin of the present invention. In addition, a combination of (A) styrene resin and (B) matte syndiotactic polystyrene will be referred to as low gloss styrene resin.

(A) styrene resin

The styrene resin used as a component of the composition of the present invention refers to a copolymer resin formed by copolymerization of a styrene monomer with another comonomer, and the rubber-modified styrene polymer, the styrene monomer, and the unsaturated ethylene compound described below. This copolymerized non-rubber modified styrene copolymer is included. Here, the unsaturated ethylene compound means a compound having a double bond of carbon-carbon and an unsaturated bond of a carbon-non-carbon element.

The styrene monomer may be understood to include not only styrene but also a styrene derivative having a substituent.

(a) Rubber modified styrene polymer

The rubber-modified styrene polymer used in the present invention is preferably formed by copolymerizing a styrene monomer and optionally an unsaturated ethylene compound in the presence of an elastomer rubber.

The elastomeric rubber may be formed by polymerization of alkyl acrylates, butadiene, isoprene, olefin compounds, and mixtures thereof having an alkyl group having 1 to 32 carbon atoms, preferably 1 to 8 carbon atoms. At this time, a compound selected from the group consisting of unsaturated ethylene compounds, styrene-based monomers and polyfunctional monomers may be used as a comonomer for producing the rubber. Comonomers for the preparation of such rubbers are added in amounts such that the rubber properties can be expressed, and the acceptable content of such comonomers is commonly known and can also be determined by experiment.

The elastomer rubber may be polybutadiene, polyisoprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, alkyl acrylate rubber, ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM) or silicone rubber Etc. can be used.

The elastic rubber is preferably contained in 5 to 50% by weight in the rubber modified styrene resin. The content of such rubber plays an important role in making the composition of the present invention have sufficient impact resistance, and when the rubber content is too high, it may adversely affect the hardness and scratch resistance. As the styrene monomer, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, 1,3-dimethylstyrene, and tert-butylstyrene may be used. Preferably, styrene, α-methylstyrene, p-methylstyrene or tert-butylstyrene, more preferably styrene or α-methylstyrene can be used.

The rubber-modified styrene-based polymer may be formed by copolymerization of the rubber and styrene-based monomer only. Preferably, the rubber-modified styrene-based polymer is copolymerized with a styrene-based monomer and an unsaturated ethylene compound.

As the unsaturated ethylene compound, acrylonitrile, methacrylonitrile, alkyl acrylates having 1 to 4 carbon atoms and alkyl methacrylates, acrylic acid, methacrylic acid, maleic anhydride, acrylamide, and the like may be used. Preferably acrylonitrile can be used.

The unsaturated ethylene compound is preferably contained in 5 to 50% by weight in the rubber-modified styrene polymer. When included in the content has the effect of improving heat resistance, chemical resistance and mechanical strength. Therefore, in this case, the styrene-based monomer is included in the rubber modified styrene-based polymer 40 to 90% by weight. More preferably, it may be included in 50 to 70% by weight. When included in the content has the effect of improving mechanical strength and impact strength.

The method for producing a rubber-modified styrene polymer is generally well known, and as such a method, bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, and the like are known, and in particular, a method for preparing by emulsion polymerization is widely used. The rubber-modified styrene resin used in the present invention can be prepared by a conventional method.

(b) non-rubber modified styrene copolymer

The styrene resin used in the present invention is a non-rubber in which a styrene monomer and an unsaturated ethylene compound are copolymerized in addition to the rubber-modified styrene polymer in order to control rubber content or to control physical properties such as impact resistance and weather resistance. It may further include a modified styrene-based copolymer.

The unsaturated ethylene compound is the same as mentioned above, it is also preferably included in 20 to 80% by weight in the styrene-based copolymer.

Examples of the styrene copolymers include styrene-acrylonitrile copolymers, styrene / acrylonitrile / methyl methacrylate terpolymers, α-methylstyrene / acrylonitrile copolymers, styrene / methyl methacrylate copolymers, and styrene / Maleic anhydride copolymer, α-methylstyrene / styrene / acrylonitrile terpolymer, styrene / acrylonitrile / maleic anhydride, styrene / acrylonitrile / acrylic acid terpolymer, or α-methylstyrene / styrene / acrylic A ronitrile terpolymer etc. can be used individually or in mixture of 2 or more types.

In particular, preference is given to using styrene / acrylonitrile copolymers, styrene / acrylonitrile / (meth) acrylate terpolymers or mixtures thereof.

(b1) Styrene / Acrylonitrile Copolymer (SAN)

The said SAN copolymer can be manufactured by a bulk polymerization method or an emulsion polymerization method. Examples of the styrene-based monomers included in the SAN copolymer may be the above-mentioned compounds, and they may have various substituents.

As the acrylonitrile monomer included in the SAN copolymer, for example, one or more compounds selected from the group consisting of acrylonitrile, methacrylonitrile, and eta acrylonitrile can be used, and in addition to these, Acrylonitrile monomers can also be used without any limitation. Thus, the term acrylonitrile-based monomer or acrylonitrile monomer herein may be understood to include acrylonitrile derivatives.

The content of acrylonitrile monomer in the styrene / acrylonitrile copolymer is preferably 10 to 50% by weight. If the content is less than 10% by weight, there is a problem such as lowering the chemical resistance on the product, when the content exceeds 50% by weight is not preferable because there is a problem such as high viscosity due to high viscosity.

On the other hand, the non-rubber modified styrene-based copolymer containing such a styrene-based monomer and acrylonitrile-based monomer, it is preferable to use those having a weight average molecular weight in the range of 50,000 to 250,000 bar, the weight average molecular weight is within the above range In the case of deviation, there is a problem that physical properties and appearance defects are not preferable.

(b2) Styrene / Acrylonitrile / (meth) acrylate copolymer (SAN-MMA)

The styrene / acrylonitrile / (meth) acrylate copolymer used in the present invention is preferably 40 to 80% by weight of methacrylic acid alkyl ester derivative or acrylic acid alkylester derivative, 15 to 40% by weight styrene monomer and 3 to 20% by weight of the acrylonitrile monomer is a copolymer formed by copolymerization. Although there is no restriction | limiting in particular in the manufacturing method of the said copolymer in this invention, suspension polymerization and block polymerization are preferable. In particular, continuous bulk polymerization is the best method in terms of manufacturing cost.

In addition, the polymerization of the bulk polymerization can increase the content of acrylonitrile. In the case of polymerization in an aqueous phase, such as emulsion polymerization or suspension polymerization, if the content of vinyl cyanide derivatives, for example, acrylonitrile is high, acrylonitrile, a hydrophilic monomer, generates a large amount of homopolymer in the aqueous phase, resulting in a yellow resin. have. In the bulk polymerization, even if the vinyl cyan derivative is raised to a certain level, the production of homopolymers is small, and thus, the color of yellow is reduced. Therefore, the content of the vinyl cyan derivative can be increased, thereby improving chemical resistance and impact resistance. Vinylcyan derivative is used in 3 to 20% by weight. When the vinyl cyan derivative is used at less than 3% by weight, chemical resistance, scratch resistance and impact strength are lowered, and when used at more than 20% by weight, the color becomes yellow.

On the other hand, when the methacrylic acid or acrylic acid alkyl ester and styrene monomer is outside the above range, the transparency becomes worse.

Styrene monomers and acrylonitrile monomers used for the polymerization of the styrene / acrylonitrile / (meth) acrylate copolymers used in the present invention are the same as those mentioned above, and the methacrylic acid or acrylic acid alkyl ester derivatives Examples include methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid propyl ester, methacrylic acid 2-ethylhexyl ester, methacrylic acid decyl ester, methacrylic acid lauryl ester and the like, among others methacrylic Most preferred are acid methyl esters, ie methyl methacrylate.

The non-rubber-modified styrenic copolymer (b) can be incorporated into the styrene-based resin using a typical extrusion formulation using a single- or twin-screw extruder known in the art. As a specific example, the melt of the rubber modified styrene polymer (a) and the non-rubber modified styrene copolymer (b) may be mixed vigorously at a temperature exceeding 200 ° C.

The styrene-based resin may further include additives such as fillers, compatible plastics, antistatic agents, antioxidants, flame retardants or lubricants. The additive may be included in an amount of 0.1 to 70 parts by weight based on 100 parts by weight of the styrene resin.

In addition, the styrene resin may further include a dye or pigment in an amount of 0.02 to 10 parts by weight based on 100 parts by weight of the styrene resin.

As the rubber-modified styrene polymer, ASA, ABS or AES resin may be used, and as the non-rubber-modified styrene copolymer (b), (b1) styrene / acrylonitrile (SAN) copolymer and (b2) styrene Resin containing / acrylonitrile / methyl methacrylate (SAN-MMA) terpolymer may be used. Preferably, a resin containing a SAN copolymer and a SAN-MMA copolymer in an ASA resin or ASA resin is used together.

Specific examples of the rubber-modified styrene resin (a) in which styrene and acrylonitrile are grafted in a weight ratio of 75:25 to butyl acrylate or tricyclodecenyl acrylate elastomer rubber, and the acrylonitrile content of 22 to 35 Styrene-based resin (A) further mixed with styrene / acrylonitrile copolymer (b1) in weight% and styrene / acrylonitrile / methyl methacrylate terpolymer (b2) in weight ratio of 60 to 80% by weight desirable.

The styrene resin (A) is preferably contained in 80 to 99.9% by weight of 100 parts by weight of the low-gloss styrene resin composition. When included in the content is excellent in mechanical strength, in particular has the effect of improving the weather resistance and matt effect.

(B) Matte

The matting agent used in the present invention is a crystalline polymer, syndiotactic polystyrene (sPS). Here, the syndiotactic polystyrene may be understood to include not only polystyrene polymerized with styrene monomers but also polystyrene copolymers formed by copolymerization of styrene monomers and comonomers. At this time, the styrene monomer is understood to include styrene derivatives as well as styrene, the comonomer copolymerized with the styrene monomer may be used in the range of 10% by weight or less, in particular 0.1 to 10% by weight, maleic anhydride, Maleic acid, fumaric acid and glycidyl methacrylate. Syndiotactic polystyrene may also be one having a carboxylic acid group formed at at least one end thereof. Thus, syndiotactic polystyrene (sPS) is polystyrene, carboxyl end-syndiotactic polystyrene (sPS-COOH), maleic anhydride-syndiotactic polystyrene (sPS-MAH), maleic acid-syndiotactic polystyrene (sPS- MA), fumaric acid-syndiotactic polystyrene (sPS-FA) glycidylmethacrylate-syndiotactic polystyrene (sPS-GMA).

The matting agent sPS has a stereostructure in which the steric structure is a syndiotactic structure, that is, a phenyl group or a substituted phenyl group which is a side to the main branch formed by a carbon-carbon bond, and is located opposite to each other. Unlike polystyrene, it is a polymer with a crystalline structure. The steric structure can be quantitatively expressed by the C13-NMR method.

As the sPS, polystyrene, polyhalogenated styrene, polyalkoxystyrene, polyalkylstyrene, polybenzoate ester styrene, having a stereoregularity of 85% or more in the case of diad and 35% or more in the case of pentad (racemic pentade), Alternatively, a copolymer such as styrene or a styrene derivative as a main component or the like may be used alone or in combination of two or more thereof.

The matting agent has a melting temperature of approximately 260 to 280 ° C., and is superior in heat resistance and mechanical properties as compared with a styrene polymer having a conventional atactic structure.

The matting agent is preferably included in 0.1 to 20% by weight, preferably 1 to 10% by weight in 100 parts by weight of the low-gloss styrene resin composition. When included in the content is not only excellent impact strength, but also has the effect of improving the matte properties.

(C) compatibilizer

In the present invention, a compatibilizer is used to increase the miscibility between syndiotactic polystyrene (sPS) and styrene resin. As such compatibilizers, styrene block copolymers comprising blocks of styrene repeating units and blocks of butadiene rubber are used, preferably hydrogenated styrene block copolymers. Here, the butadiene rubber block is formed by polymerization of butadiene or butadiene derivatives, for example, isoprene or by copolymerization of butadiene or butadiene derivatives with comonomers such as ethylene and propylene. A typical example of such a styrene block copolymer is a styrene block copolymer (SEBS), which is a styrene block-butadiene rubber block-styrene block, in which a butadiene rubber block is a rubber block formed by copolymerization of butadiene and ethylene.

The styrene block copolymer used in the present invention is preferably a hydrogenated styrene block copolymer, and weatherability can be improved by hydrogenating a butadiene rubber block. Meanwhile, in preparing the styrene block copolymer, maleic anhydride may be polymerized as a comonomer in at least one of the blocks, particularly in the styrene block, to form a block. Including maleic anhydride in a block has the effect of improving heat resistance. Maleic anhydride added as comonomer is preferably added at about 10% by weight or less, for example 0.1 to 10% by weight, based on the weight of the block to be added. As an example of the compatibilizer used in the present invention, maleic anhydride-hydrogenated styrene / butadiene / styrene copolymer (SEBS-MAH) having about 1.5% by weight maleic anhydride may be used. Such hydrogenated styrene block copolymers are sold as products and their preparation is also known.

The compatibilizer used in the present invention is 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on the total weight of the low-gloss styrene resin made of (A) the base resin and (B) the matting agent. If the content is less than 0.1% by weight, miscibility is lowered, and if it is greater than 10% by weight, especially greater than 20% by weight is not preferable because of the increase in manufacturing cost.

(D) processability improvement additive

In this invention, a plasticizer can be used as a workability improvement additive. As such plasticizers, plasticizers commonly used may be used, for example, di-butyl-phthalate (DBP), di-2-ethylhexyl phthalate (DEHP or DOP), Phthalic acid ester plasticizers such as di-isonoyl phthalate (DINP), di-isodecyl phthalate (DIDP) and butyl benzyl phthalate (BBP), triethylhexyl Trimellitic acid systems such as Tri-ethylhexyl trimellitate (TEHTM or TOTM), Tri-isononyl trimellitate (TINTM) and Tri-isodecyl trimellitate (TIDTM) Trimellitic acid ester plasticizer, Tri-cresyl phosphate (TCP), tri-2-ethylhexyl phosphate (TEHP or TOP), cresyl diphenyl phosphate (CDP) ) Phosphoric acid ester plasticizers such as tri-aryl phosphate (TAP), epoxidized soybean oil (ESO) and epoxidized linseed oil (ELO) Epoxy plasticizers such as, Polyester plasticizers such as low polymerization polyesters having an average molecular weight of about 1,000 to 8,000, Di-2-ethylhexyl adipate (DEHA or DOA), Aliphatic acid ester plasticizers such as di-2-ethylhexyl azelate (DOZ) and di-isodecyl adipate (DIDA), and anti-chlorine plasticizers Can be used.

The syndiotactic polystyrene resin (sPS) used in the present invention has a melting temperature of about 270 ° C., which lowers the melt viscosity upon mixing with the styrene resin, thereby degrading workability. Thus, the present invention uses a plasticizer as a workability improving additive to improve the processability of the composition. Particularly preferred plasticizers are di-isodecyl phthalate (DIDP). The content of the plasticizer used in the present invention is 0.1 to 30% by weight, preferably 0.5 to 15% by weight, based on the total weight of the low gloss styrene resin (A) base resin and (B) matte. If the content is less than 0.1% by weight, the miscibility is lowered, and if the content is larger than 15% by weight, especially greater than 30% by weight, it is not preferable because of the increase in manufacturing cost.

Such a low gloss styrene resin composition of the present invention may be prepared in pellet form by, for example, kneading and extruding each component by feeding it into a single screw or twin screw extruder. At this time, the barrel temperature of the extruder should not be too lower than the melting point of the matte syndiotactic polystyrene to enable kneading and extrusion of the composition. However, it is preferable to extrude the rubber-modified styrene-based polymer at a temperature as low as possible in order to prevent deterioration of properties due to thermal history. Typically the extrusion can be carried out at or above the melting point of the syndiotactic polystyrene, if possible, at a barrel temperature not lower than 10 ° C. above the melting point of the syndiotactic polystyrene, more preferably at a temperature not lower than 20 ° C. .

The low gloss styrene resin composition prepared by the above method preferably has a glossiness of 1 to 50 glossiness, preferably 15 to 35 glossiness at 75 ° as measured by TOYOSEIKI (GLOSS METER UD) glossiness meter. Do.

The low gloss styrene resin composition may further include a matte filler. When the matte filler is used together with the matte agent, the gloss is further lowered to further improve the low gloss effect and to minimize the deterioration of mechanical strength. The matte filler is a well-known crosslinked SAN B-Mat (glass transition temperature: 122 ℃) and an inorganic filler, the inorganic filler is a Silicate inorganic filler (eg talc (mica), mica (clay), clay, Montmorillonite) may be selected from the group consisting of one or more mixtures of one or more mixtures selected from platy or spherical inorganic fillers such as glass beads, silica, glass flakes, calcium carbonate and metal oxides. have.

The present invention also provides a composite composite of a sheet made from the low gloss styrene resin composition and a sheet made of this sheet and another thermoplastic resin, and a method for producing the same.

The sheet may be manufactured by sheet-processing a low gloss styrene resin composition in a pellet state using a single screw or twin screw extruder. At this time, the processing temperature at the time of sheet processing is preferably 180 ℃ or more and 20 ℃ or more lower than the melting temperature of the matting agent. In the case of processing at a temperature lower than 20 ℃ lower than the melting temperature there is an effect that the matt properties of the styrene resin is preferably expressed.

In addition, the extrusion temperature is such that the sheet of the low-gloss styrene-based resin composition according to the present invention may be made of a sheet of thermoplastic resin selected from one or more of other thermoplastic resins such as acrylonitrile-butadiene-styrene resin and polyvinylchloride resin. It is particularly suitable for coextrusion to form composites. At this time, the extrusion temperature is preferably a temperature near the melting point of the thermoplastic resin, for example, a temperature of approximately 200 ° C. which is the melting point of the polyvinyl chloride when coextruded with a sheet made of a polyvinyl chloride resin. The thermoplastic material may include an impact modifier, a processing aid, a heat stabilizer, an antioxidant, a UV stabilizer, a filler, a lubricant, or a pigment.

The present invention also provides a composite comprising an inner layer and an outer layer coupled to at least one surface of the inner layer to block the inner layer from being exposed to the external environment. In such a composite, the inner layer is formed by a thermoplastic resin having better weather resistance than the outer layer, and the outer layer is formed by the low-gloss styrene resin composition of the present invention described above. Examples of the thermoplastic resin of the inner layer may include a thermoplastic resin selected from at least one selected from acrylonitrile-butadiene-styrene resin and polyvinyl chloride resin as mentioned above, and the thermoplastic material may include an impact modifier, Processing aids, thermal stabilizers, antioxidants, UV stabilizers, fillers, lubricants or pigments and the like.

In the composite according to the present invention, the inner layer may be formed of several layers as well as a single layer, and the outer layer may be formed on both sides of the inner layer. This inner layer and outer layer may be formed by continuously bonding by co-extrusion using an extruder, as mentioned above. Since the outer layer has excellent weather resistance, the inner layer can be protected from an external environment such as light and climate. Therefore, the composite of the present invention can be suitably applied to structural exterior products such as wall panels, window frames and 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  1-4, Comparative example  1 and 2

(A) Styrene-based resins include (a) SA927-DP resin (manufactured by LG Chem.) Containing acrylic rubber and (b1) SAN 90HR (manufactured by LG Chem.) With SAN resin having 25 g / 10min (220 ° C) of MI. Was used by mixing in a weight ratio as shown in Table 2 below. (B) As a matte agent, sPS 130ZC (made by Idemitsu Co., Ltd.) whose melting temperature is 270 degreeC was used. (C) As a compatibilizer, SEBS-MAH Scona TPKD 8112 (manufactured by Kometra) was used.

The styrene resin, the matting agent, and the compatibilizer were added in the composition shown in Table 3 below (in parts by weight), and 0.5 parts by weight of titanium dioxide (Chronos 2233) was added thereto, followed by a diameter of 27 mm in Leistritz. Using a twin screw extruder was mixed in the processing conditions of Table 1 below to prepare a pellet.

Using the prepared pellets TSE16TC 3-layer extrusion and T-die of Korea EM manufactured a sheet having a thickness of 3 mm under the processing conditions of Table 2 below, wherein the matte characteristics of the sheet extruded from the Ti die In order to express, it was processed at a temperature lower than 20 ℃ than the melting temperature of the matting agent during sheet processing.

Evaluation of physical properties used in the present invention is as follows.

(1) Glossiness: TOYOSEIKI (GLOSS METER UD) 75 ° measurement (%)

(2) Impact strength: ASTM D-256 (kgcm / cm)

(3) Weather Resistance: Atlas UV-2000

Condition-LIGHT SOURCE: UV-A LAMP

                  SEGMENT 1 (UV)

                  -BLACK PANEL TEMPERATURE: 60 ℃

                  -IRRADIANCE: 0.77 W / ㎡

The arithmetic mean value of the Hunter Lab values before and after the weathering test. The closer to 0, the better the weatherability.

(4) Capillary test: RHEO-TESTER 1501 (Temp.:200℃, Shear Rate: 1 ~ 3000 s ^-1 )

Extruder Barrel 1 Barrel 2 ~ 11 die Screw rotation speed Feed rate LEISTRITZ 260 ℃ 270 ℃ 270 ℃ 250 RPM 15 kg / hr

Extruder Barrel 1 Barrel 2 ~ 11 die Screw rotation speed Feed rate Korea EM 190 ℃ 200 ℃ 200 ℃ 250 RPM 3 kg / hr

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 A a 50 50 50 50 50 b b1 47 45 43 50 45 b2 - - - - B 3 5 7 - 5 C One One One - - D - - - - - Glossiness (75 °) 27 23 20 84.5 23 Impact Strength (1/4 ”) 9.0 8.5 5.0 25 8.2

Through Table 3, it was confirmed that the styrene-based resin composition of Examples 1 to 3 containing sPS as a matting agent is excellent in low gloss characteristics as compared to the resin composition of Comparative Example 1 containing no matting agent. . In addition, as can be seen in Example 2 and Comparative Example 2, it was confirmed that the impact strength is increased by improving the miscibility of the matting agent and the styrene resin.

Example  5 ~ 7

(B2) XT500 (manufactured by LG Chem) with SAN-MMA resin having a MI of 50 g / 10min (220 ° C.) and (D) a plasticizer DIDP (manufactured by LG Chem) with processability enhancing additives in Example 1 are shown in Table 4 below. The same procedure as in Example 1 was carried out except that the composition was used.

Example 4 Example 5 Example 6 Example 7 Reference Example A a 50 50 50 50 50 b b1 35 25 35 35 45 b2 10 20 10 10 - B 5 5 5 5 5 C One One One One One D - - 5 10 - Glossiness (75 °) 22 23 22 22 24 Impact Strength (1/4 ”) 8.5 8.3 9.0 10.2 8.5

Through Table 4, the styrene-based resin composition of Examples 4 to 7 was confirmed that the low-gloss characteristics are not inferior compared to the resin composition of the reference example that does not include SAN-MMA and workability improving additives, Example 6 and In the case of Example 7, it was confirmed that the impact resistance is improved as the workability improving additive DIDP is included.

1, it can be seen that as the amount of SAN-MMA added increases, the change in DE is less, and thus the weather resistance is excellent.

2, it can be seen that the melt viscosity decreases as the workability improving additive is included, thereby making it easier to substantially produce the product.

1 is a graph showing that an embodiment of the present invention using a styrene-based resin containing SAN-MMA as a base resin exhibits excellent weather resistance compared to an example using a styrene-based resin containing no SAN-MMA as a base resin. .

Figure 2 is a graph showing the apparent viscosity against the apparent shear rate as compared with and without the plasticizer in the composition of the embodiment of the present invention.

Claims (27)

(A) 80 to 99.9% by weight of a base resin containing a rubber-modified styrene polymer, and (B) a low gloss styrene resin composed of 0.1 to 20% by weight of syndiotactic polystyrene as a matte agent, and (C) 0.1 to 20 weight of hydrogenated styrene block copolymer comprising styrene block and butadiene rubber block as compatibilizer based on the total weight of the low gloss styrene resin of (A) base resin and (B) matte agent Low gloss styrene resin composition containing%. The method of claim 1, The rubber-modified styrene-based polymer is a low gloss styrene resin composition, characterized in that formed by copolymerizing a styrene monomer and optionally an unsaturated ethylene compound in the presence of a rubber. The method of claim 2, The rubber is at least one selected from the group consisting of polybutadiene, polyisoprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, alkyl acrylate rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber and silicone rubber Low gloss styrene resin composition, characterized in that. The method of claim 2, The rubber-modified styrene-based polymer is a low gloss styrene resin composition, characterized in that the content of 5 to 30% by weight. The method of claim 2, The styrene monomer is low gloss, characterized in that selected from the group consisting of styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, 1,3-dimethylstyrene, and tert-butylstyrene Styrene-based resin composition. The method of claim 2, The unsaturated ethylene compounds are acrylonitrile, methacrylonitrile, alkyl acrylates and alkyl methacrylates having 1 to 4 carbon atoms, acrylic acid, methacrylic acid, maleic anhydride, acrylamide and vinyl methyl ether. Low gloss styrene resin composition, characterized in that at least one selected from the group consisting of. The method of claim 2, In the rubber-modified styrene polymer, the content of rubber is 5 to 30% by weight, the content of the styrene monomer is 40 to 90% by weight, and the content of the unsaturated ethylene compound is 5 to 30% by weight. Styrene-based resin composition. The method of claim 1, The base resin (A) is a low gloss styrene resin composition, characterized in that it further comprises a non-rubber modified styrene copolymer copolymerized with a styrene monomer and an unsaturated ethylene compound. The method of claim 8, The low-gloss styrene resin composition, characterized in that the content of the unsaturated ethylene compound in the non-rubber modified styrene copolymer is 20 to 80% by weight. The method of claim 8, The non-rubber modified styrene-based copolymer is a styrene-acrylonitrile copolymer, styrene-acrylonitrile-methyl methacrylate terpolymer, α-methyl styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer , Styrene-maleic anhydride copolymer, α-methylstyrene-styrene-acrylonitrile terpolymer, styrene-acrylonitrile-maleic anhydride terpolymer, styrene-acrylonitrile-acrylic acid terpolymer, and α- Low-gloss styrene resin composition, characterized in that at least one selected from the group consisting of methyl styrene- styrene- acrylonitrile terpolymer. The method of claim 8, The non-rubber-modified styrene copolymer is a low gloss styrene resin composition, characterized in that a mixture of styrene-acrylonitrile copolymer and styrene-acrylonitrile- (meth) acrylate copolymer. The method of claim 11, The styrene-acrylonitrile copolymer is formed by copolymerization of 50 to 90% by weight of a styrene monomer and 10 to 50% by weight of an acrylonitrile copolymer, and has a weight average molecular weight of 50,000 to 250,000, and the styrene-acryl The nitrile- (meth) acrylate copolymer is formed by copolymerizing 40 to 90% by weight of (meth) acrylate monomer, 15 to 40% by weight of styrene monomer and 3 to 20% by weight of acrylonitrile monomer. Low gloss styrene resin composition. The method of claim 1, The syndiotactic polystyrene is a low gloss styrene resin composition, characterized in that the stereoregularity is 85% or more in the case of a diad, 35% or more in the case of pentad (racemic pentad). The method of claim 1, The syndiotactic polystyrene has a carboxylic acid group formed on at least one end of the polystyrene, or a comonomer and styrene selected from the group consisting of maleic anhydride, maleic acid, fumaric acid and glycidyl methacrylate. Monomer is formed by copolymerization, wherein the content of the comonomer is a low gloss styrene resin composition, characterized in that 0.1 to 10% by weight. The method of claim 1, The hydrogenated styrene block copolymer is in the form of a styrene block-butadiene rubber block-styrene block, wherein the butadiene rubber block is a low gloss styrene resin, characterized in that the rubber block formed by copolymerizing butadiene and ethylene. Composition. The method of claim 15, The hydrogenated styrene block copolymer is one in which at least one block of the blocks is formed by copolymerization of monomers of the block with maleic anhydride, and the content of the comonomer maleic anhydride is based on the weight of the block. Low gloss styrene resin composition, characterized in that 0.1 to 10% by weight. The method of claim 1, The low gloss styrene resin composition further comprises 0.1 to 30% by weight of a plasticizer based on the total weight of the low gloss styrene resin comprising the (A) base resin and the (B) matte agent. Composition. The method of claim 17, The plasticizer is di-butyl-phthalate (DBP), di-2-ethylhexyl phthalate (DEHP or DOP), di-isonoyl phthalate (DINP) Phthalic acid ester plasticizer consisting of di-isodecyl phthalate (DIDP) and butyl benzyl phthalate (BPB), triethylhexyl trimellitate (TEHTM or TOTM) ), Trimellitic acid ester plasticizer, tricresyl phosphate consisting of Tri-isononyl trimellitate (TINTM) and Tri-isodecyl trimellitate (TIDTM) -cresyl phosphate (TCP), tri-2-ethylhexyl phosphate (TEHP or TOP), cresyl diphenyl phosphate (CDP) and tri-aryl phosphate (TAP) Po) Epoxy plasticizers consisting of phosphoric acid ester plasticizer, epoxidized soybean oil (ESO) and epoxidized linseed oil (ELO), average molecular weight of 1,000 to 8,000 Polyester plasticizer of low-polymerization polyester, di-2-ethylhexyl adipate (DEHA or DOA), di-2-ethylhexyl azelate (di-2-ethylhexyl) a low gloss styrene based on at least one selected from the group consisting of an aliphatic acid ester plasticizer consisting of azelate: DOZ) and di-isodecyl adipate (DIDA), and an anti-chlorine plasticizer Resin composition. The method of claim 1, The low gloss styrene resin composition may further comprise 0.1 to 20 wt% of a matte filler based on the total weight of the low gloss styrene resin comprising the base resin (A) and the matte agent (B). Resin composition. The method of claim 19, The matte filler includes B-Mat (glass transition temperature: 122 ° C.) and an inorganic filler, which is a crosslinked SAN, and an inorganic filler is a Silicate inorganic filler (eg, talc, mica, clay, montmorillonite). It is characterized in that at least one selected from the group consisting of one or more mixtures selected from plate or sphere inorganic fillers such as glass beads, silica, glass flakes, calcium carbonate, metal oxide, etc. Low gloss styrene resin composition. The method of claim 1, The low gloss styrene resin composition is a low gloss styrene resin composition, characterized in that it has a glossiness of 1 to 50 at 75 °. A sheet formed by the low gloss styrene resin composition according to any one of claims 1 to 21. The sheet is formed by extruding the low gloss styrene resin composition according to any one of claims 1 to 21 by an extruder at a temperature of 160 ° C. or higher and 20 ° C. or lower than the melting temperature of the syndiotactic polystyrene matte. Method for producing a sheet comprising the step of forming. The method of claim 23, wherein In forming the sheet by extruding with the low gloss styrene resin composition, a thermoplastic resin different from the low gloss styrene resin composition is coextruded to form a sheet made of a separate thermoplastic resin, and the two sheets are compressed to form a composite sheet. Method for producing a sheet, characterized in that. The method of claim 24, The thermoplastic resin is a method for producing a sheet, characterized in that at least one selected from acrylonitrile-butadiene-styrene resin and polyvinyl chloride resin. An inner layer and an outer layer coupled to at least one surface of the inner layer to prevent the inner layer from being exposed to the outside environment, wherein the inner layer is formed by a thermoplastic resin material having poor weatherability than the outer layer. The outer layer is a composite, characterized in that formed by the low-gloss styrene-based resin composition according to any one of claims 1 to 21. The method of claim 26, And the thermoplastic resin material of the inner layer is at least one selected from acrylonitrile-butadiene-styrene resins and polyvinylchloride resins.

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