KR20080073962A - Low surface gloss styrene resin composition, low surface gloss sheet containing the same and preparing method thereof - Google Patents

Abstract

A low-gloss styrenic resin composition is provided to realize excellent weather resistance and low surface gloss so that the resin composition is particularly suitable for exterior parts of building structures. A low-gloss styrenic resin composition comprises: (A) 80-99.9 wt% of a styrenic resin; and (B) 0.1-20 wt% of syndiotactic polystyrene, or a derivative or mixture thereof, as a mattifying agent. The styrenic resin is obtained by polymerizing at least one compound selected from the group consisting of aromatic vinyl compounds, ethylenically unsaturated compounds and mixtures thereof, in the presence of elastomeric rubber.

Description

LOW SURFACE GLOSS STYRENE RESIN COMPOSITION, LOW SURFACE GLOSS SHEET CONTAINING THE SAME AND PREPARING METHOD THEREOF}

The present invention relates to a low-gloss styrene-based resin composition, a sheet prepared therefrom and a method for producing the same. More particularly, the present invention relates to a low gloss styrene resin composition, a sheet prepared therefrom, and more particularly, to excellent weather resistance and reduced surface gloss. It relates to a suitable low gloss styrenic resin composition, a sheet prepared therefrom and a method for producing the same.

The styrene copolymer composed of a resin matrix and an elastomer or a rubber component includes acrylate-styrene-acrylonitrile (ASA), olefin-styrene-acrylonitrile (OSA), acrylonitrile-ethylenepropylenediene rubber (EPDM) -styrene Various resins are known, such as (AES) or acrylonitrile-butadiene-styrene (ABS). 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, ABS resin low temperature impact and workability.

In general, the use of thermoplastic resins such as ABS and ASA resins is rapidly increasing in a wide range of parts from daily household goods to automobile interior materials, office equipment, building materials, and the like. 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 increased in order 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 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.

Conventionally, a method of embossing and coating a low gloss coating material on the surface of a molding has been performed, but this method requires a separate process to increase the cost, and the problem of low gloss effect on the surface of the molding is poor and poor workability. there was.

As another conventional technique, 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. Patent No. 5,081,193 (registered Jan. 14, 1992) discloses a low gloss agent for thermoplastic resins comprising a graft copolymer containing rubber as a rubber component, in particular low-cis polybutadiene, and U.S. Patent No. 5,237,004 No. 1993.08.17 discloses a method for reducing surface gloss by adding 2-15 μm polymer particles to a thermoplastic polymer composition of a particular core / shell structure. U.S. Patent No. 5,475,053 (registered Dec. 12, 1995) discloses a molding composition with a matte surface comprising an impact modifying thermoplastic resin (A) such as ABS or ASA and a matting agent, and U.S. Patent No. 4,652,614 ( March 24, 1987, discloses a molding material with a matte surface based on neutral and acidic graft polymers. US Patent No. 4,169,869 (registered Oct. 2, 1979) discloses an ABS compound with a low gloss or matt finish. US Patent No. 4,668, 737 (registered May 26, 1987) has an overall rubber content of 5 to 80 weight percent, average 20 to 0.1 parts by weight of heterocyclic nitrogen substrate, 40 to 99.8 parts by weight of aromatic vinyl monomer, and 1 acid or polymerizable double bond on the particulate rubber having a particle diameter of 0.05 to 20.0 μm and a glass transition temperature of 10 ° C. or less. A graft polymer of a matte surface is disclosed which comprises 20 to 0.1 parts by weight of acid, and 0 to 40 parts by weight of acrylonitrile.

However, the above-mentioned prior arts have limitations that exhibit one or more disadvantages without even satisfying characteristics such as the physical properties of the resin, the appropriate reduction of the surface gloss, the quality of the surface appearance, the manufacturing cost and the workability.

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a low-gloss styrene resin composition is particularly suitable for use in the field of structural exterior, such as wall panels, window frames, such that the surface gloss is reduced.

In addition, an object of the present invention is to provide a sheet suitable for external siding for a structure made from the low-gloss styrene resin composition, and a method for producing the same.

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 comprises (A) 80 to 99.9% by weight of styrene resin and (B) 0.1 to 20% by weight of syndiotactic polystyrene (sPS), derivatives thereof or mixtures thereof as a matte agent. It provides a low gloss styrene resin composition.

The present invention also provides a sheet made from the low gloss styrene resin composition.

The present invention also provides a sheet comprising (I) at least one inner layer comprising a thermoplastic and (II) at least one outer layer comprising the low gloss styrene resin composition.

In addition, the present invention provides a method for producing a sheet comprising the step of sheet processing the low-gloss styrene resin composition at a temperature lower than 20 ℃ than the melting temperature of the matte agent.

Hereinafter, the present invention will be described in detail.

The inventors have included matte crystalline polymers such as weathering styrenic resins and syndiotactic polystyrenes (sPSs), syndiotactic polystyrene maleic anhydrides (sPS-MAH), derivatives of the syndiotactic polystyrenes, or mixtures thereof, The thermoplastic resin composition prepared by adjusting the rubber content of the styrene-based resin and the content of the matting agent was confirmed that the impact strength, weather resistance and low gloss effect were excellent, and completed the present invention.

The low gloss styrene resin composition of the present invention comprises (A) 80 to 99.9% by weight of styrene resin and (B) 0.1 to 20% by weight of matte, the gloss of which is measured by TOYOSEIKI (GLOSS METER UD) gloss meter When it has a glossiness of 1 to 50 at 75 °.

In addition, the low gloss styrene resin composition may further include a matte filler.

(A) Styrene series  Suzy

Styrene resins are prepared by polymerizing aromatic vinyl compounds, ethylenically unsaturated compounds or mixtures thereof in the presence of elastomeric rubber.

The elastomeric rubber is obtained by polymerizing single or two or more alkyl acrylates, butadiene or isoprene, olefin compounds, ethylenically unsaturated compounds, aromatic vinyl compounds, or polyfunctional monomers having 1 to 32 carbon atoms, preferably 1 to 8 carbon atoms. It can manufacture.

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 30% by weight based on 100 parts by weight of styrene resin.

As the aromatic vinyl compound, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, 1,3-dimethylstyrene, tert-butylstyrene or vinylnaphthalene may be used. May be used styrene, α-methylstyrene, p-methylstyrene or tert-butylstyrene, more preferably styrene or α-methylstyrene.

The aromatic vinyl compound may be included in more than 20% by weight, preferably 30 to 85% by weight, more preferably 30 to 70% by weight based on 100 parts by weight of the styrene resin. When included in the content has the effect of improving mechanical strength and impact strength.

Examples of the ethylenically unsaturated compound include acrylonitrile, methacrylonitrile, alkyl acrylates having 1 to 4 carbon atoms and alkyl methacrylates, acrylic acid, methacrylic acid, maleic anhydride, acrylamide or vinyl methyl ether. It is possible to use, preferably acrylonitrile can be used.

The ethylenically unsaturated compound is preferably contained in 5 to 30% by weight in 100 parts by weight of styrene resin. When included in the content has the effect of improving heat resistance, chemical resistance and mechanical strength.

The styrene resin may further include a copolymer (V) prepared by polymerizing an aromatic vinyl compound or an ethylenically unsaturated compound alone or two or more in order to control the rubber content.

It is preferable that the said copolymer (iii) contains 20-50 weight% of ethylenically unsaturated compounds with respect to 100 weight part of copolymers.

Examples of the copolymer include styrene-acrylonitrile copolymers, α-methylstyrene / acrylonitrile copolymers, styrene / methyl methacrylate copolymers, styrene / maleic anhydride copolymers, α-methylstyrene / styrene / Acrylonitrile terpolymers, styrene / acrylonitrile / methyl methacrylate terpolymers, styrene / acrylonitrile / maleic anhydride, styrene / acrylonitrile / acrylic acid terpolymers, or α-methylstyrene / styrene / An acrylonitrile terpolymer etc. can be used individually or in mixture of 2 or more types, Preferably, a styrene / acrylonitrile copolymer, the (alpha) -methylstyrene / acrylonitrile copolymer, or a mixture thereof is used.

The copolymer may be incorporated into the styrene-based resin using a typical extrusion blending method using a single screw or twin screw extruder, which is a method known in the art. Specific examples include vigorously mixing a melt of a styrene resin and a copolymer prepared by polymerizing an aromatic vinyl compound or an ethylenically unsaturated compound alone or two or more in the presence of the elastomer rubber at a temperature exceeding 200 ° C. can do.

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 styrene-based resin, ASA, ABS or AES resin may be used, and a styrene / acrylonitrile (SAN) copolymer may be used as the copolymer (i), and preferably, ASA resin or It is to use a resin containing a SAN copolymer in the ASA resin. Specific examples of the styrene-based resin in which styrene and acrylonitrile are grafted in a butyl acrylate or tricyclodecenyl acrylate elastomer rubber in a weight ratio of 75:25, and styrene / acrylonitrile in an amount of 22 to 35 wt% Preference is given to styrene resins in which an acrylonitrile copolymer or an α-methylstyrene / acrylonitrile copolymer is further mixed.

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 has an excellent mechanical strength, there is an effect that the matt effect is improved.

(B) Matte

Matte agents may use syndiotactic polystyrene (sPS), derivatives thereof, or mixtures thereof as crystalline polymers.

Syndiotactic polystyrene maleic anhydride (sPS-MAH) may be used as a derivative of the syndiotactic polystyrene (sPS).

The matting agent sPS has a steric structure whose 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. Is a polymer with a crystalline structure. The three-dimensional structure can be expressed by quantifying the stereotacticity (tacticity) by ¹³ C -NMR method.

As the sPS, polystyrene, polyhalogenated styrene, polyalkoxystyrene, polyalkylstyrene, polybenzoic acid ester styrene, having a stereoregularity of 85% or more in the case of dyad and 35% or more in the case of pentad (racemic pentade), Or the copolymer etc. which made these main components etc. can be used individually or in mixture of 2 or more types.

The matting agent has a melting temperature of 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.

80 to 99.9% by weight of styrenic resin and 0.1 to 20% by weight of syndiotactic polystyrene (sPS), derivatives thereof or mixtures thereof as a matte are mixed and prepared into pellets using a blending method using a single screw or twin screw extruder. Can be.

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 preferably a cross-polymerized styrene-acrylonitrile copolymer.

The present invention provides a low gloss sheet prepared from the low gloss styrene resin composition.

The low gloss 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, it is preferable that the processing temperature at the time of sheet processing is lower than 20 ℃ than the melting temperature of the matte. When processing at a temperature 20 degreeC or more lower than the melting temperature of a matte agent, there exists an effect which the matte characteristic of a styrene resin expresses preferably.

The present invention also provides a sheet comprising (I) at least one inner layer comprising a thermoplastic and (II) at least one outer layer comprising a low gloss styrene resin composition.

The composite can be applied to exterior siding applications for structures.

The inner layer (I) may be located inside the surface of the structure, and the outer layer (II) may be positioned to face the outside exposed to light and climate due to excellent weather resistance.

As the thermoplastic material included in the inner layer (I), acrylonitrile / butadiene / styrene resin or polyvinyl chloride resin may be used alone or in combination of two or more thereof.

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 sheet may be manufactured by coextrusion of the inner layer and the outer layer.

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  1-4, Comparative example  One

As the styrene resin, SA927-DP resin (manufactured by LG Chem.) Containing acrylic rubber and SAN 90HR (manufactured by LG Chem.) Were mixed according to the rubber content with a SAN resin having a MI of 25 g / 10min (220 ° C). .

As a matte agent, sPS 130ZC (made by Idemitsu Co., Ltd.) whose melting temperature is 270 degreeC was used.

The styrene resin and the matting agent were added in the composition shown in Table 3 below, and 3 parts by weight of titanium dioxide (Chronos 2233) was added, followed by mixing under the processing conditions shown in Table 1 using a twin screw extruder having a diameter of 27 mm manufactured by Leistritz. It was then made into pellets.

The prepared pellets were manufactured using a TSE16TC twin-screw extruder and a T-die having a screw diameter of 16 mm, manufactured by Thermo PRISM, and a sheet having a thickness of 0.2 mm under the processing conditions shown in Table 2 below, and TOYOSEIKI (GLOSS METER UD) gloss. Glossiness was measured at 75 ° using a degree meter and is shown in Table 3 below. At this time, in order to express the matte properties of the sheet extruded from the T-die was processed at a temperature lower 20 ℃ than the melting temperature of the matting agent during sheet processing.

Extruder Barrel 1 Barrel 2 ~ 11 die Screw rotation speed Feed rate Leistritz 250 ℃ 260 ℃ 260 ℃ 350 RPM 15 kg / hr

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

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Styrene-based resin (% by weight) 97 95 93 90 100 Matte agent (wt%) 3 5 7 10 0 Glossiness (75 °) 32.5 17.6 9.3 3.3 84.9

Through Table 3, it was confirmed that the styrene resin composition of Examples 1 to 4 containing sPS as the matting agent is excellent in low gloss characteristics as compared to the resin composition of Comparative Example 1 containing no matting agent. .

Example  5 ~ 7

Except that the content of MAH as a matte in Example 1 1.5% by weight, sPS-MAH TPSPS 8012PA (manufactured by KOMETRA Co., Ltd.) of sPS-MAH having a melting temperature of 269 ° C in the composition shown in Table 4 below. It carried out by the same method as Example 1.

division Example 5 Example 6 Example 7 Styrene-based resin (% by weight) 97 95 90 Matte agent (wt%) 3 5 10 Glossiness (75 °) 45.8 25.9 3.6

Through Table 4, it is confirmed that the styrenic resin composition of Examples 5 to 7 including sPS-MAH as a matte agent is excellent in low glossiness as compared to the resin composition of Comparative Example 1 containing no matte agent. Could.

Example  8-9

Except for using a blendex-MAT 3, 5 parts by weight of the matte filler in Example 1, respectively, was carried out in the same manner as in Example 1.

division Example 8 Example 9 Styrene-based resin (% by weight) 97 97 Matte agent (wt%) 3 3 Blendex-MAT (parts by weight) 3 5 Glossiness (75 °) 29.4 23.3

Through the above Table 5, the styrene-based resin composition of Examples 8 to 9 further comprising a matte filler with the sPS of the matte agent is lower than the resin composition of Example 1 can be confirmed that the lower gloss characteristics are more excellent. there was.

Example  10-19, Comparative example  2

In order to confirm the effect of glossiness according to the processing temperature when manufacturing the styrene resin in Example 1, 10 wt% of sPS-MAH TPSPS 8012PA (manufactured by KOMETRA) was mixed with 90 wt% of the styrene resin as a matte, The process was carried out in the same manner as in Example 1, except that it was prepared under the processing temperature condition of 5.

division Pellet Manufacturing Temperature (℃) Sheet processing temperature (℃) Glossiness (75 °) Example 10 240 200 3.8 Example 11 250 4.2 Example 12 260 3.6 Example 13 270 3.8 Example 14 280 4.2 Example 15 290 4.3 Example 16 260 200 3.6 Example 17 215 3.3 Example 18 230 3.9 Example 19 245 29.3 Comparative Example 2 260 89.8

Through the above Table 5, the styrene-based resin composition of Examples 10 to 19 which processed the processing temperature at the time of sheet processing to 20 ℃ lower than the melting temperature of the matte compared the sheet processing temperature does not fall within the scope of the present invention Compared with Example 2, it was confirmed that the matt properties were excellent.

As described above, according to the present invention, the weather resistance is excellent, and the surface gloss is reduced, thereby providing a low-gloss styrene resin composition particularly suitable for use in the exterior field of structures such as wall panels and window frames.

In addition, there is an effect of providing a sheet produced from the low-gloss styrene resin composition.

Claims (16)

(A) 80 to 99.9% by weight of styrene resin, and (B) a matte agent comprising 0.1 to 20% by weight of syndiotactic polystyrene, derivatives thereof or mixtures thereof Low gloss styrene resin composition. The method of claim 1, The styrene resin (A) is characterized in that at least one compound selected from the group consisting of aromatic vinyl compounds, ethylenically unsaturated compounds and mixtures thereof is polymerized in the presence of an elastomer rubber. Low gloss styrene resin composition. The method of claim 2, Said (A) styrene resin is an acrylate / styrene / acrylonitrile resin, It is characterized by the above-mentioned. Low gloss styrene resin composition. The method of claim 2, The styrene resin (A) further comprises a copolymer in which at least one compound selected from the group consisting of aromatic vinyl compounds, ethylenically unsaturated compounds and mixtures thereof is polymerized. Low gloss styrene resin composition. The method of claim 4, wherein The copolymer (i) may be a styrene / acrylonitrile copolymer, an α-methylstyrene / acrylonitrile copolymer, a styrene / methyl methacrylate copolymer, a styrene / maleic anhydride copolymer, an α-methylstyrene / styrene / Acrylonitrile terpolymers, styrene / acrylonitrile / methylmethacrylate terpolymers, styrene / acrylonitrile / maleic anhydride, styrene / acrylonitrile / acrylic acid terpolymers, and α-methylstyrene / styrene / Acrylonitrile terpolymer selected from the group consisting of at least one Low gloss styrene resin composition. The method of claim 4, wherein The styrene resin (A) is a resin in which an acrylate / styrene / acrylonitrile resin and a styrene / acrylonitrile copolymer are mixed. Low gloss styrene resin composition. The method of claim 1, The derivative of syndiotactic polystyrene is syndiotactic polystyrene maleic anhydride, characterized in that Low gloss styrene resin composition. The method of claim 1, The syndiotactic polystyrene is a diad polystyrene having a stereoregularity of 85% or more, a pentad (racemic pentade) polystyrene, a polyhalogenated styrene, a polyalkoxy styrene, a polyalkyl styrene, a polybenzoate ester having a stereoregularity of 35% or more. At least one member selected from the group consisting of styrene and copolymers containing these as main components; Low gloss styrene resin composition. The method of claim 1, The low gloss styrene resin composition is characterized in that the glossiness is 1 to 50 glossiness at 75 ° as measured by TOYOSEIKI (GLOSS METER UD) glossiness meter Low gloss styrene resin composition. The method of claim 1, The low gloss styrene resin composition is characterized in that it further comprises a cross-polymerized styrene-acrylonitrile copolymer-based matte filler Low gloss styrene resin composition. A sheet made from a low gloss styrene resin composition comprising 80 to 99.9% by weight of styrene resin and 0.1 to 20% by weight of syndiotactic polystyrene, derivatives thereof, or mixtures thereof as a matte agent. A low gloss styrene resin composition comprising 80 to 99.9% by weight of styrene resin and 0.1 to 20% by weight of syndiotactic polystyrene, a derivative thereof or a mixture thereof as a matte agent at a temperature lower than 20 ° C. below the melting temperature of the matte agent. Characterized in that it comprises the step of processing the sheet Manufacturing method of the sheet. (I) at least one inner layer comprising a thermoplastic, and (II) at least one outer layer comprising a low gloss styrene resin composition comprising from 80 to 99.9% by weight of styrene resin and from 0.1 to 20% by weight of syndiotactic polystyrene, derivatives thereof or mixtures thereof as a matte agent. By Sheet. The method of claim 13, The thermoplastic material of the inner layer (I) is acrylonitrile-butadiene-styrene resin, polyvinyl chloride resin or a mixture thereof. Sheet. (I) preparing an inner layer comprising a thermoplastic material; (II) preparing an outer layer comprising a low gloss styrene resin composition comprising 80 to 99.9% by weight of styrene resin and 0.1 to 20% by weight of syndiotactic polystyrene, derivatives thereof or mixtures thereof as a matte agent; And (III) continuously coextruding the manufactured inner layer and outer layer; Manufacturing method of the sheet. The method of claim 15, The step (II) is a step of sheet-processing the low-gloss styrene resin composition at a temperature lower than 20 ° C. below the melting temperature of the matte agent. Manufacturing method of the sheet.