Matte polymer composition having excellent weather resistance and impact resistance and matte sheet comprising the same

Abstract

The present invention relates to a matt polymer composition having excellent weather resistance and impact resistance, and a matte sheet comprising the same. The matt polymer composition according to the present invention, since it comprises two styrene-acrylonitrile copolymers having different acrylonitrile contents and a matting agent, a molded product manufactured by extrusion, injection molding, etc. has excellent weather resistance and impact strength and the like, and can exhibit effective matting effect and excellent appearance quality. The matt polymer composition according to the present invention can be used to manufacture a matte multilayer film, and can be applied to various fields such as building, exterior material, interior decoration, and household electrical products.

Description

Technical Field

[0001] This invention relates to a matte polymer composition with excellent weather resistance and impact resistance, and matte sheets containing the same. Background Technology

[0002] Typically, various thermoplastic resins such as polyvinyl chloride (PVC), polycarbonate (PC), polymethyl methacrylate (PMMA), and acrylonitrile-butadiene-styrene copolymer (ABS) are used in building materials. In recent years, with the increasing demand from consumers for higher emotional quality, there is a growing need for matte resins to give materials a more premium feel.

[0003] To achieve such a matte surface, methods are used to physically process the resin surface to reduce gloss. However, this presents economic challenges and issues with the matting performance decreasing due to abrasion during processing. Another method involves using thermoplastic resins with excellent mechanical and chemical properties, such as PVC and ABS, as a base layer and then laminating a matte resin. For example, ABS resin is used as the base layer and co-extruded with a matte resin containing PMMA and a matting agent to produce a multilayer sheet. However, due to the addition of the matting agent, the mechanical strength of the sheet decreases significantly, and its weather resistance is insufficient, failing to ensure a satisfactory matte surface.

[0004] In addition, sufficient weather resistance, heat resistance and mechanical properties are required for use as building exterior materials. Generally, PVC, which is used as the base layer of the above-mentioned multi-layer sheet, has excellent chemical resistance, but insufficient weather resistance and colorability. ABS has excellent molding processability and impact resistance, but weak weather resistance. Therefore, the key is to ensure a matte surface while improving the weather resistance, which is a necessary condition for building exterior materials.

[0005] Therefore, there is an urgent need to develop matte polymer compositions that exhibit excellent weather resistance, mechanical and chemical properties, while ensuring a matte surface and a high-quality surface appearance. Summary of the Invention

[0006] In order to solve the problems of the prior art as described above, the object of the present invention is to provide a matting polymer composition comprising a matting agent with excellent matting effect.

[0007] The purpose of this invention is to provide a matting polymer composition and its molded articles, wherein an acrylate-styrene-acrylonitrile graft copolymer and two styrene-acrylonitrile copolymers with different acrylonitrile contents are extruded or injection molded together with a matting agent, thereby achieving excellent mechanical properties such as weather resistance and impact strength, while having a matte surface and a high-quality surface appearance.

[0008] Another object of the present invention is to provide a matte multilayer sheet, which is formed by co-extruding the above-mentioned matte polymer composition and laminating it on a substrate layer.

[0009] To solve the above problems, the inventors of this invention discovered that when acrylate-styrene-acrylonitrile graft copolymers and two styrene-acrylonitrile copolymers with different acrylonitrile contents are extruded or injection molded together with a specific matting agent, molded articles with excellent mechanical properties such as weather resistance and impact strength, as well as excellent matting effect and high-quality surface appearance, can be manufactured, thus completing this invention.

[0010] The present invention provides a matting polymer composition comprising: (A) an acrylate-styrene-acrylonitrile graft copolymer, (B-1) a first styrene-acrylonitrile copolymer, (B-2) a second styrene-acrylonitrile copolymer, and (C) a matting agent, wherein the first styrene-acrylonitrile copolymer and the second styrene-acrylonitrile copolymer have different acrylonitrile contents.

[0011] According to one embodiment of the present invention, the acrylonitrile content in the first styrene-acrylonitrile copolymer may be 31 to 40 wt%, and the acrylonitrile content in the second styrene-acrylonitrile copolymer may be 22 to 30 wt%.

[0012] According to one embodiment of the present invention, the above-mentioned matting agent can be manufactured from a reactive extrusion composition comprising polystyrene (PS), styrene-acrylonitrile copolymer (SAN), N-phenylmaleimide copolymer (PMI), alicyclic epoxy compound and acid compound.

[0013] According to one embodiment of the present invention, the above-mentioned matting agent can be manufactured from a reactive extrusion composition comprising polycarbonate (PC), styrene-acrylonitrile copolymer (SAN), alicyclic epoxy compound and acid compound.

[0014] The aforementioned alicyclic epoxides can be selected from 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane-carboxylate, diethylene glycol bis(3,4-epoxycyclohexane-carboxylate), 2-ethyl-1,3-hexanediol bis(3,4-epoxycyclohexane-carboxylate), diethylene glycol bis(3,4-epoxy-6-methylcyclohexane-carboxylate), 3-methyl-1,5-pentanediol bis(3,4-epoxycyclohexane-carboxylate), 1 One or more of the following: 5-pentanediol bis(3,4-epoxycyclohexane-carboxylate), ethylene glycol bis(3,4-epoxycyclohexane-carboxylate), ethylene glycol bis(3,4-epoxy-6-methylcyclohexane-carboxylate), bis(3,4-epoxycyclohexylmethyl) oxalate, bis(3,4-epoxycyclohexylmethyl) succinate, bis(3,4-epoxycyclohexylmethyl) adipate, and 1,2,8,9-diepoxylimonene.

[0015] According to one embodiment of the present invention, the acid compound may be any one or a combination of two or more selected from R1COOH or R2SO3H and their salt compounds, wherein R1 and R2 are each independently C 6-30 Alkyl, C 6-30 Aryl, or C 6-30 Aryl C 6-30 alkyl.

[0016] According to one embodiment of the present invention, the above-mentioned reactive extrusion composition may contain 10 to 20 wt% polystyrene, 60 to 80 wt% styrene-acrylonitrile copolymer, 5 to 20 wt% N-phenylmaleimide copolymer, 1 to 6 wt% alicyclic epoxy compound and 0.01 to 1.5 wt% acid compound.

[0017] According to one embodiment of the present invention, the above-mentioned reactive extrusion composition may contain 15 to 35 wt% polycarbonate, 60 to 80 wt% styrene-acrylonitrile copolymer, 1 to 6 wt% alicyclic epoxy compound and 0.01 to 1.65 wt% acid compound.

[0018] According to an embodiment of the present invention, the above-mentioned matting polymer composition may contain 50 to 90 parts by weight of a first styrene-acrylonitrile copolymer, 15 to 35 parts by weight of a second styrene-acrylonitrile copolymer, and 2 to 24 parts by weight of a matting agent relative to 100 parts by weight of the acrylate-styrene-acrylonitrile graft copolymer.

[0019] According to one embodiment of the present invention, the weight ratio of the first styrene-acrylonitrile copolymer and the second styrene-acrylonitrile copolymer can be from 1:0.1 to 0.5.

[0020] According to one embodiment of the present invention, the glass transition temperature of the above-mentioned second styrene-acrylonitrile copolymer can be 110 to 130°C.

[0021] According to an embodiment of the present invention, the above-mentioned matting polymer composition may contain 5 to 50 parts by weight of a first styrene-acrylonitrile copolymer, 30 to 100 parts by weight of a second styrene-acrylonitrile copolymer, and 2 to 24 parts by weight of a matting agent relative to 100 parts by weight of the acrylate-styrene-acrylonitrile graft copolymer.

[0022] According to an embodiment of the present invention, the above-mentioned matting polymer composition may further contain a third styrene-acrylonitrile copolymer with a weight-average molecular weight of 4,000,000 g / mol or more.

[0023] According to one embodiment of the present invention, 1 to 6 parts by weight of the third styrene-acrylonitrile copolymer may be included relative to 100 parts by weight of the acrylate-styrene-acrylonitrile graft copolymer.

[0024] The present invention can provide a molded article manufactured by extruding or injection molding the above-mentioned matte polymer composition.

[0025] The present invention can provide a sheet comprising a substrate layer and a surface layer, wherein the surface layer is formed by laminating the above-mentioned matting polymer composition co-extruded on the substrate layer.

[0026] According to one embodiment of the present invention, the substrate layer may be one or more selected from polyvinyl chloride (PVC), polypropylene (PP), polyacrylate, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polymethyl methacrylate (PMMA), polycarbonate (PC), polyamide, styrene-acrylonitrile copolymer (SAN), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-styrene-acrylate (ASA), and mixtures thereof.

[0027] Molded articles manufactured by extruding and injection molding the matte polymer composition according to the present invention have excellent mechanical properties such as weather resistance and impact strength, and can also exhibit excellent matte effect and high-quality surface appearance, and are therefore preferred.

[0028] The matte polymer composition of the present invention can be used to manufacture matte multilayer sheets, which can be applied to various fields such as construction, exterior materials, interior decoration and home appliances. Attached Figure Description

[0029] Figure 1 This is a photograph showing the surface appearance of the extruded sheet described in Example 1. Detailed Implementation

[0030] The invention will now be described in more detail by way of specific examples or embodiments, including the accompanying drawings. However, the specific examples or embodiments described below are merely for reference in providing a detailed description of the invention, and the invention is not limited thereto and can be implemented in various forms.

[0031] Furthermore, unless otherwise defined, all technical and scientific terms shall have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terms used in this invention for illustrative purposes are merely for the effective description of specific examples and are not intended to limit the scope of the invention.

[0032] In addition, the singular form used in the specification and the appended claims may also be intended to include the plural form unless otherwise indicated in the context.

[0033] Furthermore, when it is stated that a part "contains / includes" a certain constituent element, unless there is a particularly contrary statement, it means that other constituent elements may be included, rather than excluding other constituent elements.

[0034] The term "dullness" as used in this specification refers to the property of reducing gloss by utilizing the diffuse reflection effect through differences in shrinkage and refractive index or surface processing between polymers in an incompatible polymer composition and between polymers and additives.

[0035] The invention can be better understood through the following embodiments, which are for illustrative purposes only and are not intended to limit the scope of protection defined by the appended claims.

[0036] The following is a more detailed description of one embodiment of the present invention.

[0037] The present invention provides a matting polymer composition comprising (A) an acrylate-styrene-acrylonitrile graft copolymer, (B-1) a first styrene-acrylonitrile copolymer, (B-2) a second styrene-acrylonitrile copolymer, and (C) a matting agent, wherein the first styrene-acrylonitrile copolymer and the second styrene-acrylonitrile copolymer have different acrylonitrile contents.

[0038] The aforementioned acrylate-styrene-acrylonitrile graft copolymer can be an acrylate-styrene-acrylonitrile copolymer (hereinafter ASA) polymerized by conventional or known methods. It can be a graft copolymer polymerized by emulsion polymerization and suspension polymerization, and commercially available products can be used without limitation. Preferably, the ASA containing 35 wt% or more or 40 to 80 wt% acrylate in the copolymer can be used, as mechanical properties such as impact strength can be improved when these ranges are met. Furthermore, the ASA content can be 10 to 90 wt% relative to the total weight of the matte polymer composition, preferably 40 to 70 wt%, but is not limited thereto. In this invention, to easily ensure the weather resistance necessary for the outer material, by using ASA instead of ABS, two or more styrene-acrylonitrile copolymers with different acrylonitrile contents are mixed in the ASA, thereby producing a matte polymer composition with further improved weather resistance and impact strength.

[0039] The aforementioned first styrene-acrylonitrile copolymer (hereinafter referred to as SAN-1) can be a copolymer of styrene and acrylonitrile polymerized by conventional or known methods. Preferably, in the copolymer, the acrylonitrile content (AN%) is... SAN-1The acrylonitrile content can be 31 to 40 wt% or 31 to 35 wt%, and the weight-average molecular weight of the above-mentioned SAN-1 can be 50,000 to 150,000 g / mol or 90,000 to 120,000 g / mol. As long as the acrylonitrile content range and the weight-average molecular weight mentioned above are met, any SAN product available on the market can be used without restriction.

[0040] The aforementioned second styrene-acrylonitrile copolymer (hereinafter referred to as SAN-2) can be a copolymer of styrene and acrylonitrile polymerized by conventional or known methods. Preferably, in the copolymer, the acrylonitrile content (AN%) is... SAN-2 The acrylonitrile content can be 22 to 30 wt% or 24 to 29 wt%. The weight-average molecular weight of the SAN-2 can be 70,000 to 250,000 g / mol, preferably 80,000 to 195,000 g / mol or 100,000 to 170,000 g / mol. The glass transition temperature of the SAN-2 can be 80 to 150 °C, preferably 90 to 130 °C. As long as the acrylonitrile content range and weight-average molecular weight mentioned above are met, commercially available SAN products can be used without restriction.

[0041] The acrylonitrile content (AN%) in the above SAN-1 SAN-1 ) and the acrylonitrile content (AN%) contained in SAN-2 SAN-2 The difference (AN%) SAN-1 -AN% SAN-2 The content can be 2 to 18 wt%, 2 to 15 wt%, 3 to 12 wt%, or 4 to 10 wt%. When the above range is met, the compatibility with the above-mentioned ASA base polymer is excellent, which can improve mechanical properties such as impact strength, and can effectively exhibit a uniform matte surface during extrusion processing, and is therefore preferred.

[0042] According to one embodiment of the present invention, the above-mentioned matte polymer composition may contain 20 to 110 parts by weight of SAN-1 and 5 to 80 parts by weight of SAN-2, preferably 50 to 90 parts by weight of SAN-1 and 15 to 35 parts by weight of SAN-2, more preferably 60 to 80 parts by weight of SAN-1, and may contain 10 to 30 parts by weight of SAN-2, relative to 100 parts by weight of SAN-1. When the above-mentioned content range is met, the acrylonitrile content contained in the composition can be appropriately adjusted, thereby effectively suppressing yellowing of the molded article, further improving compatibility with ASA, and thus achieving excellent weather resistance and impact strength. Furthermore, the above-mentioned matte polymer composition can be extruded / injected to manufacture products such as building exterior materials exposed to the external environment, which is therefore preferred.

[0043] Furthermore, the weight ratio of SAN-1 to SAN-2 can be from 1:0.05 to 1, preferably from 0.1 to 0.5, and more preferably from 0.2 to 0.3. When the above weight ratio range is met, the composition exhibits excellent dispersibility, and mechanical properties such as impact strength can be further improved. By appropriately adjusting the overall acrylonitrile content in the composition, weather resistance and surface appearance quality can be further improved.

[0044] According to another aspect of the present invention, the aforementioned second styrene-acrylonitrile copolymer may be an α-styrene-acrylonitrile copolymer (hereinafter referred to as α-SAN-2), which may contain 50 to 80 mol% or 65 to 75 mol% of α-methylstyrene relative to the total molar number of structural units constituting the copolymer. The glass transition temperature of the aforementioned α-SAN-2 may be 100 to 150°C, preferably 100 to 140°C, more preferably 110 to 130°C, and the weight-average molecular weight may be 50,000 to 150,000 g / mol or 70,000 to 130,000 g / mol. Furthermore, in the above-mentioned matting polymer composition, relative to 100 parts by weight of the ASA copolymer, it may contain 1 to 80 parts by weight of SAN-1 and 10 to 150 parts by weight of α-SAN-2, preferably 5 to 50 parts by weight of SAN-1 and 30 to 100 parts by weight of α-SAN-2, more preferably 10 to 30 parts by weight of SAN-1 and 50 to 90 parts by weight of α-SAN-2, but it is not limited thereto as long as it does not impede the target properties of the present invention. Since the above-mentioned α-SAN-2 contains α-methylstyrene, the matting polymer composition containing the above-mentioned α-SAN-2 can have better heat resistance, excellent processability during extrusion processing, and can have a surface appearance with improved quality, and is therefore preferred. In addition, when the above range is met, the thermal stability such as heat resistance can be further improved, thereby making it suitable for various applications requiring thermal properties.

[0045] According to an embodiment of the present invention, the above-mentioned matting polymeric composition further comprises a third styrene-acrylonitrile copolymer (hereinafter SAN-3) having a weight-average molecular weight of 4,000,000 g / mol or more, preferably 5,000,000 g / mol or more, but not limited to 10,000,000 g / mol or less. The above-mentioned SAN-3 may be manufactured by emulsion polymerization of a polymerizable composition comprising 20 to 30 wt% acrylonitrile and 70 to 80 wt% styrene, but is not limited thereto.

[0046] When SAN-3 resin meeting the above molecular weight range is added to the matting polymer composition, the matting properties can be further improved by imparting a fine and uniform surface roughness during extrusion processing. Furthermore, not only is there no decrease in mechanical properties such as impact resistance, but weather resistance and heat resistance are also effectively improved, making it preferable. In addition, 0.1 to 6 parts by weight of the aforementioned SAN-3, preferably 1 to 5 parts by weight, may be included relative to 100 parts by weight of ASA.

[0047] The aforementioned matting agent can be a commercially available styrene-based matting agent, but it is preferable to use a matting agent manufactured from a reactive extrusion composition comprising polystyrene (PS), styrene-acrylonitrile copolymer (SAN), N-phenylmaleimide copolymer (PMI), alicyclic epoxy compound, and acid compound. When the matting agent manufactured from the above reactive extrusion composition is mixed with ASA, SAN-1, and SAN-2, the surface gloss can be significantly reduced without a decrease in mechanical properties. In particular, molded articles with a superior surface appearance during extrusion processing can be produced.

[0048] The polystyrene (PS) contained in the above reactive extrusion composition can be commercially available general-purpose polystyrene, preferably with a weight-average molecular weight of 80,000 to 300,000 g / mol and a glass transition temperature of 95 to 110°C. Polystyrene meeting these ranges can be used without restriction. Furthermore, commercially available products can be used.

[0049] The styrene-acrylonitrile copolymer (SAN) contained in the above reactive extrusion composition may have a weight-average molecular weight of 50,000 to 300,000 g / mol, a glass transition temperature of 95 to 130°C or 95 to 120°C, and an acrylonitrile content of 5 to 50 wt% or 15 to 40 wt%, but is not limited thereto. Any styrene-acrylonitrile copolymer that meets the above ranges may be used without restriction. In addition, commercially available products may be used.

[0050] The N-phenylmaleimide copolymer (PMI) included in the above reactive extrusion composition is manufactured by copolymerizing 10 to 60 wt% of an N-substituted maleimide monomer with 40 to 90 wt% of an ethylene monomer, or 10 to 40 wt% of an N-substituted maleimide monomer with 60 to 90 wt% of an ethylene monomer. The N-substituted maleimide monomer may be selected from N-phenylmaleimide, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, etc. One or more of the following: N-isopropylmaleimide, N-butylmaleimide, N-isobutylmaleimide, N-tert-butylmaleimide, N-cyclohexylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-bromophenylmaleimide, N-naphthylmaleimide, N-laurylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, and N-benzylmaleimide.

[0051] In addition, the above-mentioned ethylene monomers can be aromatic ethylene monomers, specifically, they can be one or more selected from styrene, α-methylstyrene vinyltoluene, tert-butylstyrene, halostyrene, 1,3-dimethylstyrene, 2,4-dimethylstyrene and ethylstyrene.

[0052] The aforementioned N-phenylmaleimide copolymers can be copolymerized using commonly used or well-known methods. The weight-average molecular weight of these N-phenylmaleimide copolymers can be from 30,000 to 200,000 g / mol, and the glass transition temperature can be from 110 to 180°C or from 130 to 160°C. N-phenylmaleimide copolymers that meet the above ranges and conditions can be used largely without restriction, and commercially available products can be used.

[0053] The alicyclic epoxy compound contained in the above-mentioned reactive extrusion composition may be selected from 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane-carboxylate, diethylene glycol bis(3,4-epoxycyclohexane-carboxylate), 2-ethyl-1,3-hexanediol bis(3,4-epoxycyclohexane-carboxylate), diethylene glycol bis(3,4-epoxy-6-methylcyclohexane-carboxylate), 3-methyl-1,5-pentanediol bis(3,4-epoxycyclohexane- The following are some of the following: carboxylic acid esters, 1,5-pentanediol bis(3,4-epoxycyclohexane-carboxylic acid ester), ethylene glycol bis(3,4-epoxycyclohexane-carboxylic acid ester), ethylene glycol bis(3,4-epoxy-6-methylcyclohexane-carboxylic acid ester), bis(3,4-epoxycyclohexylmethyl) oxalate, bis(3,4-epoxycyclohexylmethyl) succinate, bis(3,4-epoxycyclohexylmethyl) adipate, and 1,2,8,9-diepoxylimonene.

[0054] The acid compound contained in the above reactive extrusion composition may be any one or a combination of two or more selected from R1COOH, R2SO3H and their salt compounds, and R1 and R2 may each be independently C 6-30 Alkyl, C 6-30 Aryl, or C 6-30 Aryl C 6-30 Alkyl groups, the salt compounds of the above-mentioned acid compounds can be represented by R1COOM and R2SO3M, where R1 and R2 are as described above, and M can be a cation. M can be an alkali metal cation or an ammonium cation. As a non-limiting example, M can be one or more selected from sodium ions, potassium ions, and lithium ions, but is not limited thereto. Preferably, the above-mentioned acid compound is R2SO3H, and R2 can be C... 6-12 Aryl C 6-18 Alkyl groups, as an example, can be selected from butylbenzenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid, and pentadecylbenzenesulfonic acid, but are not limited to these.

[0055] According to one embodiment of the present invention, the above-mentioned reactive extrusion composition may comprise 5 to 40 wt% polystyrene, 40 to 90 wt% styrene-acrylonitrile copolymer, 1 to 35 wt% N-phenylmaleimide copolymer, 1 to 6 wt% alicyclic epoxy compound, and 0.01 to 1.5 wt% acid compound. Specifically, it may comprise 10 to 20 wt% polystyrene, 60 to 80 wt% styrene-acrylonitrile copolymer, 5 to 20 wt% N-phenylmaleimide copolymer, 1 to 6 wt% alicyclic epoxy compound, and 0.01 to 1.5 wt% acid compound. When the above ranges are satisfied, a matting agent that does not decrease mechanical properties and exhibits excellent matting effect can be manufactured. When it is added to a matting polymer composition and processed, a molded article with a high-quality surface appearance can be manufactured.

[0056] According to another embodiment of the present invention, the above-mentioned matting agent may be a matting agent manufactured from a reactive extrusion composition comprising polycarbonate, styrene-acrylonitrile, alicyclic epoxy compound and acid compound.

[0057] The polycarbonate (PC) contained in the above reactive extrusion composition may have a weight-average molecular weight of 15,000 to 60,000 g / mol and a glass transition temperature of 130 to 170°C or 140 to 160°C, but is not limited thereto. As long as the polycarbonate meets the above range, it can be used without restriction. In addition, commercially available products can be used.

[0058] The styrene-acrylonitrile, alicyclic epoxy compound, and acid compound contained in the above reactive extrusion composition can be the same as those described above.

[0059] The aforementioned reactive extrusion composition comprising polycarbonate, styrene-acrylonitrile, alicyclic epoxy compound, and acid compound may contain 10 to 40 wt% polycarbonate, 55 to 85 wt% styrene-acrylonitrile copolymer, 1 to 6 wt% alicyclic epoxy compound, and 0.01 to 1.65 wt% acid compound. Specifically, it may contain 15 to 35 wt% polycarbonate, 60 to 80 wt% styrene-acrylonitrile copolymer, 1 to 6 wt% alicyclic epoxy compound, and 0.01 to 1.65 wt% acid compound. When the above ranges are met, a matting agent that does not decrease mechanical properties and exhibits excellent matting effect can be manufactured. When added to a matting polymer composition and processed, molded articles with a high-quality surface appearance can be produced.

[0060] The content of the matting agent relative to 100 parts by weight of the aforementioned ASA can be from 1 to 40 parts by weight, preferably from 1 to 30 parts by weight, more preferably from 2 to 24 parts by weight or from 2 to 20 parts by weight. When the above range is met, excellent matting effect can be exhibited without a decrease in mechanical properties, and therefore it is preferred.

[0061] Furthermore, the matting agent manufactured from the above-mentioned reactive extrusion composition can effectively reduce gloss without reducing the physical properties of the existing base polymer by adding only a small amount. It also has excellent dispersibility with the base polymer and a dense degree of crosslinking, thereby achieving further improved heat resistance and a high-quality surface appearance, and is therefore preferred.

[0062] According to one embodiment of the present invention, the above-described matting polymer composition may further include additives commonly used in the art, depending on the purpose and use. For example, it may also include ultraviolet stabilizers, ultraviolet absorbers, antioxidants, viscosity modifiers, plasticizers, heat stabilizers, dyes, pigments, colorants, release agents, antistatic agents, antibacterial agents, processing aids, metal passivators, flame retardants, friction reducers, wear-resistant agents, and lubricants. In this case, the above-described additives may be included in suitable amounts within a range that does not impair the target properties of the present invention.

[0063] The aforementioned UV stabilizers can be used largely without restriction as long as they are commonly used or well-known. For example, HALS-based UV stabilizers can be used. As a non-limiting example of the aforementioned HALS-based UV stabilizers, they can be selected from 1,1-bis(2,2,6,6-tetramethyl-4-piperidinyl)succinate, bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-N- The product may be one or more of the following, but is not limited to: butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonate, condensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine and 4-tert-octylamino-2,6-di-chloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidinyl)hydantointriacetate and tetra(2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butanetetracarboxylic acid ester, and may be a commercially available product.

[0064] The aforementioned ultraviolet absorbers can be used largely without restriction as long as they are commonly used or well-known. For example, benzotriazole-based ultraviolet absorbers can be used. As a non-limiting example of the aforementioned benzotriazole-based ultraviolet absorbers, hydroxybenzotriazole can be used. Specifically, it can be selected from 2-(2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, etc. The product may be one or more of the following, but is not limited to: 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, and 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl-5-chlorobenzotriazole, and may be a commercially available product.

[0065] The aforementioned UV stabilizer and UV absorber can be used independently, or preferably in combination. The content of the aforementioned UV stabilizer relative to 100 parts by weight of ASA can be 0.01 to 5.0 parts by weight or 0.1 to 3.0 parts by weight, and the content of the aforementioned UV absorber can be 0.01 to 5.0 parts by weight or 0.1 to 3.0 parts by weight. When the aforementioned UV stabilizer and UV absorber are used in combination, their content relative to 100 parts by weight of ASA can be 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight. Meeting the above ranges further improves weather resistance without hindering impact strength and flowability, and is therefore preferred. Furthermore, the weight ratio of the aforementioned UV stabilizer to UV absorber can be 1 to 9:9 to 1, but is not limited thereto as long as it does not impair the target properties of the present invention.

[0066] This invention provides molded articles manufactured by processing the above-mentioned matte polymer composition. The molded articles exhibit excellent impact strength and weather resistance, while also possessing a uniformly rough surface and excellent matte finish, effectively preventing defects such as pinholes, mold lines, and cracks, thus achieving a high-quality surface appearance. The processing methods for the molded articles can be used largely without restriction, as long as they are commonly used or well-known methods, such as casting, extrusion, injection molding, and blow molding, with extrusion or injection molding being preferred.

[0067] Previously, when manufacturing molded articles from polymer compositions containing matting agents via extrusion, problems arose such as pinholes, die lines, and cracks frequently appearing on the surface of the molded articles, as well as insufficient matting performance. However, according to a preferred embodiment, the matting polymer composition, containing an acrylate-styrene-acrylonitrile graft copolymer, two styrene-acrylonitrile copolymers with different acrylonitrile contents, and a matting agent manufactured from a reactive extrusion composition, allows for the production of molded articles with excellent matting performance and significantly reduced surface defects.

[0068] This invention provides a sheet comprising a substrate layer and a surface layer formed by co-extruding and laminating the aforementioned matte polymer composition onto the substrate layer. In the co-extrusion method, the co-extrusion utilizes a co-extruder maintained at a temperature above the melt temperature of both the substrate layer polymer composition and the surface layer polymer composition to melt and laminate the components, thereby producing a multilayer sheet. However, this is not a limitation; the sheet can be manufactured using known or conventional manufacturing methods. Furthermore, the sheet may also be a multilayer sheet in which one or more film or adhesive layers are laminated between the substrate layer and the surface layer, but this is not a limitation as long as it does not impede the target properties of the invention.

[0069] According to one embodiment of the present invention, the substrate layer may be selected from polyvinyl chloride (PVC), polypropylene (PP), polyacrylate, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polymethyl methacrylate (PMMA), polycarbonate (PC), polyamide, styrene-acrylonitrile copolymer (SAN), acrylonitrile-butadiene-styrene (ABS), and acrylonitrile-styrene-acrylate (ASA), or a mixture thereof, but is not limited thereto as long as it does not impede the target physical properties of the present invention.

[0070] The thickness of the sheet can be from 1 to 500 μm, but the thickness can be adjusted according to the intended application. The thickness of the surface layer can be from 0.01 to 25%, 0.1 to 20%, or 1 to 15% of the total sheet thickness, but is not limited thereto.

[0071] In addition, the aforementioned co-extrusion refers to a method of creating a multilayer structure by adding one or more layers when using two or more extruders to produce extruded coatings, films, or sheets. For example, a method of bonding a substrate layer and a surface layer extruded by two or more T-die extruders in a roller can be used, but it is not limited to this. The extruders mentioned above can be selected from conventional single-screw extruders, single-screw extruders with independent mixing sections, and twin-screw extruders.

[0072] In addition, through the co-extrusion process described above, multi-layer sheets with planar shapes can be manufactured, and molded articles with curved designs having special profile shapes can be manufactured. However, as long as the above-mentioned substrate layer polymer composition and the above-mentioned matte polymer composition can be melt-processed to manufacture products, the extrusion method or the shape of the molded article is generally not limited.

[0073] The present invention will now be described in more detail based on embodiments and comparative examples. However, the embodiments and comparative examples described below are merely illustrative examples for illustrating the present invention in more detail, and the present invention is not limited to the embodiments and comparative examples described below.

[0074] [Methods for determining physical properties]

[0075] 1) Surface gloss (GLOSS): Measured at 20°, 60° and 85° according to ASTM D523.

[0076] 2) Surface appearance: The surface of the extruded sheet was observed with the naked eye, and the surface roughness, uniformity of roughness, and presence of pinholes were evaluated using the following criteria: Excellent (◎), Good (○), Average (△), and Poor (Х).

[0077] - Excellent: Uniform surface roughness, no pinholes.

[0078] -Good: The surface roughness is uniform, and there are fewer than 5 pinholes per unit area (100mm x 100mm).

[0079] -Generally speaking: The surface roughness is uneven, with more than 5 pinholes and less than 10 pinholes per unit area (100mm x 100mm).

[0080] - Poor: The surface roughness is uneven, with more than 10 pinholes per unit area (100mm x 100mm).

[0081] 3) Noched IZOD Impact Strength: Tested according to ASTM D256 at 1 / 4” and 1 / 8”.

[0082] 4) Heat softening temperature (VST): Measured according to ISO R306 B50 (50N, 50℃ / HR).

[0083] 5) Weather resistance: It was measured according to SAE J1960. Specifically, after the sample was irradiated with a light source of 4000KJ intensity for 2000 hours, the dE / db was measured.

[0084] [Manufacturing Example 1] Manufacturing of reactive extrusion matting agent

[0085] A polymer composition consisting of 17.5 wt% polystyrene (Kumho GP-125), 70 wt% styrene-acrylonitrile copolymer (LG Chem 92HR), and 12.5 wt% N-phenylmaleimide copolymer (DENKA IP) was fed into a twin-screw extruder. Then, relative to 100 parts by weight of the polymer composition, 3.5 parts by weight of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylic acid ester and 0.1 parts by weight of dodecylbenzenesulfonic acid were added, followed by melt extrusion at 265°C to obtain a reactive extrusion matting agent containing approximately 65 wt% gel.

[0086] [Manufacturing Example 2] Manufacturing of Reactive Extrusion Matting Agent

[0087] A polymeric composition consisting of 25 wt% polycarbonate (Lotte Chemical SC-1220R) and styrene-acrylonitrile copolymer (LG Chem 92HR) was fed into a twin-screw extruder. Then, relative to 100 parts by weight of the polymeric composition, 2 parts by weight of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and 0.15 parts by weight of dodecylbenzenesulfonic acid were added, followed by melt extrusion at 270°C to obtain a reactive extrusion matting agent containing approximately 58 wt% gel.

[0088] [Examples 1 to 10 and Comparative Examples 1 to 3] Manufacturing of Injection Molded Articles and Extruded Sheets

[0089] Along with the matting polymer composition prepared according to Table 1 below, 1 part by weight of benzotriazole UV stabilizer (Tinuvin P) and 1 part by weight of HALS UV stabilizer (SanolLS-770) were added relative to 100 parts by weight of ASA. 3 parts by weight of TiO2 and 0.3 parts by weight of phenolic antioxidant were added relative to 100 parts by weight of the sum of ASA and SAN. After mixing, the mixture was extruded through a twin-screw extruder to obtain matting polymer composition particles. The particles were dried, and injection molded samples with a width, length, and thickness of 100 mm x 100 mm x 3.0 mm were manufactured using an injection molding machine. Extruded sheet samples with a width, length, and thickness of 50 mm x 500 mm x 2.0 mm were also manufactured using a single-sheet extruder. The physical properties of the manufactured injection molded articles and extruded sheets were measured and are shown in Table 2 below.

[0090] Table 1

[0091]

[0092] -ASA: Kumho Petrochemical, XC-500A (acrylate content 60wt%)

[0093] -SAN-1: LG Chem, 95HC

[0094] (Mw 100000g / mol, acrylonitrile content 32wt%, glass transition temperature 106℃)

[0095] -SAN-2: LG Chem, 92HR

[0096] (Mw 125000g / mol, acrylonitrile content 26wt%, glass transition temperature 105℃)

[0097] -α-SAN-2: LG Chem, 200 UH

[0098] (Mw 85000g / mol, acrylonitrile content 29wt%, glass transition temperature 124℃)

[0099] -SAN-3: Galata Chemical, Blendex869

[0100] (Mw approximately 5,000,000 g / mol, acrylonitrile content 25 wt%, glass transition temperature 107 °C)

[0101] –Blendex B-MAT (Galata Chemical): Styrene-acrylonitrile copolymer

[0102] -XPHERE-NGR (Pocera): Styrene-acrylonitrile copolymer

[0103] Table 2

[0104]

[0105] As shown in Table 2 above, it was confirmed that when using sheets (molded articles) manufactured by extruding or injection molding the matting polymer composition of the present invention, surface gloss is effectively reduced, while excellent weather resistance and a high-quality surface appearance can be achieved. In particular, as shown in Examples 1 to 8, when using the matting agent manufactured from the reactive extrusion composition described above, the gloss of the extruded sheet is effectively reduced, the surface roughness of the sheet is uniform, and there are almost no pinholes, thereby enabling the manufacture of extruded sheets with a high-quality surface appearance. The surface appearance of the extruded sheet according to Example 1 above is shown in... Figure 1 .

[0106] Specifically, in Examples 1 to 8 above, the 85° gloss of the extruded sheets is 20 or less, preferably 15 or less, the impact strength (1 / 8”) in the above examples is 25 J / m or more, and the dE, which indicates weather resistance, is 2.0 or less. Thus, it can be confirmed that the matting polymer composition according to the present invention has excellent physical properties.

[0107] Furthermore, comparing Example 1 with Comparative Examples 1 to 3, it can be confirmed that when SAN-1 and SAN-2 are included, products with effectively improved matting properties, weather resistance, and surface appearance can be manufactured. Comparing Examples 1 to 3, when 50 to 90 parts by weight of SAN-1 and 15 to 35 parts by weight of SAN-2 are included in 100 parts by weight of ASA, superior heat resistance and impact resistance are shown.

[0108] Furthermore, it was confirmed that in Example 5, the addition of a small amount of SAN-3 effectively reduced the 85° surface gloss of the extruded sheet, and in Examples 6 and 8, the thermal softening temperature was increased due to the inclusion of SAN-2-2.

[0109] As described above, the present invention has been illustrated with specific details, limited embodiments, and accompanying drawings. However, this is provided only to facilitate a more comprehensive understanding of the invention. The invention is not limited to the embodiments described above, and various modifications and variations can be made based on such description by those skilled in the art.

[0110] Therefore, the concept of the present invention is not limited to the illustrated embodiments, but encompasses not only the scope of protection claimed by the present invention, but also all scopes with modifications that are equivalent to or equivalent to the scope of protection claimed by the present invention.

Claims

1. A matting polymer composition comprising: (A) Acrylic ester-styrene-acrylonitrile graft copolymer, (B-1) First styrene-acrylonitrile copolymer, (B-2) Second styrene-acrylonitrile copolymer, and (C) Matting agent, in, In the first styrene-acrylonitrile copolymer, the acrylonitrile content is 31 to 40 wt%, and in the second styrene-acrylonitrile copolymer, the acrylonitrile content is 22 to 30 wt%. The matting agent is manufactured from a reactive extrusion composition comprising polystyrene (PS), styrene-acrylonitrile copolymer (SAN), N-phenylmaleimide copolymer (PMI), alicyclic epoxy compound, and acid compound. The reactive extrusion composition comprises 10 to 20 wt% polystyrene, 60 to 80 wt% styrene-acrylonitrile copolymer, 5 to 20 wt% N-phenylmaleimide copolymer, 1 to 6 wt% alicyclic epoxy compound, and 0.01 to 1.5 wt% acid compound. The alicyclic epoxy compound is selected from 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane-carboxylic acid ester, diethylene glycol bis(3,4-epoxycyclohexane-carboxylic acid ester), 2-ethyl-1,3-hexanediol bis(3,4-epoxycyclohexane-carboxylic acid ester), diethylene glycol bis(3,4-epoxy-6-methylcyclohexane-carboxylic acid ester), and 3-methyl-1,5-pentanediol bis(3,4-epoxycyclohexane-carboxylic acid ester). One or more of the following: 1,5-pentanediol bis(3,4-epoxycyclohexane-carboxylic acid ester), ethylene glycol bis(3,4-epoxycyclohexane-carboxylic acid ester), ethylene glycol bis(3,4-epoxy-6-methylcyclohexane-carboxylic acid ester), bis(3,4-epoxycyclohexylmethyl) oxalate, bis(3,4-epoxycyclohexylmethyl) succinate, bis(3,4-epoxycyclohexylmethyl) adipate, and 1,2,8,9-diepoxylimonene. The matting polymer composition comprises, relative to 100 parts by weight of the acrylate-styrene-acrylonitrile graft copolymer, 50 to 90 parts by weight of the first styrene-acrylonitrile copolymer, 15 to 35 parts by weight of the second styrene-acrylonitrile copolymer, and 2 to 24 parts by weight of the matting agent. The weight ratio of the first styrene-acrylonitrile copolymer to the second styrene-acrylonitrile copolymer is 1:0.2 to 0.

3.

2. The matting polymer composition according to claim 1, wherein, The acid compound is selected from any one or more of R1COOH or R2SO3H, wherein R1 and R2 are each independently C 6-30 Alkyl, C 6-30 Aryl, or C 6-30 Aryl C 6-30 alkyl.

3. The matting polymer composition according to claim 1, wherein, The glass transition temperature of the second styrene-acrylonitrile copolymer is 110 to 130°C.

4. The matting polymer composition according to claim 1, wherein, The matting polymer composition further comprises a tertiary styrene-acrylonitrile copolymer with a weight-average molecular weight of 4,000,000 g / mol or more.

5. The matting polymer composition according to claim 4, wherein, The third styrene-acrylonitrile copolymer comprises 1 to 6 parts by weight of the acrylate-styrene-acrylonitrile graft copolymer, relative to 100 parts by weight of the acrylate-styrene-acrylonitrile graft copolymer.

6. A molded article manufactured by extruding or injection molding the matte polymer composition of claim 1.

7. A sheet comprising a substrate layer and a surface layer, wherein the surface layer is formed by laminating the matte polymer composition of claim 1 onto the substrate layer through co-extrusion.

8. The sheet according to claim 7, wherein, The substrate layer is selected from one or more of the following: polyvinyl chloride (PVC), polypropylene (PP), polyacrylate, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polymethyl methacrylate (PMMA), polycarbonate (PC), polyamide, styrene-acrylonitrile copolymer (SAN), acrylonitrile-butadiene-styrene (ABS), and acrylonitrile-styrene-acrylate (ASA).

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