Resin composition

Abstract

A resin composition, according to one embodiment of the present invention, comprises: a graft copolymer including a rubbery polymer, an aromatic vinyl monomer unit, and a vinyl cyanide monomer unit; a matrix copolymer including an aromatic vinyl monomer unit and a vinyl cyanide monomer unit; a matting agent including an aromatic vinyl-vinyl cyanide crosslinked copolymer; a chemical resistance improver; and an appearance quality improver, wherein the matting agent may be included in an amount of 1 part by weight or more and 40 parts by weight or less, the chemical resistance improver may be included in an amount of 1 part by weight or more and 12 parts by weight or less, and the appearance quality improver may be included in an amount of 0.5 parts by weight or more and 12 parts by weight or less, with respect to 100 parts by weight of the total of the graft copolymer and the matrix copolymer.

Description

Resin composition

[0001] [Cross-reference with related applications]

[0002] This application claims the benefit of priority based on Korean Patent Application 10-2024-0181990 filed December 09, 2024, and all contents disclosed in the literature of said Korean patent applications are incorporated herein as part of this specification.

[0003]

[0004] [Technology Field]

[0005] The present invention relates to a resin composition having low gloss while maintaining chemical resistance and appearance quality.

[0006] Recently, many home appliances are adopting low-gloss materials to express a luxurious appearance. To achieve this, matte coating is applied, or the gloss of injection-molded products is reduced by etching the inside of the mold to create irregularities and molding the resin. However, since both methods result in increased costs, a method has been devised to produce a matte effect by incorporating a matting agent into the material itself.

[0007] However, matte products manufactured by the aforementioned method have a problem in that they are structurally vulnerable to chemical attacks because the surface roughness intended to reduce gloss ultimately increases the surface area of ​​the injection-molded product; consequently, when contaminants (detergents, oils, etc.) adhere, the contact surface becomes larger compared to general injection-molded products, making them relatively more susceptible to chemical attacks.

[0008] In addition, the matte product manufactured by the above-described method had a high defect rate when injecting large home appliances due to reduced fluidity, and the surface of the injection-molded product was uneven and had a poor appearance due to the difference in compatibility between the base resin and the matting agent, such as the matting agent clumping.

[0009] [Prior Art Literature]

[0010] [Patent Literature]

[0011] (Patent Document 1) CN 117866406 A

[0012]

[0013] The problem to be solved by the present invention is to provide a resin composition having low gloss while having excellent chemical resistance, fluidity, and appearance quality.

[0014] (1) The present invention provides a resin composition comprising: a graft copolymer comprising a rubbery polymer, an aromatic vinyl monomer unit and a vinyl cyanide monomer unit; a matrix copolymer comprising an aromatic vinyl monomer unit and a vinyl cyanide monomer unit; a matting agent comprising an aromatic vinyl-vinyl cyanide crosslinked copolymer; a chemical resistance improver; and an appearance quality improver, wherein, for every 100 parts by weight of the total of the graft copolymer and the matrix copolymer, the matting agent is included in an amount of 1 part by weight or more and 40 parts by weight or less, the chemical resistance improver is included in an amount of 1 part by weight or more and 12 parts by weight or less, and the appearance quality improver is included in an amount of 0.5 parts by weight or more and 12 parts by weight or less.

[0015] (2) The present invention provides a resin composition according to (1) wherein the matting agent is included in an amount of 5 parts by weight or more and 25 parts by weight or less, with respect to 100 parts by weight of the total amount of the graft copolymer and the matrix copolymer.

[0016] (3) The present invention provides a resin composition in which, in (1) or (2), the chemical resistance improving agent is included in an amount of 2 parts by weight or more and 10 parts by weight or less, with respect to 100 parts by weight of the total of the first graft copolymer, the second graft copolymer, and the matrix copolymer.

[0017] (4) The present invention provides a resin composition in which, in any one of (1) to (3), the appearance quality improving agent is included in an amount of 1 part by weight or more and 10 parts by weight or less, with respect to 100 parts by weight of the total amount of the first graft copolymer, the second graft copolymer, and the matrix copolymer.

[0018] (5) The present invention provides a resin composition in which, in any one of (1) to (4), the aromatic vinyl-vinyl cyanide crosslinked copolymer comprises an aromatic vinyl monomer unit; a vinyl cyanide monomer unit; and a crosslinked portion formed from a crosslinking functional compound.

[0019] (6) The present invention provides a resin composition in which, in any one of (1) to (5), the chemical resistance improving agent comprises a polymer comprising crystalline units.

[0020] (7) The present invention provides a resin composition in which, in any one of (1) to (6), the olefin-based polymer containing the crystalline unit contains the crystalline unit in an amount of 20% by weight or more and 80% by weight or less.

[0021] (8) The present invention provides a resin composition in which, in any one of (1) to (7), the chemical resistance improving agent is one or more selected from the group consisting of ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer and polyester-based thermoplastic elastomer (TPEE) containing crystalline units.

[0022] (9) The present invention provides a resin composition in which, in any one of (1) to (8), the appearance quality improving agent is one or more selected from the group consisting of aromatic vinyl-vinyl cyanide copolymers and acrylic copolymers.

[0023] (10) The present invention provides a resin composition in which, in any one of (1) to (9), the appearance quality improving agent has a weight-average molecular weight of 1,000,000 g / mol or more.

[0024] (11) The present invention provides a resin composition in which, in any one of (1) to (10), the glossiness (60°) measured according to the ASTM D2457 method is 20 or less.

[0025] (12) The present invention provides a resin composition in which, in any one of (1) to (11), the melt index (220°C, 10kg) measured according to the ASTM D1238 method is 20 g / 10min or higher.

[0026] (13) The present invention provides a resin composition in which, in any one of (1) to (12), the graft copolymer comprises: a first graft copolymer comprising a conjugated diene polymer, an aromatic vinyl monomer unit, and a vinyl cyanide monomer unit; and / or a second graft copolymer comprising an acrylic polymer, an aromatic vinyl monomer unit, and a vinyl cyanide monomer unit.

[0027] (14) The present invention provides a resin composition in which, in any one of (1) to (13), the matting agent is included in an amount of 30% by weight or more and 83% by weight or less with respect to the total amount of the matting agent, the chemical resistance improver is included in an amount of 10% by weight or more and 45% by weight or less with respect to the total amount of the appearance quality improver, and the appearance quality improver is included in an amount of 2% by weight or more and 25% by weight or less.

[0028] A resin composition according to one embodiment of the present invention has low gloss while having excellent chemical resistance, fluidity, and appearance quality.

[0029] Hereinafter, the present invention will be described in more detail to aid in understanding the invention.

[0030] Terms and words used in this specification and claims should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted in a meaning and concept consistent with the technical spirit of the invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0031] In the present invention, the term 'monomer unit' may refer to a component, structure, or the material itself derived from a monomer, and as a specific example, may refer to a repeating unit formed within a polymer by a monomer introduced during the polymerization of a polymer and participating in the polymerization reaction.

[0032] The term 'composition' as used in the present invention includes reaction products and decomposition products formed from the materials of the said composition, as well as mixtures of materials containing said composition.

[0033] In the present invention, the weight-average molecular weight of each component constituting the resin composition can be measured as a relative value to standard polystyrene, which is a standard sample, by using tetrahydrofuran as the eluent and gel permeation chromatography.

[0034]

[0035] <Resin Composition>

[0036] The present invention provides a resin composition.

[0037] A resin composition according to one embodiment of the present invention comprises at least a matrix copolymer comprising a graft copolymer comprising an aromatic vinyl monomer unit and a vinyl cyanide monomer unit, a rubbery polymer, an aromatic vinyl monomer unit and a vinyl cyanide monomer unit; a matting agent comprising an aromatic vinyl-vinyl cyanide crosslinked copolymer; a chemical resistance improver; and an appearance quality improver, wherein, with respect to 100 parts by weight of the total of the graft copolymer and the matrix copolymer, the matting agent is included in an amount of 1 part by weight or more and 40 parts by weight or less, the chemical resistance improver is included in an amount of 1 part by weight or more and 12 parts by weight or less, and the appearance quality improver is included in an amount of 0.5 parts by weight or more and 12 parts by weight or less.

[0038]

[0039] Generally, when a matting agent is added to a resin composition, surface roughness increases, and consequently, the surface area of ​​the injection-molded product increases, resulting in structurally weak chemical resistance. Accordingly, a method of applying a chemical resistance improver to the resin composition to which the matting agent has been applied has been proposed; however, chemical resistance improvers have the problem of increasing the glossiness of the resin composition.

[0040] In addition, cross-linked copolymers used as matting agents can effectively impart low gloss to resin compositions by inducing diffuse reflection that scatters incident light, but due to their structural characteristics that they are not linear polymers, they have low flowability, which has resulted in a problem of low fluidity in resin compositions containing cross-linked copolymers. Consequently, there is a high defect rate when injection molding large home appliances with complex structures, and the matting agent clumps together, causing the surface of the injection-molded product to be uneven and resulting in a deterioration in appearance quality.

[0041] A resin composition according to one embodiment of the present invention includes a matting agent, a chemical resistance improver, and an appearance quality improver in desirable amounts, thereby enabling excellent appearance quality, chemical resistance, and melt index while having low gloss.

[0042] In the present invention, having low gloss means that the gloss (60°) of the resin composition measured according to the ASTM D2457 method is 20 or less, and specifically, 18 or less, 16 or less, 14 or less, or 12 or less.

[0043] A resin composition according to one embodiment of the present invention may have a melt index (220°C, 10kg) measured according to the ASTM D1238 method of 20 g / 10min or higher, and specifically, as an example, may be 22 g / 10min or higher, 24 g / 10min or higher, 26 g / 10min or higher, 28 g / 10min or higher, or 30 g / 10min or higher. When the above range is satisfied, it is evaluated to have an excellent melt index.

[0044] According to one embodiment of the present invention, when an injection molded specimen of size 10 cm × 10 cm is produced by injecting the resin composition at an injection temperature of 240°C and observed visually, three or fewer foreign substances having a size of 100 μm or more can be observed within the injection molded specimen, and in this case, the appearance quality is evaluated as excellent.

[0045]

[0046] Hereinafter, each component constituting the resin composition according to one embodiment of the present invention will be described.

[0047]

[0048] Graft copolymer

[0049] A resin composition according to one embodiment of the present invention may include a graft copolymer. The graft copolymer serves to provide excellent moldability and impact resistance to the resin composition and may include a first graft copolymer comprising a conjugated diene polymer, an aromatic vinyl monomer unit, and a vinyl cyanide monomer unit; and / or a second graft copolymer comprising an acrylic polymer, an aromatic vinyl monomer unit, and a vinyl cyanide monomer unit.

[0050]

[0051] According to one embodiment of the present invention, the first graft copolymer serves to provide excellent moldability and impact resistance to the resin composition, and the first graft copolymer can generally be a commercially available resin and can be obtained through a commercially available method.

[0052] According to one embodiment of the present invention, the first graft copolymer may be an acrylonitrile-butadiene-styrene copolymer (ABS) comprising a conjugated diene polymer, an aromatic vinyl monomer unit, and a vinyl cyanide monomer unit.

[0053] According to one embodiment of the present invention, the first graft copolymer may have a core-shell structure comprising a core containing a conjugated diene monomer unit; and a shell surrounding the core and comprising an aromatic vinyl monomer unit and a vinyl cyanide monomer unit.

[0054] According to one embodiment of the present invention, the conjugated diene monomer for forming the conjugated diene polymer of the first graft copolymer may be one or more selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, and isoprene, and as a specific example, it may be 1,3-butadiene.

[0055] According to one embodiment of the present invention, the aromatic vinyl monomer for forming the aromatic vinyl monomer of the first graft copolymer may be one or more selected from the group consisting of styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, o-methylstyrene, o-butylstyrene, bromostyrene, chlorostyrene, trichlorostyrene, and derivatives thereof, and may be styrene as a specific example.

[0056] The above aromatic vinyl monomer may be added in an amount of 30 to 95 parts by weight, 40% to 90 parts by weight, 50 to 85 parts by weight, or 60 to 80 parts by weight, based on 100 parts by weight of the total monomer input amount including the aromatic vinyl monomer and the vinyl cyanide monomer. When the above range is satisfied, a copolymer can be obtained with a high polymerization conversion rate, and compatibility with the matrix copolymer described later can be improved while maintaining the mechanical properties of the copolymer.

[0057] According to one embodiment of the present invention, the vinyl cyanide monomer for forming the vinyl cyanide monomer unit of the first graft copolymer may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile and derivatives thereof, and may be acrylonitrile as a specific example.

[0058] In addition, according to one embodiment of the present invention, the vinyl cyanide monomer may be added in an amount of 5 to 70 parts by weight, 10 to 60 parts by weight, 15 to 50 parts by weight, or 20 to 40 parts by weight, based on the total monomer input content including the aromatic vinyl monomer and the vinyl cyanide monomer. When the above range is satisfied, a copolymer can be obtained with a high polymerization conversion rate, and compatibility with the matrix copolymer described later can be improved while maintaining the mechanical properties of the copolymer.

[0059] According to one embodiment of the present invention, the first graft copolymer may be prepared through emulsion polymerization and emulsion graft polymerization, for example, by preparing a rubbery polymer core (or seed) by emulsion polymerizing a conjugated diene monomer, adding a vinyl cyanide monomer and an aromatic vinyl monomer to the core, and preparing the polymer by emulsion graft polymerization.

[0060] Additionally, the first graft copolymer may comprise 30% to 70% by weight of a core containing a conjugated diene monomer-derived unit; and 30% to 70% by weight of a shell surrounding the core containing an aromatic vinyl monomer-derived unit and a vinyl cyanide monomer-derived unit, wherein the shell may contain the aromatic vinyl monomer-derived unit and the vinyl cyanide monomer-derived unit in a weight ratio of 7:3 to 8:2, and in this case, the impact resistance, mechanical properties, and moldability of the first graft copolymer may be superior.

[0061]

[0062] According to one embodiment of the present invention, the second graft copolymer serves to provide excellent moldability and impact resistance to the resin composition while simultaneously improving chemical resistance. The second graft copolymer can generally be a commercially available resin and can be obtained through a commercially available method.

[0063] According to one embodiment of the present invention, the second graft copolymer may be a graft copolymer (Acrylic-Styrene-Acrylonitrile, ASA) prepared based on an acrylic polymer comprising an acrylic polymer, an aromatic vinyl monomer unit, and a vinyl cyanide monomer unit.

[0064] According to one embodiment of the present invention, the acrylic monomer for forming the acrylic monomer unit of the acrylic polymer of the second graft copolymer is C4 to C 10It may be an alkyl (meth)acrylate-based monomer, and specifically examples may be one or more selected from the group consisting of butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, ethylhexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, and decyl (meth)acrylate, and more specifically, butyl acrylate.

[0065] According to one embodiment of the present invention, the aromatic vinyl monomer for forming the aromatic vinyl monomer unit of the second graft copolymer may be one or more selected from the group consisting of styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene, and as a specific example, it may be styrene.

[0066] According to one embodiment of the present invention, the vinyl cyanide monomer for forming the vinyl cyanide monomer unit of the second graft copolymer may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, and α-chloroacrylonitrile, and as a specific example, it may be acrylonitrile.

[0067] According to one embodiment of the present invention, the C4 to C 10 The alkyl (meth)acrylate-based monomer can be added in an amount of 35% by weight or more and 55% by weight or 40% by weight or more and 55% by weight or less, based on the total weight of the monomers added during the preparation of the second graft copolymer, and more specifically, in an amount of 50% by weight or more and 55% by weight or less. If the above-described range is satisfied, the weather resistance and impact resistance of the second graft copolymer can be further improved.

[0068] According to one embodiment of the present invention, the aromatic vinyl monomer may be added in an amount of 30% by weight or more and 50% by weight or 35% by weight or more and 45% by weight or less, based on the total weight of the monomers added during the preparation of the second graft copolymer, and more specifically, in an amount of 35% by weight or more and 45% by weight or less. If the above-described range is satisfied, the processability of the second graft copolymer can be further improved, and the second graft copolymer can be more uniformly dispersed within the resin composition.

[0069] According to one embodiment of the present invention, the vinyl cyanide monomer may be added in an amount of 10% by weight or more and 30% by weight or 10% by weight or more and 25% by weight or less, based on the total weight of the monomers added during the preparation of the second graft copolymer, and more specifically, in an amount of 10% by weight or more and 20% by weight or less. If the above-described range is satisfied, the chemical resistance of the second graft copolymer can be further improved, and the second graft copolymer can be more uniformly dispersed within the resin composition.

[0070]

[0071] A resin composition according to one embodiment of the present invention may include 10 parts by weight or more and 50 parts by weight or less of the graft copolymer with respect to 100 parts by weight of the total sum of the graft copolymer and the matrix copolymer, and as a specific example, may include 15 parts by weight or more, 20 parts by weight or more, 25 parts by weight or more, or 30 parts by weight or more, and may also include 48 parts by weight or less, 46 parts by weight or less, 44 parts by weight or less, 42 parts by weight or less, or 40 parts by weight or less. When the above-described ranges are satisfied, the impact strength and melt index of the resin composition may be further improved.

[0072] According to one embodiment of the present invention, when the graft copolymer includes both the first graft copolymer and the second graft copolymer, the ratio (A:B) of the content of the first graft copolymer (A) and the content of the second graft copolymer (B) may be 1:0.5 or more and 1:2 or less. Specifically, it may be 1:0.55 or more, 1:0.6 or more, 1:0.65 or more, 1:0.7 or more, or 1:0.75 or more. Additionally, it may be 1:1.8 or less, 1:1.6 or less, 1:1.4 or less, 1:1.2 or less, or 1:1 or less. When the above-described ranges are satisfied, the impact strength and melt index of the resin composition may be further improved.

[0073]

[0074] Matrix copolymer

[0075] A resin composition according to one embodiment of the present invention may include a matrix copolymer.

[0076] According to one embodiment of the present invention, the matrix copolymer is a non-graft copolymer that has excellent heat resistance and impact resistance and also excellent fluidity, so it can serve as a matrix for the resin composition and enable the realization of excellent physical properties in the molded article of the resin composition. The matrix copolymer can generally be a commercially available resin and can be obtained through a commercially available method.

[0077]

[0078] According to one embodiment of the present invention, the aromatic vinyl monomer for forming the aromatic vinyl monomer of the matrix copolymer may be one or more selected from the group consisting of styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, o-methylstyrene, o-butylstyrene, bromostyrene, chlorostyrene, trichlorostyrene, and derivatives thereof, and may be styrene as a specific example.

[0079] The above aromatic vinyl monomer may be added in an amount of 30 to 95 parts by weight, 40% to 90 parts by weight, 50 to 85 parts by weight, or 60 to 80 parts by weight, based on 100 parts by weight of the total monomer input amount including the aromatic vinyl monomer and the vinyl cyanide monomer. When the above range is satisfied, a copolymer can be obtained with a high polymerization conversion rate, and compatibility with the graft copolymer can be improved.

[0080]

[0081] According to one embodiment of the present invention, the vinyl cyanide monomer for forming the vinyl cyanide monomer unit of the matrix copolymer may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile and derivatives thereof, and a specific example may be acrylonitrile.

[0082] In addition, according to one embodiment of the present invention, the vinyl cyanide monomer may be added in an amount of 5 to 70 parts by weight, 10 to 60 parts by weight, 15 to 50 parts by weight, or 20 to 40 parts by weight, based on the total monomer input content including the aromatic vinyl monomer and the vinyl cyanide monomer. When the above range is satisfied, a copolymer can be obtained with a high polymerization conversion rate, and compatibility with the graft copolymer can be improved.

[0083] The weight-average molecular weight of the matrix copolymer according to one embodiment of the present invention may be 80,000 g / mol or more and 160,000 g / mol or less, and as a specific example, may be 85,000 g / mol or more, 90,000 g / mol or more, 95,000 g / mol or more, 100,000 g / mol or more, 105,000 g / mol or more, or 110,000 g / mol or more, and may also be 155,000 g / mol or less, 150,000 g / mol or less, 145,000 g / mol or less, 140,000 g / mol or less, 135,000 g / mol or less, or 130,000 g / mol or less. When the above-described ranges are satisfied, the impact strength and melt index of the resin composition may be further improved.

[0084]

[0085] A resin composition according to one embodiment of the present invention may include 10 parts by weight or more and 90 parts by weight or less of the matrix copolymer with respect to 100 parts by weight of the total sum of the graft copolymer and the matrix copolymer, and as a specific example, may include 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, or 60 parts by weight or more, and may also include 88 parts by weight or less, 86 parts by weight or less, 84 parts by weight or less, 82 parts by weight or less, or 80 parts by weight or less. When the above-described ranges are satisfied, the impact strength and melt index of the resin composition may be further improved.

[0086]

[0087] Matting agent

[0088] A matting agent according to one embodiment of the present invention suppresses surface gloss by inducing light scattering by forming fine irregularities on the surface of a product during injection molding, and may include an aromatic vinyl-vinyl cyanide crosslinked copolymer.

[0089] An aromatic vinyl-vinyl cyanide crosslinked copolymer according to one embodiment of the present invention may comprise an aromatic vinyl monomer unit; a vinyl cyanide monomer unit; and a crosslinked portion formed from a crosslinking functional compound.

[0090] According to one embodiment of the present invention, the aromatic vinyl monomer for forming the aromatic vinyl monomer unit of the aromatic vinyl-vinyl cyanide crosslinked copolymer may be one or more selected from the group consisting of styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, o-methylstyrene, ot-butylstyrene, bromostyrene, chlorostyrene, trichlorostyrene, and derivatives thereof, and may be styrene as a specific example.

[0091] According to one embodiment of the present invention, the vinyl cyanide monomer for forming the vinyl cyanide monomer unit of the aromatic vinyl-vinyl cyanide crosslinked copolymer may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile and derivatives thereof, and may be acrylonitrile as a specific example.

[0092] According to one embodiment of the present invention, the aromatic vinyl-vinyl cyanide crosslinked copolymer may comprise aromatic vinyl monomer units and vinyl cyanide monomer units in a weight ratio of 80:20 to 60:40, preferably 75:25 to 65:35. If the above conditions are satisfied, a vinyl crosslinked polymer with improved processability and chemical resistance can be produced.

[0093]

[0094] According to one embodiment of the present invention, a crosslinking functional compound for forming a crosslinking portion for forming a vinyl cyanide monomer unit of the aromatic vinyl-vinyl cyanide crosslinking copolymer may include a functional group such as a siloxane group, a vinyl group, or an acrylic group, and there may be two or more, preferably three or more, functional groups in one crosslinking functional compound. Specifically, the crosslinking functional compound may be a silicone-based compound or a polyene-based compound.

[0095] According to one embodiment of the present invention, the polyene-based crosslinking agent may be, for example, a vinyl-based crosslinking agent or an acrylic-based crosslinking agent, and specifically, one or more selected from the group consisting of divinylbenzene, trivinylbenzene, ethylene glycol di(meth)acrylate, allyl(meth)acrylate, diallyl phthalate, diallyl maleate, trialyl isocyanurate, and trialkyl isocyanurate may be applied, and allyl(meth)acrylate may be preferably used.

[0096] According to one embodiment of the present invention, the silicone-based crosslinking agent is, for example, 1,3,5-triisopropyl-1,3,5-trivinyl-cyclotrisiloxane, 1,3,5,7-tetraisopropyl-1,3,5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7,9-pentavinyl-cyclopentasiloxane, 1,3,5-trisec-butyl-1,3,5-trivinyl-cyclotrisiloxane, 1,3,5,7-tetrasec-butyl-1,3,5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7,9-pentasec-butyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane, It may be 1,3,5-trimethyl-1,3,5-trivinyl-cyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane, 1,3,5-triethyl-1,3,5-trivinyl-cyclotrisiloxane, 1,3,5,7-tetraethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7,9-pentaethyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane, or a mixture thereof, and may be divinylsilane, trivinylsilane, dimethyldivinylsilane, divinylmethylsilane, methyltrivinylsilane, diphenyldivinylsilane, Divinylphenylsilane, trivinylphenylsilane, divinylmethylphenylsilane, tetravinylsilane, dimethylvinyl disiloxane, divinyldiphenylchlorosilane, etc. can be used in combination.

[0097] The above silicone-based crosslinking agent may preferably be 1,3,5-trimethyl-1,3,5-trivinyl-cyclotrisiloxane, divinylmethylsilane, disiloxane, or a mixture thereof, and more preferably divinylmethylsilane.

[0098]

[0099] As described above, the matting agent comprises an aromatic vinyl-vinyl cyanide crosslinked copolymer, thereby effectively lowering the glossiness of the resin composition even with a small amount, and accordingly, the reduction in chemical resistance caused by the matting agent can be minimized.

[0100]

[0101] A resin composition according to one embodiment of the present invention may include the matting agent in an amount of 1 part by weight or more and 40 parts by weight or less, based on 100 parts by weight of the total of the graft copolymer and the matrix copolymer. Specifically, it may include 2 parts by weight or more, 3 parts by weight or more, 4 parts by weight or more, or 5 parts by weight or more, and may also include 35 parts by weight or less, 32 parts by weight or less, 30 parts by weight or less, 28 parts by weight or less, or 25 parts by weight or less.

[0102] A resin composition according to one embodiment of the present invention can satisfy excellent appearance quality, chemical resistance, and melt index while having low gloss by including the matting agent within the range described above. If the matting agent is included in an amount less than the range described above, the low gloss of the resin composition may not be exhibited. Furthermore, if the matting agent is included in an amount exceeding the range described above, the melt index of the resin composition may decrease, and the impact strength and appearance quality may be degraded.

[0103] According to one embodiment of the present invention, the resin composition may contain the matting agent in an amount of 30% by weight or more and 83% by weight or less with respect to the total sum of the matting agent, the chemical resistance improver, and the appearance quality improver. Specifically, it may contain 35% by weight or more, 40% by weight or more, 45% by weight or more, 50% by weight or more, or 60% by weight or more, and may also contain 82% by weight or less, 81% by weight or less, 80% by weight or less, 79% by weight or less, or 78% by weight or less. When the above-described ranges are satisfied, the appearance quality, chemical resistance, and melt index can be further improved while having low gloss without deterioration of other physical properties.

[0104]

[0105] Chemical resistance improver

[0106] A chemical resistance improving agent according to one embodiment of the present invention imparts chemical resistance to a resin composition, and can generally use a commercially available resin and can be obtained through a commercially available method.

[0107] According to one embodiment of the present invention, the chemical resistance improving agent may be a polymer comprising crystalline units. In the present invention, the crystalline unit refers to a unit derived from a crystalline monomer capable of forming crystals, and may be one or more selected from ethylene units, propylene units, and butylene units.

[0108] According to one embodiment of the present invention, the polymer comprising the crystalline unit may include the crystalline unit in an amount of 20 wt% or more and 80 wt% or less, and as a specific example, may include 22 wt% or more, 24 wt% or more, 26 wt% or more, 28 wt% or more, or 30 wt% or more, and may also include 75 wt% or less, 70 wt% or less, 65 wt% or less, 60 wt% or less, 55 wt% or less, or 50 wt% or less.

[0109] According to one embodiment of the present invention, the chemical resistance improving agent may be one or more selected from the group consisting of ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, and polyester-based thermoplastic elastomer (TPEE) comprising crystalline units.

[0110] A resin composition according to one embodiment of the present invention may contain the chemical resistance improving agent in an amount of 1 part by weight or more and 12 parts by weight or less, based on 100 parts by weight of the total of the graft copolymer and the matrix copolymer. Specifically, it may contain 1.2 parts by weight or more, 1.4 parts by weight or more, 1.6 parts by weight or more, 1.8 parts by weight or more, 2 parts by weight or more, 2.2 parts by weight or more, 2.4 parts by weight or more, 2.6 parts by weight or more, 2.8 parts by weight or more, or 3 parts by weight or more. Additionally, it may contain 11 parts by weight or less, 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less.

[0111] A resin composition according to one embodiment of the present invention may have improved impact strength and melt index while having low gloss by including the chemical resistance improving agent in an amount within the range described above. If the chemical resistance improving agent is included in an amount less than the range described above, the chemical resistance of the resin composition may be reduced. Furthermore, if the chemical resistance improving agent is included in an amount exceeding the range described above, low gloss may not be exhibited in the resin composition.

[0112] According to one embodiment of the present invention, the resin composition may contain the chemical resistance improving agent in an amount of 10% by weight or more and 45% by weight or less with respect to the total sum of the matting agent, the chemical resistance improving agent, and the appearance quality improving agent. Specifically, it may contain 12% by weight or more, 14% by weight or more, 16% by weight or more, 18% by weight or more, or 19% by weight or more, and may also contain 42% by weight or less, 40% by weight or less, 36% by weight or less, 34% by weight or less, or 32% by weight or less. When the above-described ranges are satisfied, the appearance quality, chemical resistance, and melt index can be further improved while having low gloss without deterioration of other physical properties.

[0113]

[0114] Appearance quality improver

[0115] An appearance quality improving agent according to one embodiment of the present invention prevents the formation of foreign matter when a resin composition is injected, and generally, a commercially available resin can be applied and can be obtained through a commercially available method.

[0116] An appearance quality improving agent according to one embodiment of the present invention may be an ultra-high molecular weight copolymer having a weight-average molecular weight of 1,000,000 g / mol or more, and may be one or more selected from the group consisting of aromatic vinyl-vinyl cyanide copolymers and acrylic copolymers. According to one embodiment of the present invention, the appearance quality improving agent may be a non-crosslinked copolymer.

[0117] According to one embodiment of the present invention, the appearance quality improver may be an aromatic vinyl-vinyl cyanide copolymer comprising an aromatic vinyl monomer unit and a vinyl cyanide monomer unit.

[0118] According to one embodiment of the present invention, when the appearance quality improving agent is an aromatic vinyl-vinyl cyanide copolymer, the aromatic vinyl monomer for forming the aromatic vinyl monomer unit of the aromatic vinyl-vinyl cyanide copolymer may be one or more selected from the group consisting of styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, o-methylstyrene, o-butylstyrene, bromostyrene, chlorostyrene, trichlorostyrene, and derivatives thereof, and may be styrene as a specific example.

[0119] According to one embodiment of the present invention, when the appearance quality improving agent is an aromatic vinyl-vinyl cyanide copolymer, the vinyl cyanide monomer for forming the vinyl cyanide monomer unit of the aromatic vinyl-vinyl cyanide copolymer may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile and derivatives thereof, and a specific example may be acrylonitrile.

[0120] According to one embodiment of the present invention, the appearance quality improving agent may include the aromatic vinyl monomer in an amount of 50% by weight or more and 80% by weight or less, and as a specific example, may include 52% by weight or more, 54% by weight or more, 56% by weight or more, 58% by weight or more, or 60% by weight or more, and may also include 78% by weight or less, 76% by weight or less, 74% by weight or less, 72% by weight or less, or 70% by weight or less.

[0121]

[0122] An appearance quality improver according to one embodiment of the present invention may be an acrylic copolymer comprising alkyl acrylate monomer units and alkyl methacrylate monomer units.

[0123] According to one embodiment of the present invention, the alkyl acrylate monomer for forming the alkyl acrylate monomer unit of the acrylic copolymer may be linear, branched, or cyclic having 1 to 18 carbon atoms of the alkyl group, and preferably may be one or more selected from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, lauryl acrylate, stearyl acrylate, 2-ethylhexyl acrylate, and cyclohexyl acrylate.

[0124] According to one embodiment of the present invention, the alkyl methacrylate monomer for forming the alkyl methacrylate monomer unit of the acrylic copolymer may be linear or cyclic having 2 to 18 carbon atoms of the alkyl group, and preferably may be one or more selected from the group consisting of n-butyl methacrylate, lauryl methacrylate, stearyl methacrylate, tridecyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, and cyclohexyl methacrylate.

[0125]

[0126] The weight-average molecular weight of the appearance quality improving agent according to one embodiment of the present invention may be 1,000,000 g / mol or more, and specifically, as an example, may be 1,200,000 g / mol or more, 1,400,000 g / mol or more, 1,600,000 g / mol or more, 1,800,000 g / mol or more, or 2,000,000 g / mol or more, and may also be 10,000,000 g / mol or less, 9,000,000 g / mol or less, 8,000,000 g / mol or less, 7,000,000 g / mol or less, or 6,000,000 g / mol or less. When the above range is satisfied, the appearance characteristics of the resin composition may be further improved.

[0127] A resin composition according to one embodiment of the present invention may contain 0.5 parts by weight or more and 12 parts by weight or less of the appearance quality improving agent based on 100 parts by weight of the total sum of the graft copolymer, the matrix copolymer, and the matting agent, and as a specific example, may contain 0.6 parts by weight or more, 0.7 parts by weight or more, 0.8 parts by weight or more, 0.9 parts by weight or more, or 1 part by weight or more, and may also contain 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less.

[0128] A resin composition according to one embodiment of the present invention can satisfy both excellent appearance quality and melt index while having low gloss by including the appearance quality improving agent within the range described above. If the appearance quality improving agent is included in an amount less than the range described above, the appearance quality of the resin composition may be degraded. Additionally, if the appearance quality improving agent is included in an amount exceeding the range described above, the melt index of the resin composition may be reduced.

[0129] According to one embodiment of the present invention, the resin composition may contain the appearance quality improver in an amount of 2% by weight or more and 25% by weight or less with respect to the total sum of the matting agent, chemical resistance improver, and appearance quality improver. Specifically, it may contain 2.2% by weight or more, 2.4% by weight or more, 2.6% by weight or more, 2.8% by weight or more, or 3% by weight or more, and may also contain 20% by weight or less, 15% by weight or less, 10% by weight or less, 8% by weight or less, or 7% by weight or less. When the above-described ranges are satisfied, the appearance quality, chemical resistance, and melt index can be further improved while having low gloss without deterioration of other physical properties.

[0130]

[0131] Other additives

[0132] A resin composition according to one embodiment of the present invention may further include additives.

[0133] According to one embodiment of the present invention, the additive may be one or more selected from the group consisting of flame retardants, lubricants, antioxidants, light stabilizers, hydrolysis stabilizers, release agents, pigments, antistatic agents, conductivity enhancers, electromagnetic shielding agents, magnetizing agents, mineral fillers, crosslinking agents, antibacterial agents, processing aids, metal deactivators, flame suppressants, anti-friction and anti-wear agents, compatibilizers, anti-dripping agents, and coupling agents.

[0134] The above additives may be used without limitation as long as they are used in the technical field of the present invention, and a person skilled in the art may select the additives included in the present invention according to the purpose.

[0135]

[0136] <Molded Product>

[0137] The present invention provides a molded article formed from the resin composition.

[0138] According to one embodiment of the present invention, the molded article may be extruded and injection-molded from the resin composition and may be applied to a product family requiring a transparent plastic that exhibits a matte finish, and as a specific example, may be a part such as a washing machine or a housing (exterior) of an office machine.

[0139]

[0140] Hereinafter, embodiments of the present invention are described in detail so that those skilled in the art can easily implement the invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

[0141]

[0142] Examples and Comparative Examples

[0143] The compounds used in the examples and comparative examples are as follows.

[0144]

[0145] (1) First graft copolymer: ABS copolymer with an average particle size of butadiene rubber of 300 nm (60 wt% of 1,3-butadiene monomer units, 30 wt% of styrene monomer units, and 10 wt% of acrylonitrile monomer units)

[0146]

[0147] (2) Second graft copolymer: ASA copolymer having an average particle size of 500 nm of butyl acrylate rubbery polymer (50 wt% butyl acrylate monomer units, 35 wt% styrene monomer units, 15 wt% acrylonitrile monomer units)

[0148]

[0149] (3) Matrix copolymer: SAN resin manufactured by bulk polymerization and having a weight-average molecular weight of 100,000 g / mol or more and 120,000 g / mol or less (70-80 wt% styrene monomer units, 20-30 wt% acrylonitrile monomer units)

[0150]

[0151] (4) Matting agent: A cross-linked SAN copolymer prepared by the following method was used as a matting agent.

[0152] 120 parts by weight of ion-exchanged water, 75 parts by weight of styrene, 25 parts by weight of acrylonitrile, 0.3 parts by weight of 1-1'azobis(cyclohexane-1-carbonitrile), 0.1 parts by weight of t-dodecyl mercaptan, and 0.5 parts by weight of divinylmethylsilane were added, and the temperature of the reactor was raised to 70°C. Then, 0.25 parts by weight of allyl methacrylate were added to the reactor three times at 1-hour intervals, and polymerization was carried out for a total of 5 hours. Afterward, the mixture was washed, dehydrated, and dried to produce a cross-linked SAN copolymer in powder form.

[0153]

[0154] (5) Chemical resistance improver: Manufactured by Dow, Product name: Acrylate Copolymer (ELVALOY TM AC 1224)

[0155]

[0156] (6) Appearance quality improver: Non-crosslinked styrene-acrylonitrile copolymer with weight-average molecular weight: 5,000,000 g / mol (Manufactured by Zibo Huaxing Additives, Product name: ZB-869)

[0157]

[0158] The graft copolymer, matrix copolymer, matting agent, and appearance quality improving agent having the compositions described in Tables 1 and 2 below were added, and pellets were prepared by melt-mixing at 230°C.

[0159]

[0160] Experimental Example

[0161] The resin composition pellets prepared in the above examples and comparative examples were injected at a temperature of 220°C, and their physical properties were measured in the following manner.

[0162]

[0163] * Melt index (220℃, 10kg): Values ​​measured according to the ASTM D1238 method are listed in Tables 1 and 2 below.

[0164]

[0165] * Impact strength (1 / 8", kg·cm / cm): Values ​​measured according to the ASTM D256 method are listed in Tables 1 and 2 below.

[0166]

[0167] * Glossiness (60°): Values ​​measured according to the ASTM D2457 method for injection specimens produced at a molding temperature of 240°C using resin composition pellets prepared in the examples and comparative examples are listed in Tables 1 and 2 below. In the present invention, a value of 20 or less was evaluated as having low glossiness.

[0168]

[0169] * Chemical resistance: After placing gauze (15 mm x 50 mm) on the surface of each tensile specimen (ASTM D638 standard) of the example and comparative example fixed to a 1% strain jig, 1 ml of laundry detergent (Nanox) was applied, and the occurrence of a crack was observed inside the walk-in larynx. The time taken for a crack of 3 mm or larger to occur was measured and recorded in Tables 1 and 2 below. A longer time taken for a crack to occur indicates superior chemical resistance. In the present invention, a time of 10 hours or more was evaluated as having excellent chemical resistance.

[0170]

[0171] * Appearance quality: Injection specimens of 10 cm × 10 cm were produced by injecting the resin composition pellets prepared in the above examples and comparative examples at an injection temperature of 240°C, and when observed visually, if three or fewer foreign substances with a size of 100 μm or more were observed in the injection specimen, it was evaluated as ◎ (very good); if there were 4 or more foreign substances and 10 or fewer, it was evaluated as ○ (good); and if there were more than 10 foreign substances, it was evaluated as X (poor).

[0172]

[0173] Example 1 2 3 4 5 First graft copolymer (parts by weight) 30 3 0 4 0 - 20 Second graft copolymer (parts by weight) --- 4 0 1 5 Matrix copolymer (parts by weight) 70 70 60 60 6 5 Matte-reducing agent (parts by weight) 10 20 20 10 10 Chemical resistance improver (parts by weight) 55 5 5 5 Appearance quality improver (parts by weight) 11 1 1 1 Melt index (g / 10 min) 35 27 24 25 2 9 Impact strength (1 / 8``, kg·cm / cm) 18 14 16 2 1 2 0 Gloss (60°) 13 9 8 1 2 1 1 Chemical resistance (hr) 10 10 10 13 1 2 Appearance quality ◎○○◎◎

[0174] Comparative Example 1 2345678 1st Graft Copolymer (parts by weight) 960 30 30 30 30 30 2nd Graft Copolymer (parts by weight) -------- Matrix Copolymer (parts by weight) 91 40 70 70 70 70 70 Matte Agent (parts by weight) 10 100 0.545 10 10 20 20 Chemical Resistance Improver (parts by weight) 55 50 51 5 55 Appearance Quality Improver (parts by weight) 11 11 11 -15 Melt Index (g / 10 min) 50 13 42 93 22 52 73 Impact Strength (1 / 8``, kg·cm / cm) 34 52 68 21 13 12 13 Gloss (60°) 14 88 02 12 80 98 Chemical Resistance (hr) 10 10 10 10 215 10 12 Appearance Quality ◎◎◎X◎○X◎

[0175] Referring to Tables 1 and 2 above, it was confirmed that Examples 1 to 5, which contain graft copolymer, matrix copolymer, matting agent, chemical resistance improver, and appearance quality improver in desirable amounts, exhibit low gloss while simultaneously having excellent chemical resistance and surface properties.

[0176]

[0177] In the case of Comparative Example 1, where the content of the graft copolymer was below the desirable range, it was confirmed that the impact strength decreased compared to Examples 1 to 5.

[0178]

[0179] In the case of Comparative Example 2, where the content of the graft copolymer exceeds the desirable range, it was confirmed that the melt index decreased compared to Examples 1 to 5.

[0180]

[0181] In the case of Comparative Example 3, which contains a matting agent below a desirable range, it was confirmed that a low gloss level could not be achieved compared to Examples 1 to 5.

[0182]

[0183] In the case of Comparative Example 4, which contains a matting agent in an amount less than the desirable range, it was confirmed that the melt index, impact strength, and surface appearance were inferior compared to Examples 1 to 5.

[0184]

[0185] In the case of Comparative Example 5, which contains a chemical resistance improving agent below a desirable range, it was confirmed that the chemical resistance was reduced compared to Examples 1 to 5.

[0186]

[0187] In the case of Comparative Example 6, which contains a chemical resistance improver in excess of the desirable range, it was confirmed that the glossiness was significantly higher compared to Examples 1 to 5.

[0188]

[0189] In the case of Comparative Example 7, which contains an appearance quality improving agent below a desirable range, it was confirmed that the appearance quality deteriorated compared to Examples 1 to 5.

[0190]

[0191] In the case of Comparative Example 8, which contains an appearance quality improver in excess of the desirable range, it was confirmed that the melt index was lowered compared to Examples 1 to 4.

Claims

1. A graft copolymer comprising a rubbery polymer, an aromatic vinyl monomer unit, and a vinyl cyanide monomer unit; A matrix copolymer comprising aromatic vinyl monomer units and vinyl cyanide monomer units; A matting agent comprising an aromatic vinyl-vinyl cyanide crosslinked copolymer; Chemical resistance improver; and Includes an appearance quality improver, Based on 100 parts by weight of the total sum of the graft copolymer and matrix copolymer, The above matting agent is included in an amount of 1 part by weight or more and 40 parts by weight or less, and The above chemical resistance improving agent is included in an amount of 1 part by weight or more and 12 parts by weight or less, A resin composition comprising 0.5 parts by weight or more and 12 parts by weight or less of the above-mentioned appearance quality improving agent.

2. In Paragraph 1, Based on 100 parts by weight of the total sum of the graft copolymer and matrix copolymer, A resin composition comprising 5 parts by weight or more and 25 parts by weight or less of the above matting agent.

3. In Paragraph 1, Based on 100 parts by weight of the total sum of the graft copolymer and matrix copolymer, A resin composition comprising 2 parts by weight or more and 10 parts by weight or less of the above chemical resistance improving agent.

4. In Paragraph 1, Based on 100 parts by weight of the total sum of the graft copolymer and matrix copolymer, A resin composition comprising 1 part by weight or more and 10 parts by weight or less of the above-mentioned appearance quality improving agent.

5. In Paragraph 1, The above aromatic vinyl-vinyl cyanide crosslinked copolymer is, Aromatic vinyl monomer unit; Vinyl cyanide monomer units; and A resin composition comprising a crosslinked portion formed from a crosslinking functional compound.

6. In Paragraph 1, The above chemical resistance improving agent is a resin composition comprising a polymer containing crystalline units.

7. In Paragraph 6, A resin composition comprising a polymer containing the above-mentioned crystalline unit in an amount of 20% by weight or more and 80% by weight or less of the above-mentioned crystalline unit.

8. In Paragraph 1, A resin composition in which the chemical resistance modifier is one or more selected from the group consisting of ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, and polyester-based thermoplastic elastomer (TPEE) containing crystalline units.

9. In Paragraph 1, The above-mentioned appearance quality improving agent is a resin composition comprising one or more selected from the group consisting of aromatic vinyl-vinyl cyanide copolymers and acrylic copolymers.

10. In Paragraph 9, The above appearance quality improver is a resin composition having a weight-average molecular weight of 1,000,000 g / mol or more.

11. In Paragraph 1, A resin composition having a glossiness (60°) of 20 or less as measured according to the ASTM D2457 method.

12. In Paragraph 1, A resin composition having a melt index (220°C, 10kg) of 20 g / 10min or higher as measured according to the ASTM D1238 method.

13. In Paragraph 1, The above graft copolymer is, A first graft copolymer comprising a conjugated diene polymer, an aromatic vinyl monomer unit, and a vinyl cyanide monomer unit; and / or A resin composition comprising a second graft copolymer comprising an acrylic polymer, an aromatic vinyl monomer unit, and a vinyl cyanide monomer unit.

14. In Paragraph 1, With respect to the total of the above matting agent, chemical resistance improver, and appearance quality improver, The above matting agent is included in an amount of 30% by weight or more and 83% by weight or less, and The above chemical resistance improving agent is included in an amount of 10% by weight or more and 45% by weight or less, A resin composition comprising the above-mentioned appearance quality improving agent in an amount of 2% by weight or more and 25% by weight or less.