Resin composition

Abstract

A resin composition according to one embodiment of the present invention comprises: a graft copolymer comprising a rubbery polymer, an aromatic vinyl-based monomer unit and a vinyl cyanide-based monomer unit; a matrix copolymer comprising an aromatic vinyl-based monomer unit and a vinyl cyanide-based monomer unit; a matting agent comprising an aromatic vinyl-vinyl cyanide-based cross-linked copolymer; and an exterior quality improver, wherein on the basis of 100 parts by weight in total of the graft copolymer, the matrix copolymer and the matting agent, the matting agent is included in an amount of 1-25 parts by weight, and the exterior quality improver is included in an amount of 0.1-5 parts by weight, and the ratio (W1:W2) of the amount (W1) of the exterior quality improver to the amount (W2) of the matting agent can be 1:3 to 1:30.

Description

Resin composition

[0001] [Cross-reference with related applications]

[0002] This application claims the benefit of priority based on Korean patent application 10-2024-0181991 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 having a uniform surface of an injection-molded product.

[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, when a matting agent is added to the material itself to produce a matting effect, fluidity is reduced, resulting in a high defect rate during injection molding of large home appliances. Additionally, due to differences in compatibility between the base resin and the matting agent, the matting agent clumps, causing the surface of the injection-molded product to be uneven and resulting in a poor appearance.

[0008] [Prior Art Literature]

[0009] [Patent Literature]

[0010] (Patent Document 0001) CN 117866406 A

[0011] The problem to be solved by the present invention is to provide a resin composition that satisfies excellent appearance quality and melt index while having low gloss.

[0012] (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; and an appearance quality improving agent, wherein, for every 100 parts by weight of the total of the graft copolymer, the matrix copolymer and the matting agent, the matting agent is included in an amount of 1 part by weight or more and 25 parts by weight or less, and the appearance quality improving agent is included in an amount of 0.1 part by weight or more and 5 parts by weight or less, and the ratio (W1:W2) of the content of the appearance quality improving agent (W1) and the content of the matting agent (W2) is 1:3 or more and 1:30 or less.

[0013] (2) The present invention provides a resin composition according to (1), wherein the weight-average molecular weight of the matrix copolymer is 80,000 g / mol or more and 160,000 g / mol or less.

[0014] (3) The present invention provides a resin composition according to (1) or (2) wherein, for every 100 parts by weight of the total of the graft copolymer, matrix copolymer, and matting agent, the graft copolymer is included in an amount of 15 parts by weight or more and 50 parts by weight or less, and the matrix copolymer is included in an amount of 40 parts by weight or more and 75 parts by weight or less.

[0015] (4) The present invention provides a resin composition in which, in any one of (1) to (3), 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.

[0016] (5) The present invention provides a resin composition in which, in any one of (1) to (4), the appearance quality improving agent is one or more selected from the group consisting of aromatic vinyl-vinyl cyanide copolymers and acrylic copolymers.

[0017] (6) The present invention provides a resin composition in which, in any one of (1) to (5), the appearance quality improving agent has a weight-average molecular weight of 1,000,000 g / mol or more.

[0018] (7) The present invention provides a resin composition in which, in any one of (1) to (6) above, the glossiness (60°) measured according to the ASTM D2457 method is 20 or less.

[0019] (8) The present invention provides a resin composition in which, in any one of (1) to (7) above, the melt index (220°C, 10kg) measured according to the ASTM D1238 method is 20 g / 10min or higher.

[0020] A resin composition according to one embodiment of the present invention has low gloss while satisfying excellent appearance quality and melt index.

[0021] Hereinafter, the present invention will be described in more detail to aid in understanding the invention.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] 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.

[0026]

[0027] <Resin Composition>

[0028] The present invention provides a resin composition.

[0029] A resin composition according to one embodiment of the present invention comprises at least: 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; and an appearance quality improving agent, wherein, for every 100 parts by weight of the total of the graft copolymer, the matrix copolymer, and the matting agent, the matting agent is included in an amount of 1 part by weight or more and 25 parts by weight or less, and the appearance quality improving agent is included in an amount of 0.1 parts by weight or more and 5 parts by weight or less, and the ratio (W1:W2) of the content of the appearance quality improving agent (W1) and the content of the matting agent (W2) must be 1:3 or more and 1:30 or less.

[0030]

[0031] Generally, cross-linked copolymers can effectively impart low gloss to resin compositions by inducing diffuse reflection that scatters incident light. However, 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 was a problem of high defect rates during injection molding of large home appliances with complex structures, and the matting agent clumping together, causing the surface of the injection-molded product to be uneven and degrading the appearance quality. The inventors discovered that by adjusting the input amounts of the matting agent and the appearance quality improving agent to appropriate levels, it is possible to satisfy both excellent appearance quality and melt index while maintaining low gloss, and thus completed the present invention.

[0032]

[0033] A resin composition according to one embodiment of the present invention includes a preferred amount of a matting agent and an appearance quality improving agent, thereby enabling excellent appearance quality and a melt index while having low gloss.

[0034] 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.

[0035] 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.

[0036] In one embodiment of the present invention, when an injection molded specimen of size 10 cm × 10 cm is prepared 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.

[0037]

[0038] Hereinafter, each component constituting the resin composition according to one embodiment of the present invention will be described.

[0039]

[0040] Graft copolymer

[0041] A resin composition according to one embodiment of the present invention may include a graft copolymer.

[0042] According to one embodiment of the present invention, the graft copolymer serves to provide excellent moldability and impact resistance to the resin composition, and the graft copolymer can generally be a commercially available resin and can be obtained through a commercially available method.

[0043] According to one embodiment of the present invention, the graft copolymer comprises a rubbery polymer, an aromatic vinyl monomer unit, and a vinyl cyanide monomer unit, and as a specific example, it may be an acrylonitrile-butadiene-styrene copolymer (ABS) or an acrylonitrile-styrene-acrylonitrile copolymer (ASA).

[0044]

[0045] According to one embodiment of the present invention, the graft copolymer may have a core-shell structure comprising a core comprising a rubbery polymer; and a shell surrounding the core and comprising an aromatic vinyl monomer unit and a vinyl cyanide monomer unit.

[0046]

[0047] According to one embodiment of the present invention, the rubbery polymer of the graft copolymer may be a conjugated diene polymer comprising conjugated diene monomer units, and the conjugated diene monomer for forming the conjugated diene monomer units 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.

[0048] According to one embodiment of the present invention, the rubbery polymer of the graft copolymer may be an acrylic polymer comprising acrylic monomer units, and the acrylic monomer for forming the acrylic monomer units of the acrylic polymer is C4 to C 10 It 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.

[0049]

[0050] According to one embodiment of the present invention, the aromatic vinyl monomer for forming the aromatic vinyl monomer of the 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.

[0051] 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.

[0052]

[0053] According to one embodiment of the present invention, the vinyl cyanide monomer for forming the vinyl cyanide monomer unit of the graft 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.

[0054] 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.

[0055]

[0056] According to one embodiment of the present invention, the 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.

[0057] Additionally, the 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 copolymer may be superior.

[0058]

[0059] A resin composition according to one embodiment of the present invention may comprise 15 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, the matrix copolymer, and the matting agent. Specifically, it may comprise 16 parts by weight or more, 17 parts by weight or more, 18 parts by weight or more, 19 parts by weight or more, or 20 parts by weight or more, and may also comprise 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.

[0060] According to one embodiment of the present invention, the graft copolymer may comprise 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.

[0061] 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 1:0.2 or higher and 1:2 or lower. Specifically, it may be 1:0.25 or higher, 1:0.3 or higher, 1:0.35 or higher, 1:0.4 or higher, or 1:0.5 or higher, and may also be 1:1.8 or lower, 1:1.6 or lower, 1:1.4 or lower, 1:1.2 or lower, or 1:1 or lower. When the above-described ranges are satisfied, the mechanical properties of the resin composition may be further improved.

[0062]

[0063] Matrix copolymer

[0064] A resin composition according to one embodiment of the present invention may include a matrix copolymer.

[0065] 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.

[0066]

[0067] 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.

[0068] 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.

[0069]

[0070] 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.

[0071] 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.

[0072] 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.

[0073]

[0074] A resin composition according to one embodiment of the present invention may include the matrix copolymer in an amount of 40 parts by weight or more and 75 parts by weight or less, based on 100 parts by weight of the total sum of the graft copolymer, the matrix copolymer, and the matting agent. Specifically, it may include 42 parts by weight or more, 44 parts by weight or more, 46 parts by weight or more, 48 parts by weight or more, or 50 parts by weight or more, and may also include 74 parts by weight or less, 73 parts by weight or less, 72 parts by weight or less, 71 parts by weight or less, or 70 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.

[0075]

[0076] Matting agent

[0077] 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.

[0078]

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083]

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088]

[0089] 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.

[0090]

[0091] 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 25 parts by weight or less, based on 100 parts by weight of the total sum of the graft copolymer, the matrix copolymer, and the matting agent. 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 24 parts by weight or less, 23 parts by weight or less, 22 parts by weight or less, 21 parts by weight or less, or 20 parts by weight or less.

[0092] 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 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 appearance quality may deteriorate.

[0093]

[0094] Appearance quality improver

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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.

[0101]

[0102] 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.

[0103] 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.

[0104] 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.

[0105]

[0106] 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 quality of the resin composition may be further improved.

[0107] A resin composition according to one embodiment of the present invention may contain an appearance quality improving agent in an amount of 0.1 parts by weight or more and 5 parts by weight or less, based on 100 parts by weight of the total sum of the graft copolymer, the matrix copolymer, and the matting agent. Specifically, it may contain an amount of 0.2 parts by weight or more, 0.4 parts by weight or more, 0.6 parts by weight or more, 0.8 parts by weight or more, or 1 part by weight or more, and may also contain an amount of 4.8 parts by weight or less, 4.6 parts by weight or less, 4.4 parts by weight or less, 4.2 parts by weight or less, or 4 parts by weight or less.

[0108]

[0109] 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.

[0110]

[0111] According to one embodiment of the present invention, the ratio (W1:W2) of the content of the appearance quality improving agent (W1) and the content of the matting agent (W2) may be 1:3 or higher and 1:30 or lower. Specifically, the ratio (W1:W2) of the content of the appearance quality improving agent (W1) and the content of the matting agent (W2) may be 1:3.2 or higher, 1:3.4 or higher, 1:3.6 or higher, 1:3.8 or higher, 1:4 or higher, 1:4.2 or higher, 1:4.4 or higher, 1:4.6 or higher, or 1:4.8 or higher. Additionally, it may be 1:29.5 or lower, 1:29 or lower, 1:28.5 or lower, 1:28 or lower, 1:27.5 or lower, 1:27 or lower, 1:26.5 or lower, 1:26 or lower, 1:25.5 or lower, 1:25 or lower, or 1:24.5. It may be less than or equal to 1:24. When the above-mentioned range is satisfied, low glossiness can be achieved without deterioration of other physical properties of the resin composition, while maintaining excellent appearance quality.

[0112]

[0113] Other additives

[0114] A resin composition according to one embodiment of the present invention may further include additives.

[0115] 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.

[0116] 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.

[0117]

[0118] Molded product

[0119] The present invention provides a molded article formed from the resin composition.

[0120] 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.

[0121]

[0122] 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.

[0123]

[0124] Examples and Comparative Examples

[0125] The compounds used in the examples and comparative examples are as follows.

[0126]

[0127] (1-1) Graft copolymer (A-1): ABS copolymer with an average butadiene rubber particle size of 300 nm (60 wt% 1,3-butadiene monomer units, 30 wt% styrene monomer units, 10 wt% acrylonitrile monomer units)

[0128]

[0129] (1-2) Graft copolymer (A-2): ASA copolymer of acrylic rubber with an average particle size of 500 nm (50 wt% butacrylate monomer units, 35 wt% styrene monomer units, 15 wt% acrylonitrile monomer units)

[0130]

[0131] (2) Matrix copolymer: Styrene-acrylonitrile copolymer with a weight-average molecular weight of 110,000 g / mol (manufactured by LG Chem, product name 83SF)

[0132]

[0133] (3) Matting agent: A cross-linked SAN copolymer prepared by the following method was used as a matting agent.

[0134] 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.

[0135]

[0136] (4) Appearance quality improver: Styrene-acrylonitrile copolymer with a weight-average molecular weight of 5,000,000 g / mol (manufactured by Zibo Huaxing, product name ZB869)

[0137]

[0138] The above graft copolymer, matrix copolymer, matting agent, and appearance quality improver were fed into an extruder with the compositions described in Tables 1 and 2 below, and melt-mixed at 230°C to produce pellets.

[0139]

[0140] Experimental Example 1

[0141] The resin composition pellets prepared in the above examples and comparative examples were injected, and their physical properties were measured by the following method.

[0142]

[0143] * Melt index (220℃, 10kg): Values ​​measured according to the ASTM D1238 method are listed in Tables 1 and 2 below.

[0144]

[0145] * Impact strength (1 / 4", Notched Izod): Values ​​measured according to the ASTM D256 method are listed in Tables 1 and 2 below.

[0146]

[0147] * Tensile strength: Values ​​measured according to ASTM D638 are listed in Tables 1 and 2 below.

[0148]

[0149] * 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.

[0150]

[0151] * Appearance quality: When the resin composition pellets prepared in the examples and comparative examples were molded into injection specimens of size 10 cm × 10 cm at a molding temperature of 240°C and observed visually, the quality was evaluated as ○ (Excellent) when three or fewer foreign substances with a size of 100 μm or more were observed in the injection specimen, as △ (Average) when four or more and ten or fewer foreign substances were observed, and as X (Poor) when more than ten foreign substances were observed.

[0152]

[0153] Example 1 2 3 4 5 6 7 Graft copolymer (A-1) (parts by weight) 20 30 40 30 30 20 - Graft copolymer (A-2) (parts by weight) ----- 10 3 0 Matrix copolymer (parts by weight) 70 60 50 65 50 60 60 Matting agent (parts by weight) 10 10 10 52 10 10 Appearance quality improver (parts by weight) 11 11 11 1 Melt index (g / 10 min) 40 37 33 43 30 35 3 2 Impact strength (1 / 4``, kg·cm / cm) 12 15 19 17 11 14 1 3 Tensile strength (kg / cm 2 )520490450510470480470Gloss (60°)8761251012Appearance Quality○○○○○○○

[0154] Comparative Example 1 2 3 4 5 6 Graft copolymer (A-1) (parts by weight) 30 30 30 30 30 30 Matrix copolymer (parts by weight) 70 40 60 60 68 50 Matting agent (parts by weight) -30 10 10 220 Appearance quality improver (parts by weight) 11 -8 50.5 Melt index (g / 10 min) 46 18 40 19 20 3 4 Impact strength (1 / 4``, kg·cm / cm) 20 8 14 19 18 7 Tensile strength (kg / cm 2 )520450490510500470Gloss (60°)95448336Appearance Quality○△X○○X

[0155] Referring to Tables 1 and 2 above, it was confirmed that Examples 1 to 7, which contain the composition of the resin composition in a desirable amount, satisfy excellent fluidity, impact strength, tensile strength, and appearance quality while exhibiting low gloss.

[0156] In the case of Comparative Example 1, which does not contain a matting agent, it was confirmed that low glossiness was not exhibited compared to Examples 1 to 7.

[0157] In the case of Comparative Example 2, which contains a matting agent in excess of the desired content range, it was confirmed that the melt index, impact strength, and appearance quality were reduced compared to Examples 1 to 7.

[0158] In the case of Comparative Example 3, which does not contain an appearance quality improving agent, it was confirmed that the appearance quality was degraded compared to Examples 1 to 7.

[0159] In the case of Comparative Example 4, which contains an appearance quality improver in excess of the desired content range, it was confirmed that the melt index was lower compared to Examples 1 to 7.

[0160] In the case of Comparative Example 5, which contains appearance quality improving agent and matting agent in desirable amounts respectively, but in which the ratio of their contents is less than the desirable range, it was confirmed that the melt index and glossiness were reduced compared to Examples 1 to 7.

[0161] In the case of Comparative Example 6, which contains appearance quality improving agent and matting agent in desirable amounts respectively but has a ratio of their contents exceeding the desirable range, it was confirmed that the impact strength and appearance quality were reduced compared to Examples 1 to 7.

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; and Includes an appearance quality improver, Based on 100 parts by weight of the total sum of the above graft copolymer, matrix copolymer, and matting agent, The above matting agent is included in an amount of 1 part by weight or more and 25 parts by weight or less, and The above-mentioned appearance quality improver is included in an amount of 0.1 parts by weight or more and 5 parts by weight or less, and A resin composition having a ratio (W1:W2) of the content of the appearance quality improving agent (W1) and the content of the matting agent (W2) of the above-mentioned appearance quality improving agent of 1:3 or more and 1:30 or less.

2. In Paragraph 1, A resin composition having a weight-average molecular weight of the matrix copolymer of the above-mentioned amount of 80,000 g / mol or more and 160,000 g / mol or less.

3. In Paragraph 1, Based on 100 parts by weight of the total sum of the above graft copolymer, matrix copolymer, and matting agent, The above graft copolymer is included in an amount of 15 parts by weight or more and 50 parts by weight or less, and A resin composition comprising 40 parts by weight or more and 75 parts by weight or less of the above matrix copolymer.

4. 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.

5. 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.

6. In Paragraph 5, The above appearance quality improver is a resin composition having a weight-average molecular weight of 1,000,000 g / mol or more.

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

8. 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.