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-based monomer unit, and a vinylcyan-based monomer unit; a matrix copolymer including an aromatic vinyl-based monomer unit and a vinylcyan-based monomer unit; a matting agent including a crosslinked copolymer; and an appearance quality improving agent, wherein an insoluble content (X) calculated by Equation 1 below may be 0.2-3%. [Equation 1] In Equation 1, X is the insoluble content (%), A is the weight (g) of the insoluble product obtained by dissolving the resin composition in a tetrahydrofuran (THF) solution, filtering same through 325 mesh, and drying the remaining residue, and B is the weight (g) of the resin composition.

Description

Resin composition

[0001] [Cross-reference with related applications]

[0002] This application claims the benefit of priority based on Korean Patent Application 10-2024-0181992 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 1) CN 117866406 A

[0011] The problem to be solved by the present invention is to provide a resin composition that has low gloss while satisfying excellent appearance quality.

[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 a crosslinking copolymer; and an appearance quality improving agent, wherein the insoluble content (X) calculated by the following mathematical formula 1 is 0.2% or more and 3% or less.

[0013] [Mathematical Formula 1]

[0014]

[0015] In the above mathematical formula 1,

[0016] X is the insoluble matter content (%), and

[0017] A is the weight (g) of the insoluble material obtained by dissolving the resin composition in a tetrahydrofuran (THF) solvent, filtering it through a 325 mesh, and drying the remaining residue.

[0018] B is the weight (g) of the resin composition before dissolving in the tetrahydrofuran solvent.

[0019]

[0020] (2) The present invention provides a resin composition according to (1), wherein the insoluble content is 0.5% by weight or more and 2% by weight or less.

[0021] (3) The present invention provides a resin composition in which, in (1) or (2), the matting agent is included in an amount of 0.5 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the total amount of the graft copolymer and the matrix copolymer.

[0022] (4) The present invention provides a resin composition in which, in any one of (1) to (3) above, the crosslinking copolymer is one or more selected from the group consisting of acrylic crosslinking copolymers and aromatic vinyl-vinyl cyanide crosslinking copolymers.

[0023] (5) The present invention provides a resin composition in which, in any one of (1) to (4), the appearance quality improving agent is included in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the graft copolymer and the matrix copolymer.

[0024] (6) The present invention provides a resin composition in which, in any one of (1) to (5), the appearance quality improving agent is one or more selected from the group consisting of aromatic vinyl-vinyl cyanide copolymers and acrylic copolymers.

[0025] (7) The present invention provides a resin composition in which, in any one of (1) to (6), the appearance quality improving agent has a weight-average molecular weight of 1,000,000 g / mol or more.

[0026] (8) The present invention provides a resin composition in which, in any one of (1) to (7), the gloss (60°) measured according to the ASTM D2457 method is 20 or less.

[0027] A resin composition according to one embodiment of the present invention satisfies excellent appearance quality while having low gloss.

[0028] Hereinafter, the present invention will be described in more detail to aid in understanding the invention.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033]

[0034] <Resin Composition>

[0035] The present invention provides a resin composition.

[0036] 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 a crosslinking copolymer; and an appearance quality improving agent, wherein the insoluble content (X) calculated by the following mathematical formula 1 is 0.2% or more and 3% or less.

[0037] [Mathematical Formula 1]

[0038]

[0039] In the above mathematical formula 1,

[0040] X is the insoluble matter content (%), and

[0041] A is the weight (g) of the insoluble material obtained by dissolving the resin composition in a tetrahydrofuran (THF) solvent, filtering it through a 325 mesh, and drying the remaining residue.

[0042] B is the weight (g) of the resin composition before dissolving in the tetrahydrofuran solvent.

[0043]

[0044] 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, 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 an appropriate amount to satisfy Equation 1 above, it is possible to achieve excellent appearance quality while maintaining low gloss, and thus completed the present invention.

[0045]

[0046] The insoluble content represented by the above mathematical formula 1 of the resin composition according to one embodiment of the present invention is derived from the crosslinked portion (formed from a crosslinking functional compound) of the crosslinked copolymer included in the matting agent, and may be proportional to the ratio of the crosslinked portion present in the resin composition.

[0047] A resin composition according to one embodiment of the present invention may have an insoluble content represented by the above mathematical formula 1 of 0.2% or more and 3% or less, and as specific examples, may be 0.3% or more, 0.4% or more, 0.5% or more, or 0.6% or more, and may also be 2.8% or less, 2.6% or less, 2.4% or less, or 2.2% or less. When the above range is satisfied, the resin composition can satisfy excellent appearance quality while having low gloss.

[0048] If the above-mentioned insoluble content is less than the range described above, it may be that a sufficient amount of matting agent has not been added to the resin composition or an excessive amount of appearance quality improving agent has been added, and thus the low gloss of the resin composition may not be expressed. In addition, if the above-mentioned insoluble content exceeds the range described above, it may be that an excessive amount of matting agent has been added to the resin composition or a sufficient amount of appearance quality improving agent has not been added, and thus the appearance characteristics of the resin composition may be degraded.

[0049]

[0050] A resin composition according to one embodiment of the present invention satisfies the above mathematical formula 1, thereby enabling excellent appearance characteristics while having low gloss.

[0051] 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.

[0052] In one embodiment of the present invention, when an injection molded specimen of 10 cm × 10 cm is prepared and observed visually, five 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 characteristics are evaluated as excellent.

[0053]

[0054] Graft copolymer

[0055] A resin composition according to one embodiment of the present invention may include a graft copolymer.

[0056] 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.

[0057] 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).

[0058] 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.

[0059]

[0060] 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.

[0061] 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 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.

[0062]

[0063] 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.

[0064] 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 input amount of 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.

[0065]

[0066] 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.

[0067] 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 100 parts by weight of the total input amount of 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.

[0068]

[0069] 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.

[0070] 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.

[0071]

[0072] A resin composition according to one embodiment of the present invention may contain the graft copolymer in an amount of 10% by weight or more and 50% by weight or less with respect to the total weight of the graft copolymer and the matrix copolymer. 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 20% by weight or more, and may also contain 48% by weight or less, 46% by weight or less, 44% by weight or less, 42% by weight or less, or 40% by weight or less. When the above-described ranges are satisfied, the physical properties of the resin composition may be improved.

[0073] 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.

[0074] 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.

[0075]

[0076] Matrix copolymer

[0077] A resin composition according to one embodiment of the present invention may include a matrix copolymer.

[0078] 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.

[0079]

[0080] 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.

[0081] 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 input amount of 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.

[0082]

[0083] 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.

[0084] 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 100 parts by weight of the total input amount of 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.

[0085]

[0086] A resin composition according to one embodiment of the present invention may contain the matrix copolymer in an amount of 50% by weight or more and 90% by weight or less with respect to the total weight of the graft copolymer and the matrix copolymer. Specifically, it may contain 55% by weight or more, 60% by weight or more, 65% by weight or more, 70% by weight or more, or 75% by weight or more, and may also contain 88% by weight or less, 86% by weight or less, 84% by weight or less, 82% by weight or less, or 80% by weight or less. When the above-described ranges are satisfied, the physical properties of the resin composition may be improved.

[0087]

[0088] Matting agent

[0089] A matting agent according to one embodiment of the present invention suppresses surface gloss by inducing light scattering through the formation of fine irregularities on the surface of a product during injection molding, and can generally be obtained through commercially available resins or commercially available methods.

[0090] According to one embodiment of the present invention, the matting agent may include a crosslinking copolymer, and the crosslinking copolymer may include a crosslinking portion formed from a crosslinking functional compound.

[0091] According to one embodiment of the present invention, the crosslinking functional compound for forming the crosslinking portion may include functional groups such as siloxane groups, vinyl groups, or acrylic groups, and in one crosslinking functional compound, two or more, preferably three or more, of the functional groups may be present. Specifically, the crosslinking functional compound may be a silicone-based compound or a polyene-based compound.

[0092] 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, may be 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, and allyl(meth)acrylate may be preferably used.

[0093] 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.

[0094] 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.

[0095]

[0096] According to one embodiment of the present invention, the crosslinking copolymer may be one or more selected from the group consisting of acrylic crosslinking copolymers and aromatic vinyl-vinyl cyanide crosslinking copolymers.

[0097] In the case where the crosslinked copolymer according to one embodiment of the present invention is an acrylic crosslinked copolymer, it may include a crosslinked portion formed from an alkyl acrylate monomer unit, an alkyl methacrylate monomer unit, and a crosslinking functional compound. Since the crosslinked portion is as described above, a detailed description thereof will be omitted below.

[0098] According to one embodiment of the present invention, the alkyl acrylate monomer for forming the alkyl acrylate monomer unit of the acrylic crosslinked copolymer may be linear, branched, or cyclic having 1 to 18 carbon atoms in 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.

[0099] According to one embodiment of the present invention, the alkyl methacrylate monomer for forming the alkyl methacrylate monomer unit of the acrylic crosslinked 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.

[0100] In the case where the crosslinked copolymer according to one embodiment of the present invention is an aromatic vinyl-vinylcyanide crosslinked copolymer, it may comprise an aromatic vinyl monomer unit; a vinylcyanide monomer unit; and a crosslinked portion formed from a crosslinking functional compound. Since the crosslinked portion is as described above, a detailed description thereof will be omitted below.

[0101] 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.

[0102] 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.

[0103]

[0104] According to one embodiment of the present invention, the matting agent may be included in an amount of 0.1 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the total amount of the graft copolymer and the matrix copolymer, and as a specific example, may be included in 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 be included in an amount of 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.

[0105] A resin composition according to one embodiment of the present invention satisfies Equation 1 by including the matting agent in the range described above, and can satisfy superior appearance quality and melt index while having low gloss.

[0106]

[0107] Appearance quality improver

[0108] 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.

[0109] 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.

[0110] 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.

[0111] 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.

[0112] 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.

[0113] 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.

[0114]

[0115] 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.

[0116] 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.

[0117] 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.

[0118]

[0119] 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.

[0120] A resin composition according to one embodiment of the present invention may include an appearance quality improving agent in an amount of 0.1 parts by weight or more and 10 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 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 include an amount of 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.

[0121] A resin composition according to one embodiment of the present invention satisfies Equation 1 by including the appearance quality improving agent in the range described above, and can satisfy superior appearance quality and melt index while having low gloss.

[0122]

[0123] Other additives

[0124] A resin composition according to one embodiment of the present invention may further include additives.

[0125] 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.

[0126] 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.

[0127]

[0128] Molded product

[0129] The present invention provides a molded article formed from the resin composition.

[0130] 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.

[0131]

[0132] 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.

[0133]

[0134] 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.

[0135]

[0136] Examples and Comparative Examples

[0137] The compounds used in the examples and comparative examples are as follows.

[0138]

[0139] (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)

[0140]

[0141] (1-2) Graft copolymer (A-2): ASA copolymer of acrylic rubber with an average particle size of 400 nm (50 wt% butacrylate monomer units, 35 wt% styrene monomer units, 15 wt% acrylonitrile monomer units)

[0142]

[0143] (2) 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)

[0144]

[0145] (3) Matting agent (C-1): A cross-linked SAN copolymer prepared by the following method was used as a matting agent.

[0146] 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.

[0147]

[0148] (4) Matting agent (C-2): Cross-linked PMMA bead with a diameter of 20 µm (manufactured by ASP, product name: MH-20FD)

[0149]

[0150] (4) Appearance quality improver (D-1): Non-crosslinked styrene-acrylonitrile copolymer with weight-average molecular weight: 5,000,000 g / mol (Manufactured by Zibo Huaxing Additives, Product name: ZB-869)

[0151]

[0152] (5) Appearance quality improver (D-2): Non-crosslinked acrylic copolymer with weight-average molecular weight: 1,000,000 g / mol (15 wt% butyl acrylate and 85 wt% methyl methacrylate; manufactured by LG Chem, product name: PA912)

[0153]

[0154] 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.

[0155]

[0156] Experimental Example 1

[0157] * Insoluble matter content (%): 1 g of each pellet prepared in the above examples and comparative examples was sufficiently dissolved by stirring in a 40 g solution of tetrahydrofuran (THF) for 24 hours, then filtered through a 325 mesh, and the remaining residue (particles with a particle size of 44 μm or more) was dried at 80°C for 24 hours to obtain the insoluble matter. Subsequently, the weight of the insoluble matter was calculated according to the following mathematical formula 1 and listed in Tables 1 and 2 below.

[0158] [Mathematical Formula 1]

[0159]

[0160] In the above mathematical formula 1,

[0161] X is the insoluble matter content (%), and

[0162] A is the weight (g) of the obtained insoluble material, and

[0163] B is the weight (g) of the resin composition (pellet).

[0164]

[0165] Experimental Example 2

[0166] The resin composition pellets prepared in the above examples and comparative examples were injected, and their physical properties were measured by the following method.

[0167]

[0168] * Melt index (220℃, 10kg): Values ​​measured according to the ASTM D1238 method are listed in Table 1 and Table 2 below.

[0169]

[0170] * Impact strength (1 / 8", kgf·cm / cm): Values ​​measured according to the ASTM D256 method are listed in Table 1 and Table 2 below.

[0171]

[0172] * Glossiness (60°): Injection specimens measuring 10 cm × 10 cm and 2 mm in thickness were prepared using resin composition pellets prepared in the examples and comparative examples under conditions of a molding temperature of 240°C and a mold temperature of 40°C. The values ​​measured for the injection specimens according to the ASTM D2457 method are listed in Tables 1 and 2 below. In the present invention, a value of 20 or less was evaluated as having low glossiness.

[0173]

[0174] * Appearance quality: When the resin composition pellets prepared in the examples and comparative examples were molded into injection specimens measuring 10 cm × 10 cm and 2 mm in thickness at a molding temperature of 240°C and observed visually, the quality was evaluated as ○ (Excellent) when five or fewer foreign substances with a size of 100 μm or more were observed in the injection specimen, as △ (Average) when six or more and ten or fewer foreign substances were observed, and as X (Poor) when more than 10 foreign substances were observed.

[0175]

[0176] Example 1 2 3 4 5 6 (A-1) Graft copolymer (parts by weight) 30 30 30 30 20 - (A-2) Graft copolymer (parts by weight) 10 30 Matrix copolymer (parts by weight) 70 70 70 70 70 70 Matte-absorbing agent type C-1 C-1 C-1 C-2 C-1 C-1 part by weight 10 10 10 20 10 10 Appearance quality improver type D-1 D-1 D-2 D-2 D-1 D-2 part by weight 14 1 1 11 Melt index (g / 10 min) 35 2 3 3 4 3 7 3 2 31 Impact strength (1 / 8``, kgf·cm / cm) 15 1 4 1 3 9 1 2 11 Gloss (60°) 13 1 5 1 5 2 0 1 5 17 Insoluble matter content (X, %) 1 6 0 7 2 1 0 2 1 8 1 9 Appearance Quality

[0177] Comparative Example 1234(A-1) Graft copolymer (parts by weight) 30303030 Matrix copolymer (parts by weight) 70707070 Matte-extinguishing agent type -C-1C-2C-2 parts by weight -10201 Appearance quality improver type D-1D-2D-2 parts by weight 1-0.210 Melt index (g / 10min) 42382819 Impact strength (1 / 8``, kgf·cm / cm) 20171021 Gloss (60°) 101121165 Insoluble matter content (X, %) 03.34.30.1 Appearance quality ○X△○

[0178] Referring to Tables 1 and 2 above, it was confirmed that in the case of Examples 1 to 6, which satisfy the desired insoluble content range, excellent appearance quality is exhibited along with low glossiness.

[0179] In the case of Comparative Example 1, which does not contain a matting agent, it was confirmed that the insoluble content was below the desirable range and that it could not exhibit low gloss compared to Examples 1 to 6.

[0180] In the case of Comparative Example 2, which does not contain an appearance quality improving agent, it was confirmed that the insoluble content exceeded the desirable range and the appearance quality deteriorated compared to Examples 1 to 6.

[0181] In the case of Comparative Example 3, where the content of the matting agent and the appearance quality improver satisfies the desirable range but exceeds the desirable insoluble content, it was confirmed that the appearance quality deteriorated compared to Examples 1 to 6.

[0182] In the case of Comparative Example 4, where the content of the matting agent and the appearance quality improver satisfies the desirable range but is less than the desirable insoluble content, it was confirmed that it could not exhibit a low gloss compared to Examples 1 to 6.

Claims

A graft copolymer comprising a rubbery polymer, aromatic vinyl monomer units, and vinyl cyanide monomer units; A matrix copolymer comprising aromatic vinyl monomer units and vinyl cyanide monomer units; A matting agent comprising a cross-linked copolymer; and Includes an appearance quality improver, A resin composition having an insoluble content (X) calculated by the following mathematical formula 1 of 0.2% or more and 3% or less: [Mathematical Formula 1] In the above mathematical formula 1, X is the insoluble matter content (%), and A is the weight (g) of the insoluble material obtained by dissolving the resin composition in a tetrahydrofuran (THF) solvent, filtering it through a 325 mesh, and drying the remaining residue. B is the weight (g) of the resin composition before dissolving in the tetrahydrofuran solvent. In paragraph 1, A resin composition having an insoluble content of 0.5% by weight or more and 2% by weight or less. In paragraph 1, With respect to 100 parts by weight of the total sum of the graft copolymer and the matrix copolymer, A resin composition comprising 0.5 parts by weight or more and 30 parts by weight or less of the above matting agent. In paragraph 1, A resin composition in which the above-mentioned crosslinking copolymer is one or more selected from the group consisting of acrylic crosslinking copolymers and aromatic vinyl-vinyl cyanide crosslinking copolymers. In paragraph 1, With respect to 100 parts by weight of the total sum of the graft copolymer and the matrix copolymer, A resin composition comprising 0.1 parts by weight or more and 10 parts by weight or less of the above-mentioned appearance quality improver. 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. In paragraph 6, The above appearance quality improver is a resin composition having a weight-average molecular weight of 1,000,000 g / mol or more. In paragraph 1, A resin composition having a glossiness (60°) of 20 or less as measured according to the ASTM D2457 method.

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