Resin composition

Abstract

A resin composition according to an embodiment of the present invention comprises: a graft copolymer including a conjugated diene-based polymer, an aromatic vinyl-based monomer unit, and a vinyl cyan-based monomer unit; a matrix copolymer including an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit; a matting agent including an aromatic vinyl-vinyl cyan-based crosslinked copolymer; and a chemical resistance improving agent, wherein the insoluble matter content (X) calculated by Equation 1 is 0.3-7%, and 0.75-10 parts by weight of the chemical resistance improving agent may be included per 100 parts by weight in total of the graft copolymer and the matrix copolymer. [Equation 1] In Equation 1, X is the insoluble matter content (%), A is the weight (g) of the insoluble matter obtained by dissolving the resin composition in a tetrahydrofuran (THF) solvent and then filtering through 325 mesh and drying the remaining residue, and B is the weight (g) of the resin composition before being dissolved in a tetrahydrofuran solvent.

Description

Resin composition

[0001] [Cross-reference with related applications]

[0002] This application claims the benefit of priority based on Korean Patent Application 10-2024-0181938 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 excellent melt index, impact strength, and chemical resistance by creating roughness on the 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 involve increased costs, a method was devised to produce a matte effect by incorporating a matting agent into the material itself; although this method has the disadvantage of maintaining a higher gloss level compared to the previous two methods.

[0007] Matte products manufactured by this method have a structural problem of being vulnerable to chemical attacks. Since the surface roughness intended to reduce gloss ultimately increases the surface area of ​​the injection-molded part, the contact surface is relatively larger compared to standard injection-molded parts when contaminants (detergents, oils, etc.) adhere, making them relatively more susceptible to chemical attack.

[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 having low gloss while having excellent melt index, impact strength, and chemical resistance.

[0012] (1) The present invention provides a resin composition comprising: a graft copolymer comprising a conjugated diene 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 a chemical resistance improving agent, wherein the insoluble content (X) calculated by the following mathematical formula 1 is 0.3% or more and 7% or less, and the chemical resistance improving agent is included in an amount of 0.75 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the total of the graft copolymer and the matrix copolymer.

[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] (2) The present invention provides a resin composition according to (1), wherein 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.

[0020] (3) The present invention provides a resin composition in which, in either (1) or (2), the chemical resistance improving agent comprises a polymer comprising crystalline units.

[0021] (4) The present invention provides a resin composition in which, in any one of (1) to (3), the polymer comprising the crystalline unit comprises 20% by weight or more and 80% by weight or less of the monomer forming the crystalline unit.

[0022] (5) The present invention provides a resin composition in which, in any one of (1) to (4), 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.

[0023] (6) The present invention provides a resin composition in which, in any one of (1) to (5), the gloss (60°) measured according to the ASTM D523 method for an injection product produced by injecting the resin composition under conditions of an injection temperature of 230°C, an injection speed of 10 mm / s, and a mold temperature of 40°C is 50 or less.

[0024] (7) The present invention provides a resin composition that satisfies the following mathematical formula 2 in any one of (1) to (6).

[0025] [Mathematical Formula 2]

[0026]

[0027] In the above mathematical formula 2,

[0028] Y is the content (parts by weight) of the chemical resistance improving agent relative to 100 parts by weight of the total sum of the graft copolymer, the matrix copolymer, and the matting agent, and

[0029] Ra is the centerline average roughness (μm) measured according to the ASME B46.1 method on a specimen of 10 cm × 10 cm in a planar shape by injecting the resin composition under conditions of injection temperature 230°C, injection speed 10 mm / s and mold temperature 40°C.

[0030] A resin composition according to one embodiment of the present invention has low gloss while having excellent melt index, impact strength, and chemical resistance.

[0031] Hereinafter, the present invention will be described in more detail to aid in understanding the invention.

[0032] 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.

[0033] 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.

[0034] 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.

[0035]

[0036] <Resin Composition>

[0037] The present invention provides a resin composition.

[0038] A resin composition according to one embodiment of the present invention comprises at least: a graft copolymer comprising a conjugated diene 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 a chemical resistance improving agent, wherein the insoluble content (X) calculated by the following mathematical formula 1 is 0.3% or more and 7% or less, and wherein, for a total of 100 parts by weight of the graft copolymer and the matrix copolymer, the matting agent is included in an amount of 1 part by weight or more and 30 parts by weight or less, and the chemical resistance improving agent is included in an amount of 0.1 part by weight or more and 10 parts by weight or less.

[0039] [Mathematical Formula 1]

[0040]

[0041] In the above mathematical formula 1,

[0042]

[0043] X is the insoluble matter content (%), and

[0044] 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.

[0045] B is the weight (g) of the resin composition before dissolving in the tetrahydrofuran solvent.

[0046] 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 was proposed to apply a chemical resistance improver to the resin composition to which the matting agent was applied, but it was discovered that the chemical resistance improver increases the glossiness of the resin composition.

[0047] Accordingly, the inventors discovered that when a matting agent comprising an aromatic vinyl-vinyl cyanide crosslinked copolymer is added to a resin composition, the glossiness of the resin composition can be effectively reduced even with a small amount, and that when the matting agent and a chemical resistance improver are included within a preferred range, low glossiness and chemical resistance, which are in a trade-off relationship, are simultaneously satisfied, and excellent melt index and impact strength are exhibited, leading to the completion of the present invention.

[0048] The insoluble content represented by the above mathematical formula 1 of the resin composition according to one embodiment of the present invention is mainly 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.

[0049] A resin composition according to one embodiment of the present invention may have an insoluble content represented by the above mathematical formula 1 of 0.3% or more and 7% or less, and as specific examples, may be 0.32% or more, 0.34% or more, 0.36% or more, 0.38% or more, or 0.4% or more, and may also be 6.5% or less, 6% or less, 5.5% or less, 5% or less, 4.5% or less, or 4.1% or less. When the above range is satisfied, the resin composition can satisfy excellent appearance quality while having low gloss.

[0050] If the above-mentioned insoluble content is less than the range described above, it means that a sufficient amount of matting agent has not been added to the resin composition, 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 means that an excessive amount of matting agent has been added to the resin composition, and thus the chemical resistance of the resin composition may be reduced.

[0051]

[0052] A resin composition according to one embodiment of the present invention may further satisfy the following mathematical formula 2.

[0053] [Mathematical Formula 2]

[0054]

[0055] In the above mathematical formula 2,

[0056] Y is the content (parts by weight) of the chemical resistance improving agent relative to 100 parts by weight of the total sum of the graft copolymer, the matrix copolymer, and the matting agent, and

[0057] Ra is the centerline average roughness (μm) measured according to the ASME B46.1 method on a specimen of 10 cm × 10 cm in a planar shape by injecting the resin composition under conditions of injection temperature 230°C, injection speed 10 mm / s and mold temperature 40°C.

[0058] A resin composition according to one embodiment of the present invention may have a ratio of the centerline average roughness (μm; Ra) of the resin composition to the content (parts by weight; Y) of the chemical resistance improving agent relative to 100 parts by weight of the total sum of the graft copolymer and the matrix copolymer, i.e., Y / Ra, which may be 0.5 or more and 14 or less. Specifically, as an example, it may be 0.51 or more, 0.52 or more, 0.53 or more, 0.54 or more, 0.55 or more, 0.56 or more, 0.57 or more, 0.58 or more, 0.59 or more, 0.6 or more, 0.6 or more, 0.61 or more, 0.62 or more, 0.63 or more, 0.64 or more, 0.65 or more, 0.66 or more, or 0.67 or more, and 13.5 or less, 13 or less, 12.5 or less, 12 or less, 11.5 or less, 11 or less, 10.5 or less. It may be 10 or less, 9.5 or less, 9 or less, 8.5 or less, 8 or less, 7.5 or less, 7 or less, 6.5 or less, 6 or less, 5.5 or less, or 5 or less. If the above range is satisfied, low gloss and chemical resistance can be satisfied simultaneously.

[0059]

[0060] If the above Y / Ra is below the aforementioned range, the centerline average roughness is excessively large, and chemical resistance may be reduced even with low gloss. Furthermore, if the above Y / Ra exceeds the aforementioned range, the chemical resistance improver is included in excess, and consequently, a level of glossiness that can be considered low may not be satisfied.

[0061] In the present invention, having low gloss means that the gloss (60°) of the resin composition measured according to the ASTM D523 method is 50 or less, and specifically means 40 or less, 30 or less, 20 or less, 15 or less, or 10 or less.

[0062]

[0063] A resin composition according to one embodiment of the present invention may have an impact strength (1 / 8'') of 10 kgcm / cm or more as measured according to the ASTM D256 method, and specifically, as an example, may be 10.5 kgcm / cm or more, 11 kgcm / cm or more, 11.5 kgcm / cm or more, 12 kgcm / cm or more, 12.5 kgcm / cm or more, or 13 kgcm / cm or more. In the present invention, when the above range is satisfied, it is evaluated to have excellent impact strength.

[0064] A resin composition according to one embodiment of the present invention may have a melt index (220°C, 10kg) of 20 g / 10min or higher as measured according to the ASTM D1238 method, and specifically, as an example, may be 21 g / 10min or higher, 22 g / 10min or higher, 23 g / 10min or higher, or 24 g / 10min or higher. In the present invention, when the above range is satisfied, it is evaluated as having an excellent melt index.

[0065]

[0066] Hereinafter, each component constituting the resin composition according to one embodiment of the present invention will be described.

[0067]

[0068] Graft copolymer

[0069] A resin composition according to one embodiment of the present invention may include a graft copolymer.

[0070] 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.

[0071] According to one embodiment of the present invention, the 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.

[0072] According to one embodiment of the present invention, the 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.

[0073]

[0074] According to one embodiment of the present invention, the conjugated diene monomer for forming the conjugated diene polymer of the 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.

[0075]

[0076] 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.

[0077] 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.

[0078]

[0079] 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.

[0080] 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.

[0081]

[0082] 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.

[0083] 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.

[0084]

[0085] 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.

[0086]

[0087] Matrix copolymer

[0088] A resin composition according to one embodiment of the present invention may include a matrix copolymer.

[0089] 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.

[0090]

[0091] 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.

[0092] 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.

[0093]

[0094] 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.

[0095] 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.

[0096]

[0097] 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.

[0098]

[0099] Matting agent

[0100] 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.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] According to one embodiment of the present invention, the aromatic vinyl-vinyl cyanide crosslinked copolymer may contain aromatic vinyl monomer units and vinyl cyanide monomer units in a weight ratio of 95:5 to 55:45, preferably 85:15 to 65:35. If the above conditions are satisfied, a vinyl crosslinked polymer with improved processability and chemical resistance can be produced.

[0105]

[0106] 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.

[0107] 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.

[0108] 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.

[0109] 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.

[0110]

[0111] 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.

[0112]

[0113] A resin composition according to one embodiment of the present invention may contain 0.5 parts by weight or more and 30 parts by weight or less of the matting agent based on 100 parts by weight of the total of the graft copolymer and the matrix copolymer. Specifically, it may contain 0.6 parts by weight or more, 0.8 parts by weight or more, 1 part by weight or more, 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, or 2 parts by weight or more, and may also contain 28 parts by weight or less, 26 parts by weight or less, 24 parts by weight or less, 22 parts by weight or less, or 20 parts by weight or less.

[0114] A resin composition according to one embodiment of the present invention may exhibit excellent chemical resistance, impact strength, and melt index while having low gloss by including the matting agent in an amount 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 and impact strength of the resin composition may be reduced.

[0115]

[0116] Chemical resistance improver

[0117] 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.

[0118] 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.

[0119] 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.

[0120] 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.

[0121] A resin composition according to one embodiment of the present invention may contain 0.75 parts by weight or more and 10 parts by weight or less of the chemical resistance improving agent based on 100 parts by weight of the total sum of the graft copolymer and the matrix copolymer, and as a specific example, may contain 0.8 parts by weight or more, 0.85 parts by weight or more, 0.9 parts by weight or more, 0.95 parts by weight or more, or 1 part by weight or more, and may also contain 9.8 parts by weight or less, 9.6 parts by weight or less, 9.4 parts by weight or less, 9.2 parts by weight or less, 9 parts by weight or less, 8.8 parts by weight or less, 8.6 parts by weight or less, 8.4 parts by weight or less, 8.2 parts by weight or less, or 8 parts by weight or less.

[0122] A resin composition according to one embodiment of the present invention may exhibit excellent chemical resistance, 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.

[0123] According to one embodiment of the present invention, the content of the chemical resistance modifier in the resin composition can be calculated through infrared spectroscopy (FT-IR). Depending on the type of chemical resistance modifier, the peaks expressed through infrared spectroscopy (FT-IR) may vary. Since the method of calculating the content of a target substance present in a material through infrared spectroscopy (FT-IR) is widely known in the art, a detailed explanation thereof will be omitted.

[0124]

[0125] Other additives

[0126] A resin composition according to one embodiment of the present invention may further include additives.

[0127] 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.

[0128] 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.

[0129]

[0130] <Molded Product>

[0131] The present invention provides a molded article formed from the resin composition.

[0132] 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 transparent window or an office equipment transparent window.

[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] * Graft copolymer: Manufactured by LG Chem, Product name: DP270E

[0140]

[0141] * Matrix Copolymer: Manufactured by LG Chem, Product Name: S83SF

[0142]

[0143] * Matting agent (A-1): A cross-linked SAN copolymer prepared by the following method was used as the matting agent (A-1).

[0144] 130 parts by weight of ion-exchanged water, 74 parts by weight of styrene, 26 parts by weight of acrylonitrile, 0.2 parts by weight of 1-1'azobis(cyclohexane-1-carbonitrile), 0.25 parts by weight of n-dodecyl mercaptan, and 0.65 parts by weight of divinylmethylsilane were added, and the temperature of the reactor was raised to 70°C. Then, 0.2 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 7 hours. Afterward, the mixture was washed, dehydrated, and dried to produce a cross-linked SAN copolymer in powder form. Here, each of the above parts by weight is based on a total monomer input amount of 100 parts by weight.

[0145]

[0146] * Mattening Agent (A-2): Manufactured by ASP (Advanced Specialty Polymer), Product Name: MH-20FD

[0147]

[0148] * Matting agent (A-3): A cross-linked SAN copolymer prepared by the following method was used as the matting agent (A-3).

[0149] 130 parts by weight of ion-exchanged water, 74 parts by weight of styrene, 26 parts by weight of acrylonitrile, 0.2 parts by weight of 1-1'azobis(cyclohexane-1-carbonitrile), 0.25 parts by weight of n-dodecyl mercaptan, and 0.65 parts by weight of divinylmethylsilane were added, and the temperature of the reactor was raised to 70°C. Then, 0.5 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 7 hours. Afterward, the mixture was washed, dehydrated, and dried to produce a cross-linked SAN copolymer in powder form. Here, each of the above parts by weight is based on a total monomer input amount of 100 parts by weight.

[0150]

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

[0152] 130 parts by weight of ion-exchanged water, 74 parts by weight of styrene, 26 parts by weight of acrylonitrile, 0.2 parts by weight of 1-1'azobis(cyclohexane-1-carbonitrile), 0.25 parts by weight of n-dodecyl mercaptan, and 0.65 parts by weight of divinylmethylsilane were added, and the temperature of the reactor was raised to 70°C. Then, 0.05 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 7 hours. Afterward, the mixture was washed, dehydrated, and dried to produce a cross-linked SAN copolymer in powder form. Here, each of the above parts by weight is based on a total monomer input amount of 100 parts by weight.

[0153]

[0154] * Chemical Resistance Improver (B-1): Manufactured by DOW, Product Name: Acrylate Copolymer (ELVALOY TM AC 1224)

[0155]

[0156] * Chemical resistance modifier (B-2): Manufactured by LG Chem, Product name: TPEE (KEYFLEX BT 1030D)

[0157]

[0158] * Additives: Manufactured by Seon-gu Co., Product Name: SUNLUBE EBS

[0159]

[0160] The above graft copolymer, matrix copolymer, matting agent, chemical resistance improver, and additives were fed into an extruder with the compositions described in Tables 1 and 2 below and melt-mixed at 230°C to produce pellets.

[0161]

[0162] Experimental Example

[0163] The resin composition pellets prepared in the above examples and comparative examples were injected, and their physical properties were measured by the following method.

[0164]

[0165] * Melt index (220℃, 10kg): Values ​​measured according to the ASTM D1238 method are listed in Tables 1 and 2 below.

[0166]

[0167] * Impact strength (1 / 8): Values ​​measured according to the ASTM D256 method are listed in Tables 1 and 2 below.

[0168]

[0169] * Glossiness (60°): The values ​​measured according to the ASTM D523 method for injection-molded products produced by injecting each of the resin composition pellets prepared in the above examples and comparative examples under conditions of an injection temperature of 230°C, an injection speed of 10 mm / s, and a mold temperature of 40°C are listed in Tables 1 and 2 below. In the present invention, a value of 50 or less was evaluated as having low glossiness.

[0170]

[0171] * Centerline Average Roughness (Ra): Each resin composition pellet prepared in the above examples and comparative examples was injected under conditions of an injection temperature of 230°C, an injection speed of 10 mm / s, and a mold temperature of 40°C to produce a planar specimen of 10 cm × 10 cm, and the produced specimen was evaluated according to the ASME B 46.1 method (optical profiler (manufactured by Zygo, product name: New View) TM 8300), measurement area: 1.7mm × 1.7mm) The centerline average roughness was measured and recorded in Tables 1 and 2 below.

[0172]

[0173] * Insoluble matter content (%): 1 g of each pellet prepared in the above examples and comparative examples was stirred for 24 hours to dissolve it sufficiently in a 40 g solution of tetrahydrofuran (THF), 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.

[0174] [Mathematical Formula 1]

[0175]

[0176] In the above mathematical formula 1,

[0177] X is the insoluble matter content (%), and

[0178] A is the weight (g) of the obtained insoluble material, and

[0179] B is the weight (g) of the resin composition (pellet).

[0180]

[0181] * Chemical resistance: After placing gauze on the surface of each tensile specimen of the example and comparative example fixed to a 1% strain jig, 1 ml of laundry detergent (Nanox) was applied, and the occurrence of cracks 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.

[0182] The longer the time taken for a crack to occur, the better the chemical resistance. In the present invention, it was evaluated that it has excellent chemical resistance when the time is 10 hours or more.

[0183]

[0184] Example 1 23456 Graft copolymer (parts by weight) 282828282828 Matrix copolymer (parts by weight) 727272727272 Matting agent type A-1A-1A-1A-1A-1A-1A-1 parts by weight 5112525125 Chemical resistance improver type B-1B-1B-1B-2B-1B-1 parts by weight 15881010 Additives (parts by weight) 1.51.51.51.51.51.5 Y / Ra 0.632.53.23.3312.508.33 Insoluble matter Content (%) 1.5 1.9 4 4.1 0.4 4.1 Melt Index (g / 10 min) 35 30 25 24 37 25 Impact Strength (kg cm / cm) 20 16 14 16 21 15 Ra (㎛) 1.6 2.0 2.5 2.4 0.8 1.2 Gloss (60°) 14 10 89 43 29 Chemical Resistance (hr) 10 11 10 10 14 15

[0185] Comparative Example 1 2345678 Graft copolymer (parts by weight) 2828282828282828 Matrix copolymer (parts by weight) 727272727272727272 Matting agent type A-1A-1A-1A-1A-1A-1A-2A-3A-4 parts by weight 511400 0.555252525 Chemical resistance improver type B-1B-1B-1B-1B-2B-1B-1 parts by weight 0.51251081010 Additives (parts by weight) 1.51.51.51.51.51.51.51.51.5Y / Ra 00.1824252.4482.613 Insoluble matter Content (%) 1.5 2.0 4.2 0.1 10 19 8 0.2 Melting Index (g / 10 min) 3 4 28 25 40 89 25 25 Impact Strength (kg cm / cm) 20 15 15 30 8 13 15 18 Ra (㎛) 1.9 2.8 0.5 0.2 4.1 1.0 3.8 0.7 Gloss (60°) 14 9 55 90 6 33 15 71 Chemical Resistance (hr) 24 15 13 6 12 6 15

[0186] Referring to Tables 1 and 2, it can be seen that the resin compositions according to Examples 1 to 6, which satisfy a desirable range of insoluble matter content and contain a desirable amount of chemical resistance improving agent, satisfy excellent melt index and impact strength, and have low gloss while having excellent chemical resistance.

[0187] It was confirmed that the resin compositions of Comparative Example 1, which does not contain a chemical resistance improver, and Comparative Example 2, which contains a chemical resistance improver in an amount less than the desirable amount, do not satisfy the above mathematical formula 1, and that the chemical resistance is reduced compared to Examples 1 to 6.

[0188] It was confirmed that the resin composition of Comparative Example 3, which contains a chemical resistance improving agent in excess of a desirable amount, did not satisfy the low gloss level compared to Examples 1 to 6.

[0189] It was confirmed that the resin compositions of Comparative Examples 4 and 8, which had an insoluble content below the desirable range, did not satisfy low gloss compared to Examples 1 to 6.

[0190] It was confirmed that the resin compositions of Comparative Examples 5 and 7, in which the insoluble content exceeded the desirable range, had reduced melt index and impact strength, and reduced chemical resistance compared to Examples 1 to 6.

[0191] It was confirmed that the resin composition of Comparative Example 6, which includes a compound other than an aromatic vinyl-vinyl cyanide crosslinked copolymer as a matting agent, did not satisfy the above Equation 1 despite being included in a desirable amount, and that the melt index was lowered compared to Examples 1 to 4.

Claims

1. A graft copolymer comprising a conjugated diene 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 chemical resistance improvers, The insoluble matter content (X) calculated by the following mathematical formula 1 is 0.3% or more and 7% or less, and A resin composition comprising 0.75 parts by weight or more and 10 parts by weight or less of the chemical resistance improving agent, based on 100 parts by weight of the total sum of the graft copolymer and the matrix copolymer: [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.

2. 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.

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

4. In Paragraph 3, A resin composition comprising a polymer containing the above-mentioned crystalline unit, wherein the monomer forming the above-mentioned crystalline unit comprises 20% by weight or more and 80% by weight or less.

5. 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.

6. In Paragraph 1, A resin composition having a gloss (60°) of 50 or less, measured according to the ASTM D523 method for an injection-molded product produced under conditions of an injection temperature of 230°C, an injection speed of 10 mm / s, and a mold temperature of 40°C.

7. In Paragraph 1, A resin composition satisfying the following mathematical formula 2: [Mathematical Formula 2] In the above mathematical formula 2, Y is the content (parts by weight) of the chemical resistance improving agent relative to 100 parts by weight of the total sum of the graft copolymer, the matrix copolymer, and the matting agent, and Ra is the centerline average roughness (μm) of the resin composition, measured according to the ASME B46.1 method on the specimen produced by injecting the resin composition under conditions of an injection temperature of 230°C, an injection speed of 10 mm / s, and a mold temperature of 40°C to produce a 10 cm × 10 cm planar specimen.

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