Cross-linked copolymer and resin composition comprising same

Abstract

A resin composition according to one embodiment of the present invention comprises: a graft copolymer comprising a conjugated diene-based 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; and a cross-linked copolymer having a Mark-Houwink constant (M-H constant) of 0.2-0.6, wherein insoluble amount (X) calculated by mathematical relation 1 can be 0.3-7%. [Mathematical relation 1] In mathematical relation 1, X is an insoluble amount (%), A is the weight (g) of an insoluble matter obtained by dissolving the resin composition in tetrahydrofuran (THF) solvent, filtering same through 325-mesh and drying a remaining residue, and B is the weight (g) of the resin composition before dissolving same in THF solvent.

Description

Crosslinked copolymer and resin composition containing the same

[0001] [Cross-reference with related applications]

[0002] This application claims the benefit of priority based on Korean Patent Application 10-2024-0181939 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 capable of achieving a matte finish.

[0006] Generally, acrylonitrile-butadiene-styrene (hereinafter referred to as ABS) resin is widely used in various applications such as automobiles, electrical and electronic equipment, office equipment, home appliances, toys, and stationery due to its excellent impact resistance and processability. However, because the double bonds of butadiene rubber used as an impact modifier cause ABS resin to oxidize easily upon contact with oxygen, ultraviolet rays, light, and heat, its use as an exterior material is severely limited due to its fragility, which leads to discoloration and deterioration of appearance quality. Furthermore, even in interior materials, it fails to meet consumer requirements due to discoloration.

[0007] Recently, driven by the trend toward premiumization in home appliances and automotive interiors, there has been a growing interest in "emotional resins" capable of expressing a soft, unpainted, low-gloss texture, replacing cold and artificial glossy materials. Consequently, the automotive industry is also increasingly opting to directly use low-gloss resins, bypassing coating and painting processes, due to indoor air quality regulations and environmental concerns.

[0008] A method was proposed to produce a low-gloss resin by applying a vinyl-based cross-linked copolymer to exhibit a low-gloss effect through diffuse reflection that scatters incident light; however, since vinyl-based cross-linked copolymers are not linear polymers, there was a problem in that the fluidity of the resin composition containing them was reduced, making molding difficult.

[0009] Accordingly, there is a need to develop a new low-gloss material that simultaneously exhibits excellent weather resistance, heat resistance, fluidity, and low-gloss properties, while also uniformly displaying low-gloss properties across the entire surface area of ​​the molded product.

[0010] [Prior Art Literature]

[0011] [Patent Literature]

[0012] (Patent Document 1) U.S. Registered Patent No. 4,460,742

[0013] The problem to be solved by the present invention is to provide a resin composition that has excellent fluidity while achieving low gloss.

[0014] Another problem to be solved by the present invention is to provide a crosslinked copolymer for manufacturing a resin composition that has excellent fluidity while achieving low gloss.

[0015] Another problem to be solved by the present invention is to provide a method for manufacturing a cross-linked copolymer for producing a resin composition that has excellent fluidity while achieving low gloss.

[0016] (1) The present invention comprises 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; and a crosslinked copolymer having an MH constant (Mark-Houwink constant) of 0.2 or more and 0.6 or less, and

[0017] A resin composition is provided having an insoluble content (X) calculated by the following mathematical formula 1 of 0.3% or more and 7% or less.

[0018] [Mathematical Formula 1]

[0019]

[0020] In the above mathematical formula 1,

[0021] X is the insoluble matter content (%), and

[0022] 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.

[0023] B is the weight (g) of the resin composition before dissolving in the tetrahydrofuran solvent.

[0024] (2) The present invention provides a resin composition according to (1), wherein the crosslinking copolymer comprises an aromatic vinyl monomer unit, a vinyl cyanide monomer unit, and a crosslinking portion derived from a crosslinking functional compound.

[0025] (3) The present invention provides a resin composition in which, in either (1) or (2), the crosslinking copolymer has an MH constant of 0.4 or more and 0.55 or less.

[0026] (4) The present invention provides a resin composition in which, in any one of (1) to (3) above, the glossiness (60°) measured according to the ASTM D523 method is 25 or less, and the coefficient of variation of light reflection calculated by the following mathematical formula 1 is 2.0 or less.

[0027] [Mathematical Formula 1]

[0028] C LR = D L / M L

[0029] The above C LR is the coefficient of variation of light reflection, and D L is the standard deviation of luminous intensity, and M Lis the average luminous intensity.

[0030] (5) The present invention provides a resin composition in which, in any one of (1) to (4), the glossiness (60°) measured according to the ASTM D523 method is 20 or less.

[0031] (6) The present invention provides a resin composition in which, in any one of (1) to (5), the coefficient of change in light reflection is 1.5 or less.

[0032] (7) The present invention provides a resin composition in which, in any one of (1) to (6) above, the melt index (220°C, 10kg) measured according to the ASTM D1238 method is 20 g / 10min or higher.

[0033] (8) The present invention provides a crosslinked copolymer comprising an aromatic vinyl monomer unit, a vinyl cyanide monomer unit and a crosslinking functional compound, wherein the MH constant is 0.2 or more and 0.6 or less.

[0034] (9) The present invention provides a crosslinked copolymer according to (8), wherein the MH constant is 0.4 or more and 0.55 or less.

[0035] (10) The present invention provides a method for manufacturing a crosslinked copolymer comprising the steps of: introducing a first reaction solution containing an aromatic vinyl monomer, a vinyl cyanide monomer, a silicone-based crosslinking functional compound and a molecular weight regulator to initiate polymerization (S1); and introducing a second reaction solution containing a polyene-based crosslinking functional compound or a polyene-based crosslinking functional compound and a molecular weight regulator into the reactor in two or more separate steps (S2), wherein the amount of the crosslinking functional compound introduced into the second reaction solution and the total amount of the molecular weight regulator introduced into the first reaction solution and the second reaction solution have a ratio of 1:1.5 or more and 1:4.5 or less.

[0036] A resin composition incorporating a crosslinked copolymer according to one embodiment of the present invention has low gloss and excellent fluidity while containing a crosslinked copolymer.

[0037] Hereinafter, the present invention will be described in more detail to aid in understanding the invention.

[0038] Terms and words used in this specification and claims shall not be interpreted as being limited to their ordinary or dictionary meanings, but shall 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.

[0039]

[0040] Unless otherwise defined, the terms and measurement methods used in the present invention may be defined as follows.

[0041] 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.

[0042] The terms 'monomer unit,' 'crosslinking unit,' or 'crosslinking part' used in the present invention may refer to a repeating unit formed by a compound used as a monomer or a compound used as a crosslinking agent participating in a polymerization reaction or a crosslinking reaction, a structure derived therefrom, or the material itself.

[0043] The term 'derivative' used in the present invention may refer to a compound having a structure in which one or more of the hydrogen atoms constituting the original compound are formed as a halogen group, an alkyl group, or a hydroxyl group.

[0044]

[0045] <Resin Composition>

[0046] The present invention provides a resin composition.

[0047] 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; and a crosslinked copolymer having an MH constant of 0.2 or more and 0.6 or less, wherein the insoluble content (X) calculated by the following mathematical formula 1 is 0.3% or more and 7% or less.

[0048] [Mathematical Formula 1]

[0049]

[0050] In the above mathematical formula 1,

[0051] X is the insoluble matter content (%), and

[0052] 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.

[0053] B is the weight (g) of the resin composition before dissolving in the tetrahydrofuran solvent.

[0054]

[0055] Although cross-linked copolymers can effectively impart low gloss to resin compositions by inducing diffuse reflection that scatters incident light, there was a problem with low fluidity of resin compositions containing cross-linked copolymers because their flowability is low due to their structural characteristics that they are not linear polymers. The inventors discovered that by adjusting the MH constant (degree of branching) of the cross-linked copolymer to an appropriate range and adjusting the insoluble content calculated by the above mathematical formula 1 to an appropriate range, low gloss is imparted to the resin composition without reducing fluidity, and thus completed the present invention.

[0056]

[0057] 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 crosslinking portion (formed from a crosslinking functional compound) of the crosslinking copolymer included in the matting agent, and may vary depending on the crosslinking structure of the crosslinking copolymer.

[0058] 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, 4% or less, 3.5% or less, or 3% or less. When the above range is satisfied, the resin composition can satisfy excellent appearance quality while having low gloss.

[0059] If the above-mentioned insoluble content is less than the range described above, it means that the cross-linking structure of the cross-linking copolymer introduced into the resin composition is not uniform, and accordingly, 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 the cross-linking structure of the cross-linking copolymer introduced into the resin composition is excessively uniform, and accordingly, the fluidity of the resin composition may be reduced.

[0060] A resin composition according to one embodiment of the present invention may have a glossiness (60°) of 25 or less as measured according to the ASTM D523 method, and as a specific example, may be 24 or less, 22 or less, or 20 or less. Glossiness is a representative value that can express the glossiness (high gloss, low gloss) or matte finish of a resin. Generally, commercially available matte molded products exceed 30, which cannot be considered substantially matte. However, when using the resin composition of the present invention, a glossiness of 25 or less can be achieved at a very low level, making it possible to realize a matte product.

[0061] A resin composition according to one embodiment of the present invention may have a coefficient of variation in light reflection calculated by the following mathematical formula 2 of 2.0 or less.

[0062] [Mathematical Formula 2]

[0063] C LR = D L / M L

[0064] The above C LR is the coefficient of variation of light reflection, and D L is the standard deviation of luminous intensity, and M L is the average luminous intensity.

[0065] Conventional matte products are typically produced by roughening the surface of injection molds through methods such as etching before injecting resin, thereby giving the surface diffuse reflection properties. However, this method is not suitable for mass production because processability is poor due to mold wear.

[0066] Meanwhile, there are also molded products designed to achieve a matte finish on low-gloss products through post-processing. For example, there are methods that form a pattern on the surface by co-extruding and attaching a film containing a crosslinker, or by applying a crosslinker to the product and then UV-curing it to impart a pattern to the surface. However, this method has the problem of being significantly economically disadvantageous due to its very high defect rate, low reproducibility of the physical properties of the produced product, and the requirement for additional processes such as coating and curing.

[0067] On the other hand, a resin composition according to one embodiment of the present invention can provide a matte molded article with guaranteed surface uniformity, having a glossiness as described above and a coefficient of variation of light reflection of 2.0 or less. The coefficient of variation of light reflection is 2.0 or less, preferably 1.9 or less, more preferably 1.8 or less, even more preferably 1.7 or less, and most preferably 1.5 or less.

[0068] The above coefficient of light reflection variation indicates the uniformity of the surface of the molded product and also reflects glossiness, meaning that while the surface is matte, the entire surface is uniform, and diffuse reflection occurs equally everywhere on the surface of the molded product, thus enabling the provision of a high-quality matte molded product. In other words, a coefficient of light reflection variation exceeding 2.0 may mean that the surface is not uniform and that diffuse reflection does not occur in any part of the surface.

[0069] The above optical reflection variation coefficient can be derived using Python in the following way.

[0070] 1) Sample imaging: Using a DSLR camera (Canon 750D) and a 200 mm x 200 mm surface light (White LED, Collimated Backlight LTS-3PFT), the prepared sample is photographed and imaged with the distance between the camera and the sample set to 40 cm, the distance between the sample and the light set to 100 cm, and the angle set to 90°.

[0071] 2) Grayscale conversion of the sample image: The sample image is converted to grayscale (0~255) using the OpenCV library. At this time, a grayscale value is assigned to each pixel within the sample image, and this grayscale value is used as the luminosity.

[0072] 3) Reconstruction of the image: The above image is divided into a grid of 200 µm x 200 µm, and the image is reconstructed by averaging the luminance values ​​(grayscale values) of the pixels within each grid. At this time, each grid has a single averaged luminance value.

[0073] 4) Luminous intensity correction: The target grid is designated as Zone 1, the 8 grids adjacent to Zone 1 as Zone 2, and the 16 grids adjacent to Zone 2 as Zone 3. After assigning zone-specific correction coefficients of 1 to Zone 1, -0.0625 to Zone 2, and -0.03125 to Zone 3, the corrected luminous intensity value of the target grid is derived using the following Equation 3.

[0074] [Mathematical Formula 3]

[0075]

[0076] In the above mathematical formula 3, L is the corrected luminosity value of the target grating, and L 1 is the luminosity of the Zone 1 grid, L 2 1, L 2 2, L 2 3, ..., L 2 8 is the luminous intensity of each of the 8 grids in Zone 2, L 3 1, L 3 2, L 3 3, ..., L 3 16 is the luminosity of each of the 16 grids in Zone 3.

[0077] The above correction factor is intended to readjust the luminosity by taking into account the visual suppression effect, and may be intended to minimize errors caused by optical illusions, where the luminosity of the target grid may be evaluated differently depending on the luminosity of surrounding grids when observed with the naked eye. Specifically, since the judgment of "matte" based on human visual perception is more important when the product is manufactured, the value measured by the device must not only indicate matte but also be perceived as matte visually in reality. Accordingly, the above correction factor may be applied to the measurement value so that the measurement value derived by the device becomes equivalent to the actual visual effect considering optical illusions.

[0078] 5) Derivation of mean and standard deviation: The mean and standard deviation are calculated from the corrected luminous intensity values ​​of each grid, and the coefficient of variation in light reflection is derived through the above mathematical formula 2 using the mean and standard deviation of the luminous intensity calculated in this way.

[0079]

[0080] 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 as specific examples, may be 22 g / 10min or higher, 24 g / 10min or higher, 26 g / 10min or higher, or 28 g / 10min or higher, and may also be 50 g / 10min or lower, 48 g / 10min or lower, 46 g / 10min or lower, 44 g / 10min or lower, 42 g / 10min or lower, or 40 g / 10min or lower. As described above, by adjusting the MH constant (degree of branching) of the crosslinking copolymer to an appropriate range, the fluidity of the resin composition can be excellent while satisfying the degree of crosslinking and molecular weight in an appropriate range that allows the crosslinking copolymer to impart low gloss to the resin composition.

[0081]

[0082] Hereinafter, each component constituting the resin composition according to one embodiment of the present invention will be described.

[0083]

[0084] Graft copolymer

[0085] A resin composition according to one embodiment of the present invention may include a graft copolymer.

[0086] 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.

[0087] 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.

[0088] 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.

[0089]

[0090] 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.

[0091]

[0092] 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.

[0093] 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.

[0094]

[0095] 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.

[0096] 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.

[0097]

[0098] 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.

[0099] 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.

[0100]

[0101] Matrix copolymer

[0102] A resin composition according to one embodiment of the present invention may include a matrix copolymer.

[0103] 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.

[0104]

[0105] 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.

[0106] 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.

[0107]

[0108] 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.

[0109] 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.

[0110]

[0111] cross-linked copolymer

[0112] A resin composition according to one embodiment of the present invention may include a cross-linked copolymer having an MH constant of 0.2 or more and 0.6 or less.

[0113] The above-mentioned crosslinked copolymer imparts surface characteristics to allow light to be diffusely reflected from the surface of the resin composition. It is manufactured in a form with higher strength due to crosslinking and may be uniformly distributed within the matrix resin. When the above-mentioned crosslinked copolymer is included in the resin composition, very low gloss and coefficient of variation of light reflection can be achieved. The above effects can be realized even better when the above-mentioned crosslinked copolymer is included within the aforementioned range.

[0114] According to one embodiment of the present invention, the crosslinked copolymer may comprise a crosslinking portion derived from a crosslinking functional compound, an aromatic vinyl monomer unit, and a vinyl cyanide monomer unit.

[0115] According to one embodiment of the present invention, the crosslinking portion may include a crosslinking functional compound unit, and the crosslinking functional compound may include one or more selected from the group consisting of silicone-based compounds, acrylic-based compounds and vinyl-based compounds, and the crosslinking portion may be composed of a unit derived from these compounds.

[0116] A crosslinked copolymer according to one embodiment of the present invention may have crosslinked portions within it that are very uniformly distributed, and the degree of distribution of the crosslinked portions may be appropriate so that the fluidity between the entire chains is maintained.

[0117] According to one embodiment of the present invention, the crosslinked copolymer may be a random copolymer, and the composition of aromatic vinyl monomer units and vinyl cyanide monomer units within the copolymer may be uniform. The uniform composition of the monomer units may mean that the ratio of each monomer unit present within the polymer that is polymerized and grown by the polymerization reaction of the monomers is maintained uniformly. As a specific example, it may mean that when a portion of the polymer is taken from the reactor as polymerization proceeds, that is, as the polymerization time changes during polymerization, the ratio of each monomer unit forming the polymer is maintained uniformly.

[0118] According to one embodiment of the present invention, the aromatic vinyl monomer unit and the vinyl cyanide monomer unit may each refer to a repeating unit formed by the participation of the aromatic vinyl monomer and the vinyl cyanide monomer in a polymerization reaction. As a specific example, the polymerization reaction may be a radical polymerization reaction, and accordingly, may refer to a repeating unit derived from a carbon-carbon double bond present in the aromatic vinyl monomer and the vinyl cyanide monomer.

[0119] A crosslinked copolymer according to one embodiment of the present invention may have an MH constant (Mark-Houwink constant) of 0.2 or more and 0.6 or less, and as specific examples, may be 0.25 or more, 0.3 or more, 0.35 or more, or 0.4 or more, and may also be 0.59 or less, 0.58 or less, 0.57 or less, 0.56 or less, or 0.55 or less. The MH constant is the slope when showing a proportional relationship between weight-average molecular weight and intrinsic viscosity, and may have a smaller value as the degree of branching of the crosslinked copolymer increases, and can be measured by the GPC-TDA method.

[0120] If the MH constant of the crosslinked copolymer according to one embodiment of the present invention satisfies the above range, the fluidity of the resin composition may be excellent. If the MH constant of the crosslinked copolymer exceeds the above range, the degree of branching of the crosslinked copolymer is low, and thus the flowability is reduced, which may result in a decrease in the fluidity of the resin composition. Furthermore, if the MH constant of the crosslinked copolymer is below the above range, an excessive amount of molecular weight regulator is added to induce branching of the crosslinked copolymer, causing the movement of polymer chains to be greater than the growth, which leads to a decrease in the reaction and thus a decrease in the yield of the crosslinked copolymer.

[0121] According to one embodiment of the present invention, the resin composition may contain the crosslinking copolymer in an amount of 1 part by weight or more and 40 parts by weight or less per 100 parts by weight of the resin composition. Specifically, it may contain 1.5 parts by weight or more, 2 parts by weight or more, 2.5 parts by weight or more, or 3 parts by weight or more, and may also contain 35 parts by weight or less, 30 parts by weight or less, 25 parts by weight or less, or 20 parts by weight or less. When the above-described ranges are satisfied, low glossiness is effectively expressed in the resin composition, and excellent fluidity may be achieved.

[0122]

[0123] According to one embodiment of the present invention, a method for manufacturing a crosslinked copolymer having an MH constant of 0.2 or more and 0.6 or less comprises: a step (S1) of initiating polymerization by introducing a first reaction solution containing an aromatic vinyl monomer, a vinyl cyanide monomer, and a molecular weight regulator; and a step (S2) of polymerizing while introducing a second reaction solution containing a crosslinking functional compound into the reactor in two or more divided portions, wherein the amount of the crosslinking functional compound introduced into the second reaction solution and the total amount of the molecular weight regulator introduced into the first reaction solution and the second reaction solution have a ratio of 1:2 or more and 1:4 or less.

[0124] According to one embodiment of the present invention, step (S1) is a step of initiating polymerization, and may involve introducing a reaction solution into a reactor and then raising the temperature of the reactor to a predetermined temperature. Even in step (S1), if the internal temperature of the reactor rises above a predetermined temperature, polymerization proceeds in the presence of a polymerization initiator, and in step (S1), the internal temperature of the reactor may be raised to about 60°C to 120°C, and preferably to 70°C to 110°C.

[0125] According to one embodiment of the present invention, the aromatic vinyl monomer 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.

[0126] 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, and within this range, a copolymer can be obtained with a high polymerization conversion rate, and while maintaining the mechanical properties of the copolymer, it has the effect of excellent compatibility with the thermoplastic resin. Preferably, 10% to 50% by weight of the above aromatic vinyl monomer may be added to the first reaction solution of step (S1) relative to the total input amount, and the remaining 50% to 90% by weight may be included in the second reaction solution of step (S2) and added in two or more divided portions.

[0127] According to one embodiment of the present invention, the vinyl cyanide monomer may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile and derivatives thereof, and a specific example may be acrylonitrile.

[0128] 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, and within this range, a copolymer can be obtained with a high polymerization conversion rate, and while maintaining the mechanical properties of the copolymer, it has the effect of excellent compatibility with a thermoplastic resin. Preferably, 10% to 50% by weight of the vinyl cyanide monomer relative to the total input amount may be added to the first reaction solution of step (S1), and the remaining 50% to 90% by weight may be included in the second reaction solution of step (S2) and added in two or more divided portions.

[0129] According to one embodiment of the present invention, the method for manufacturing the crosslinked copolymer may be carried out by a suspension polymerization method, and the first reaction solution of step (S1) may further include one or more additives selected from the group consisting of a polymerization initiator, a water-soluble solvent, a dispersant, a dispersant aid, and a molecular weight regulator as a solvent for carrying out polymerization, and may be carried out in the presence of these.

[0130] According to one embodiment of the present invention, the polymerization initiator is used to facilitate polymerization and is not particularly limited as long as it does not adversely affect the polymerization, but, for example, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di(t-butylperoxy-isopropyl)benzene, t-butyl cumyl peroxide, di-(t-amyl)-peroxide, dicumyl peroxide, butyl 4,4-di(t-butylperoxy)valerate, t-butylperoxybenzoate, 2,2-di(t-butylperoxy)butane, t-amyl peroxy-benzoate, t-butylperoxy-acetate, t-butylperoxy-(2-ethylhexyl)carbonate, t-butylperoxyisopropyl carbonate, t-butylperoxy-3,5,5-trimethyl-hexanoate, It may be one or more selected from the group consisting of 1,1-di(t-butylperoxy)cyclohexane, t-amyl peroxyacetate, t-amylperoxy-(2-ethylhexyl)carbonate, 1,1-di(t-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-di(t-amylperoxy)cyclohexane, t-butyl-monoperoxy-maleate, 1,1'-azodi(hexahydrobenzonitrile), and 1,1'-azobis(cyclohexane-1-cyclonitrile), and specifically, it may be one or more selected from the group consisting of dicumyl peroxide, 1,1-di(t-butylperoxy)cyclohexane, and 1,1'-azobis(cyclohexane-1-cyclonitrile).

[0131] In addition, the polymerization initiator can be used in an amount of 0.001 to 0.5 parts by weight, specifically 0.003 to 0.45 parts by weight or 0.06 to 0.25 parts by weight, based on 100 parts by weight of the total amount of monomers used in polymerization, namely aromatic vinyl monomers and vinyl cyanide monomers. When used within this range, the polymerization reaction can be facilitated, thereby increasing the polymerization conversion rate.

[0132] According to one embodiment of the present invention, the water-soluble solvent may be ion-exchanged water or deionized water. Meanwhile, according to one embodiment of the present invention, the monomer droplet may contain a water-soluble solvent, wherein the water-soluble solvent may be ion-exchanged water or deionized water and may be the same as the water-soluble solvent introduced before the start of polymerization.

[0133] According to one embodiment of the present invention, the dispersant may be one or more selected from the group consisting of water-soluble polyvinyl alcohol, partially saponified polyvinyl alcohol, polyacrylic acid, copolymer of vinyl acetate and maleic anhydride, hydroxypropyl methylcellulose, gelatin, calcium phosphate, tricalcium phosphate, hydroxyapatite, sorbitan monolaurate, sorbitan trioleate, polyoxyethylene, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, and sodium dioctylsulfosuccinate, and a specific example may be calcium phosphate.

[0134] According to one embodiment of the present invention, the dispersant may be used in an amount of 0.5 to 2.0 parts by weight, 0.5 to 1.5 parts by weight, or 1.0 to 1.5 parts by weight based on 100 parts by weight of the total monomer input amount, and within this range, the dispersion stability of the monomers in the polymerization system can be increased to produce a copolymer having more uniform particles.

[0135] In addition, according to one embodiment of the present invention, the method for manufacturing the crosslinked copolymer may further include a dispersion aid during polymerization, and as a specific example, the dispersion aid may be a polyoxyethylene-based dispersion aid, and as a more specific example, may be a polyoxyethylene alkyl ether phosphate, and in this case, the polymerization stability is excellent.

[0136] According to one embodiment of the present invention, the molecular weight regulator may be, for example, one or more selected from the group consisting of α-methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, octyl mercaptan, carbon tetrachloride, methylene chloride, methylene bromide, tetraethyl thiuram disulfide, dipentamethylene thiuram disulfide, and diisopropylxantogen disulfide, and a specific example may be n-dodecyl mercaptan.

[0137] According to one embodiment of the present invention, the molecular weight regulator may be used in an amount of 0.01 to 1.0 parts by weight, 0.05 to 0.8 parts by weight, or 0.10 to 0.6 parts by weight based on 100 parts by weight of total monomer input, and a copolymer having an appropriate weight-average molecular weight can be produced within this range.

[0138] According to one embodiment of the present invention, in step (S2), the second reaction solution containing the crosslinking functional compound may be divided and added two or more times, preferably three or more times. In addition, the crosslinking functional compound may include functional groups such as siloxane groups, vinyl groups, or acrylic groups, and in one crosslinking functional compound, the functional groups may be two or more, preferably three or more.

[0139] When the above-mentioned crosslinking functional compound (hereinafter also referred to as "crosslinking agent") is added only at the beginning of polymerization, the crosslinking effect may be relatively reduced. This is because a high concentration of the crosslinking agent at the beginning of polymerization may increase the possibility of side reactions involving mutual bonding between the crosslinking agents. Furthermore, as the concentration of the crosslinking agent decreases towards the later stages of polymerization, it becomes difficult to achieve a uniform distribution of crosslinked sites within the copolymer chains, hindering the smooth formation of the crosslinked copolymer and potentially leading to a significantly lower yield of the crosslinked copolymer. These problems can ultimately result in an increase in glossiness and the coefficient of variation of light reflection.

[0140] According to one embodiment of the present invention, the crosslinking functional compound is introduced in step (S2), and introduction may begin immediately after step (S1), and may be introduced in two or more divided portions during polymerization, and preferably in three or more divided portions.

[0141] According to one embodiment of the present invention, the time difference between divided inputs when the crosslinking functional compound is introduced in step (S2) may be 1% to 30% of the total polymerization time. When a time difference between divided inputs is provided, the crosslinking structure within the entire copolymer chain in the crosslinking copolymer may become uniform, which can play an important role in performing the function of imparting diffuse reflection to the surface of the resin molded article. In addition, the divided input of the crosslinking agent may be performed for 20% to 70% of the total polymerization time, and it may be desirable to start and end the divided input within this time range to impart a sufficient crosslinking effect.

[0142] According to one embodiment of the present invention, the crosslinking functional compound may be introduced immediately after step (S1), and may be introduced in divided portions so that the introduction is terminated before the polymerization conversion rate reaches 50% to 75%.

[0143] According to one embodiment of the present invention, the crosslinking functional compound divided and added during the polymerization of step (S2) may be added in an amount of 0.01 to 0.5 parts by weight per 100 parts by weight of the total monomer input amount, preferably 0.05 to 0.4 parts by weight, and more preferably 0.05 to 0.3 parts by weight. If the amount of the crosslinking functional compound added is less than the weight of the range described above, there is a lack of crosslinking functional compounds capable of constituting the crosslinked body overall, making it difficult to achieve a desired level of crosslinking and thus difficult to achieve low gloss. If the amount added is excessive compared to the weight of the range described above, a problem of loss of uniformity may occur due to the excessively high degree of crosslinking, and the formation of oligomers due to reactions between crosslinking agents, reactions between crosslinking agents and monomers may adversely affect matte properties, and there may be a problem of polymerization failure or low yield due to significantly worsening polymerization stability. In addition, the amount of the crosslinking functional compound added between each divided input may be the same or different, and it is preferable to control the amount so that the deviation between the input amounts is not large, and the above-mentioned amount may refer to the total amount added in each divided input.

[0144] The above-mentioned crosslinking functional compound is a compound having two or more vinyl groups, acrylic groups, or siloxane groups as described above, for example, a silicone-based crosslinking functional compound or a polyene-based crosslinking functional compound, and the above-mentioned polyene-based crosslinking functional compound 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.

[0145] The above silicone-based crosslinking functional compound 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. may be used in combination, but are not limited thereto.

[0146] The above silicone-based crosslinking functional compound may preferably be 1,3,5-trimethyl-1,3,5-trivinyl-cyclotrisiloxane, divinylmethylsilane, disiloxane, or a mixture thereof, and more preferably divinylmethylsilane.

[0147] According to one embodiment of the present invention, the second reaction solution may further include one or more of a molecular weight regulator and a polymerization initiator.

[0148] In this way, when a molecular weight regulator and / or a polymerization initiator are included in the second reaction solution and added in portions together with the crosslinking functional compound, it can create a synergistic effect with the desired effect of adding the crosslinking functional compound in portions. Furthermore, since it is easier to control the reactivity between monomers and the reactivity between the polymer chain and the crosslinking agent, a uniform and matte molded product can be obtained with low gloss and low coefficient of variation of light reflection.

[0149] According to one embodiment of the present invention, the crosslinking functional compound is divided and added in step (S2), but polymerization can be initiated by including it in the first reaction solution. Although inclusion in the first reaction solution cannot replace addition in step (S2), if an additional crosslinking effect is desired, a method of adding a crosslinking agent before the start of polymerization can be applied. However, when adding the crosslinking functional compound to the first reaction solution of step (S1), one must be careful of the formation of oligomers due to reaction with monomers or the destruction of polymerization stability due to the high reactivity of the crosslinking agent; therefore, it may be desirable to add a compound with relatively low reactivity and a slow reaction rate. The crosslinking functional compound added at this time may be 0.1 to 5.0 parts by weight per 100 parts by weight of the total monomer added, preferably 0.5 to 3.0 parts by weight, and preferably 0.7 to 1.0 parts by weight, and it is preferable to use a crosslinking functional compound different from the one added in step (S2). In this case, the crosslinking functional compound added in step (S1) may be a silicon-based crosslinking functional compound, and the crosslinking functional compound added in step (S2) may be a polyene-based crosslinking functional compound.

[0150] According to one embodiment of the present invention, in the method for manufacturing the crosslinked copolymer, a molecular weight regulator may be further added during the polymerization of step (S2), and the molecular weight regulator may be added in two or more divided portions. In this case, effects and functions similar to those of adding a polyene-based crosslinked functional compound in divided portions can be expected, and a synergistic effect can be achieved with the effects of adding a polyene-based crosslinked functional compound in divided portions.

[0151] Meanwhile, in the method for manufacturing the copolymer according to one embodiment of the present invention, the polymerization in step (S2) may be performed in a temperature range of 50°C to 150°C, preferably 60°C to 130°C, and more preferably 65°C to 120°C. Performing polymerization in this temperature range may be advantageous for obtaining a final polymerization conversion rate, desired particle size characteristics, and other polymer properties.

[0152] According to one embodiment of the present invention, the amount of a crosslinking functional compound introduced into the second reaction solution (for example, if a silicone-based crosslinking functional compound is introduced in step (S1) and a polyene-based crosslinking functional compound is introduced in step (S2), the polyene-based crosslinking functional compound) and the total amount of a molecular weight regulator introduced into the first reaction solution and the second reaction solution may have a ratio of 1:1.5 to 1:4.5, and as a specific example, may have a ratio of 1:1.6 to 1:4.4, 1:1.7 to 1:4.3, 1:1.8 to 1:4.2, 1:1.9 to 1:4.1, or 1:2 to 1:4. If the above range is satisfied, a cross-linked copolymer having an MH constant (Mark-Houwink constant) of 0.2 or more and 0.6 or less can be produced.

[0153] If the ratio of the total amount of the crosslinking functional compound to the total amount of the molecular weight regulator exceeds the above range (e.g., when the ratio of the total amount of the crosslinking functional compound to the total amount of the molecular weight regulator is 1:5, etc.), the crosslinking structure of the crosslinked copolymer produced by adding a relatively small amount of the crosslinking functional compound is not uniform, and thus it may not be possible to impart low gloss to the resin composition. In addition, if the ratio of the total amount of the crosslinking functional compound to the total amount of the molecular weight regulator is less than the above range (e.g., when the ratio of the total amount of the crosslinking functional compound to the total amount of the molecular weight regulator is 1:1.4, etc.), the degree of branching of the crosslinked copolymer produced is lowered (i.e., the MH constant increases), and thus the flowability is reduced, so excellent fluidity may not be exhibited in the resin composition.

[0154]

[0155] Other additives

[0156] A resin composition according to one embodiment of the present invention may further include additives.

[0157] 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.

[0158] 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.

[0159]

[0160] <Molded Product>

[0161] The present invention provides a molded article formed from the resin composition.

[0162] 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.

[0163]

[0164] 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.

[0165]

[0166] 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.

[0167]

[0168] Preparation Example 1

[0169] 120 parts by weight of ion-exchanged water, 77 parts by weight of styrene, 23 parts by weight of acrylonitrile, 0.2 parts by weight of 1,1'-azobis(cyclohexane-1-carbonitrile), 0.2 parts by weight of n-dodecyl mercaptan, and 0.7 parts by weight of divinylmethylsilane were added to a reactor, and the temperature of the reactor was raised to 70°C. Then, 0.1 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 cross-linked copolymer (in bead form) was prepared by washing, dehydrating, and drying, and the yield was 98%.

[0170] Here, each of the above weight parts is a weight part based on 100 weight parts of the total monomer input amount.

[0171] In addition, the yield (polymerization conversion rate) of the cross-linked copolymer indicates the degree to which monomers are polymerized by a polymerization reaction to form a desired polymer. Here, the desired polymer is understood as a concept excluding olegoromers that failed to form a polymer, unreacted monomers, and aggregates that are deformed due to polymers aggregating together and attaching to the structure of the reactor during polymer formation. In the present invention, the yield (polymerization conversion rate) of the cross-linked copolymer was calculated using the following Equation 4 after drying the polymer obtained after polymerization at 85°C for 24 hours so that the moisture content of the polymer obtained after polymerization was 3% or less.

[0172] [Mathematical Formula 4]

[0173] Polymerization yield (%) = [(Weight of polymer obtained by drying) / (Total weight of monomers added during reaction)] × 100

[0174]

[0175] Preparation Example 2

[0176] A cross-linked copolymer was prepared in the same manner as in Preparation Example 1, except that the amount of n-dodecyl mercaptan added was changed from 0.2 parts by weight to 0.3 parts by weight and the amount of allyl methacrylate added was changed from 0.1 parts by weight to 0.15 parts by weight, and the yield was 97.5%.

[0177]

[0178] Preparation Example 3

[0179] A cross-linked copolymer was prepared in the same manner as in Preparation Example 1, except that the amount of n-dodecyl mercaptan added was changed from 0.2 parts by weight to 0.375 parts by weight and the amount of allyl methacrylate added was changed from 0.1 parts by weight to 0.15 parts by weight, and the yield was 96.7%.

[0180]

[0181] Preparation Example 4

[0182] A cross-linked copolymer was prepared in the same manner as in Preparation Example 1, except that the amount of n-dodecyl mercaptan added was changed from 0.2 parts by weight to 0.3 parts by weight, and the yield was 97.1%.

[0183]

[0184] Comparative Manufacturing Example 1

[0185] A cross-linked copolymer was prepared in the same manner as in Preparation Example 1, except that the amount of allyl methacrylate added was changed from 0.1 parts by weight to 0.14 parts by weight, and the yield was 96%.

[0186]

[0187] Comparative Manufacturing Example 2

[0188] A cross-linked copolymer was prepared in the same manner as in Preparation Example 1, except that the amount of allyl methacrylate added was changed from 0.1 parts by weight to 0.2 parts by weight, and the yield was 95%.

[0189]

[0190] Comparative Manufacturing Example 3

[0191] A cross-linked copolymer was prepared in the same manner as in Preparation Example 1, except that t-dodecyl mercaptan was not added, and the yield was 92%.

[0192]

[0193] Comparative Manufacturing Example 4

[0194] A cross-linked copolymer was prepared in the same manner as in Preparation Example 1, except that the amount of t-dodecyl mercaptan added was changed from 0.2 parts by weight to 0.1 parts by weight and the amount of allyl methacrylate added was changed from 0.1 parts by weight to 0.2 parts by weight, and the yield was 94%.

[0195]

[0196] Comparative Manufacturing Example 5

[0197] A cross-linked copolymer was prepared in the same manner as in Preparation Example 1, except that the amount of t-dodecyl mercaptan added was changed from 0.2 parts by weight to 1 part by weight and the amount of allyl methacrylate added was changed from 0.1 parts by weight to 0.2 parts by weight, and the yield was 83%.

[0198]

[0199] Comparative Manufacturing Example 6

[0200] 120 parts by weight of ion-exchanged water, 77 parts by weight of styrene, 23 parts by weight of acrylonitrile, 0.2 parts by weight of 1,1'-azobis(cyclohexane-1-carbonitrile), and 0.2 parts by weight of n-dodecyl mercaptan were added to a reactor, and the temperature of the reactor was raised to 70°C. Then, 0.16 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 cross-linked copolymer (in bead form) was prepared by washing, dehydrating, and drying, and the yield was 92%.

[0201]

[0202] Example 1

[0203] A resin composition was prepared by mixing 20 parts by weight of the crosslinked copolymer prepared in Preparation Example 1 above, 55 parts by weight of a matrix copolymer (LG Chem, 83SF), 25 parts by weight of a graft copolymer (LG Chem, DP270M), and 0.1 parts by weight of a heat stabilizer (BASF, IRGANOX 1010).

[0204]

[0205]

[0206] Example 2

[0207] A resin composition was formulated in the same manner as in Example 1, except that 20 parts by weight of the cross-linked copolymer prepared in Preparation Example 2 were used instead of 20 parts by weight of the cross-linked copolymer prepared in Preparation Example 1.

[0208]

[0209] Example 3

[0210] A resin composition was formulated in the same manner as in Example 1, except that 20 parts by weight of the cross-linked copolymer prepared in Preparation Example 3 were used instead of 20 parts by weight of the cross-linked copolymer prepared in Preparation Example 1.

[0211]

[0212] Example 4

[0213] A resin composition was formulated in the same manner as in Example 1, except that 20 parts by weight of the cross-linked copolymer prepared in Preparation Example 4 were used instead of 20 parts by weight of the cross-linked copolymer prepared in Preparation Example 1.

[0214]

[0215] Comparative Example 1

[0216] A resin composition was formulated in the same manner as in Example 1, except that 20 parts by weight of the cross-linked copolymer prepared in Comparative Example 1 was used instead of 20 parts by weight of the cross-linked copolymer prepared in Preparation Example 1.

[0217]

[0218] Comparative Example 2

[0219] A resin composition was formulated in the same manner as in Example 1, except that 20 parts by weight of the cross-linked copolymer prepared in Comparative Example 2 was used instead of 20 parts by weight of the cross-linked copolymer prepared in Preparation Example 1.

[0220]

[0221] Comparative Example 3

[0222] A resin composition was formulated in the same manner as in Example 1, except that 20 parts by weight of the cross-linked copolymer prepared in Comparative Example 3 was used instead of 20 parts by weight of the cross-linked copolymer prepared in Preparation Example 1.

[0223]

[0224] Comparative Example 4

[0225] A resin composition was formulated in the same manner as in Example 1, except that 20 parts by weight of the cross-linked copolymer prepared in Comparative Example 4 was used instead of 20 parts by weight of the cross-linked copolymer prepared in Preparation Example 1.

[0226]

[0227] Comparative Example 5

[0228] A resin composition was formulated in the same manner as in Example 1, except that 20 parts by weight of the cross-linked copolymer prepared in Comparative Example 5 was used instead of 20 parts by weight of the cross-linked copolymer prepared in Preparation Example 1.

[0229]

[0230] Comparative Example 6

[0231] A resin composition was formulated in the same manner as in Example 1, except that 20 parts by weight of the cross-linked copolymer prepared in Comparative Example 6 was used instead of 20 parts by weight of the cross-linked copolymer prepared in Preparation Example 1.

[0232]

[0233] Experimental Example 1 - Measurement of Physical Properties of Crosslinked Copolymer

[0234] The physical properties of each cross-linked copolymer prepared in the above Preparation Examples 1 to 4 and Comparative Preparation Examples 1 to 6 were measured as follows and are listed in Table 1 below.

[0235]

[0236] * MH constant (Mark-Houwink constant): 5g of each cross-linked copolymer prepared in the above preparation example and comparative preparation example is added to 50g of tetrahydrofuran (THF) solution and stirred for 24 hours to dissolve it sufficiently, then filtered through a 325 mesh, and the solution that passed through the mesh is dried at 80°C for 24 hours. Then, the weight of the dried polymer is measured and added to the tetrahydrofuran (THF) solution to prepare a sample solution at a concentration of 0.1 wt%.

[0237] Subsequently, GPC-viscometry analysis was performed using a triple detector system consisting of a Light Scattering Detector and three columns (two PL-gel Olexis and one PL-gel mixed-C) connected in series, a Light Scattering Detector, a Viscometer, and an RI Detector (Viscotek TDA 305) connected in series. THF was used as the mobile phase (flow rate 1.0 ml / min), and 100 µl of each sample solution was added at 40°C. Here, PS STD 113K was used as the standard sample, and the dn / dc value was set to 0.1760–0.1772 for data analysis (Omni SEC).

[0238] Subsequently, a Mark-Houwink plot was constructed using the molecular weight (M) and intrinsic viscosity (η) of each sample measured by GPC-viscometry analysis, and the slope values ​​(a, MH constant) were calculated and listed in Table 1 below.

[0239]

[0240] Experimental Example 2 - Measurement of Physical Properties of Resin Composition

[0241] The resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 6 were fed into a twin-screw extruder, kneaded and extruded at 200°C to produce pellets, and after injecting the pellets at 220°C, the insoluble matter content, melt index, glossiness, and coefficient of variation of light reflection were measured by the following method and are shown in Table 1 below.

[0242]

[0243] * 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.

[0244] [Mathematical Formula 1]

[0245]

[0246] In the above mathematical formula 1,

[0247] X is the insoluble matter content (%), and

[0248] A is the weight (g) of the obtained insoluble material, and

[0249] B is the weight (g) of the resin composition (pellet).

[0250]

[0251] * Gloss: The gloss at 60° was measured using a gloss meter (Gloss meter, Nippon Denshoku, VG7000) according to the evaluation method of ASTM D523.

[0252]

[0253] * Coefficient of variation in light reflection (C LR ): It was derived using Python with the following method.

[0254] 1) Sample imaging: Using a DSLR camera (Canon 750D) and a 200 mm x 200 mm surface light (White LED, Collimated Backlight LTS-3PFT), the prepared sample is photographed and imaged with the distance between the camera and the sample set to 40 cm, the distance between the sample and the light set to 100 cm, and the angle set to 90°.

[0255] 2) Grayscale conversion of the sample image: The sample image is converted to grayscale (0~255) using the OpenCV library. At this time, a grayscale value is assigned to each pixel within the sample image, and this grayscale value is used as the luminosity.

[0256] 3) Reconstruction of the image: The above image is divided into a grid of 200 µm x 200 µm, and the image is reconstructed by averaging the luminance values ​​(grayscale values) of the pixels within each grid. At this time, each grid has a single averaged luminance value.

[0257] 4) Luminous intensity correction: The target grid is designated as Zone 1, the 8 grids adjacent to Zone 1 as Zone 2, and the 16 grids adjacent to Zone 2 as Zone 3. After assigning zone-specific correction coefficients of 1 to Zone 1, -0.0625 to Zone 2, and -0.03125 to Zone 3, the corrected luminous intensity value of the target grid is derived using the following Equation 3.

[0258] [Mathematical Formula 3]

[0259]

[0260] In the above mathematical formula 3, L is the corrected luminosity value of the target grating, and L 1 is the luminosity of the Zone 1 grid, L 2 1, L 2 2, L 2 3, ..., L 2 8 is the luminous intensity of each of the 8 grids in Zone 2, L 3 1, L 3 2, L 3 3, ..., L 3 16 is the luminosity of each of the 16 grids in Zone 3.

[0261] 5) Derivation of mean and standard deviation: The mean and standard deviation are calculated from the corrected luminous intensity values ​​of each grid, and the coefficient of variation in light reflection is derived using the following mathematical formula 2 using the mean and standard deviation of the luminous intensity calculated in this way.

[0262] [Mathematical Formula 2]

[0263] C LR = D L / M L

[0264] The above C LR is the coefficient of variation of light reflection, and D L is the standard deviation of luminous intensity, and M L is the average luminous intensity.

[0265]

[0266] * Melt index (g / 10 min): Measured at 220°C and 10 kg according to the ASTM D1238 method.

[0267]

[0268] Examples Comparative Examples 1234123456 Crosslinked Copolymer MH Constant 0.54 0.52 0.5 0.45 0.63 0.68 0.78 0.63 0.5 0.62 Resin Composition Insoluble Content (%) 1.0 2.5 0.9 0.62 3 1.3 0.54 0.13 1 Gloss (60°) 1215 1416 19 1118 2235 15C LR 111.21.11.11.32.21.51.72.6 Melt Index (g / 10min) 30 28 32 35 15 17 10 12 3125

[0269] Referring to Table 1 above, it was confirmed that the resin compositions of Examples 1 to 4, which include a cross-linked copolymer satisfying a desirable range of MH constants and a desirable range of insoluble content, exhibit low gloss, excellent coefficient of variation of light reflection, and melt index.

[0270] It was confirmed that the resin compositions of Comparative Examples 1 to 4 and 6, which contain crosslinked copolymers that do not satisfy the desired MH constant, showed a lower melt index compared to Examples 1 to 4. In particular, in the case of Comparative Example 6, it was confirmed that the coefficient of variation of light reflection also increased.

[0271] It was confirmed that the resin composition of Comparative Example 5, which has an insoluble content below the desirable range, did not exhibit a lower gloss 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; and It comprises a cross-linked copolymer having an MH constant (Mark-Houwink constant) of 0.2 or more and 0.6 or less, and A resin composition having an insoluble content (X) calculated by the following mathematical formula 1 of 0.3% or more and 7% 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.

2. In Paragraph 1, The above-mentioned crosslinked copolymer is, A resin composition comprising an aromatic vinyl monomer unit, a vinyl cyanide monomer unit, and a crosslinking portion derived from a crosslinking functional compound.

3. In Paragraph 1, The above-mentioned crosslinked copolymer is, A resin composition having an MH constant of 0.4 or more and 0.55 or less.

4. In Paragraph 1, The glossiness (60°) measured according to the ASTM D523 method is 25 or less, and A resin composition having a coefficient of variation in light reflection calculated by the following mathematical formula 2 of 2.0 or less: [Mathematical Formula 2] C LR = D L / M L The above C LR is the coefficient of variation of light reflection, and D L is the standard deviation of luminous intensity, and M L is the average luminous intensity.

5. In Paragraph 4, A resin composition having a glossiness (60°) of 20 or less as measured according to the ASTM D523 method.

6. In Paragraph 4, A resin composition having a coefficient of variation of light reflection of 1.5 or less.

7. 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.

8. Comprising a crosslinked portion formed from an aromatic vinyl monomer unit, a vinyl cyanide monomer unit, and a crosslinking functional compound, A cross-linked copolymer having an MH constant of 0.2 or more and 0.6 or less.

9. In Paragraph 1, A cross-linked copolymer having an MH constant of 0.4 or more and 0.55 or less.

10. A step (S1) of initiating polymerization by introducing a first reaction solution comprising an aromatic vinyl monomer, a vinyl cyanide monomer, a silicone-based crosslinking functional compound, and a molecular weight regulator; and The method includes a step (S2) of polymerizing while adding a second reaction solution, which includes a polyene-based crosslinking functional compound or a polyene-based crosslinking functional compound and a molecular weight regulator, to the reactor in two or more divided portions. A method for manufacturing a crosslinked copolymer, wherein the amount of a polyane-based crosslinking functional compound added to the second reaction solution and the total amount of a molecular weight regulator added to the first reaction solution and the second reaction solution have a ratio of 1:1.5 or more and 1:4.5 or less.

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