Resin composition and preparation method therefor

Abstract

The present invention relates to a resin composition comprising: a crosslinked copolymer and a first matrix copolymer in appropriate amounts, wherein the crosslinked copolymer satisfies desired ranges of the particle size when a cumulative percentage on the basis of weight reaches 50% in a particle size distribution (D50), and an average H-W ratio, and the first matrix copolymer includes an aromatic vinyl-based monomer unit, a vinyl cyanide-based monomer unit, and an alkyl (meth) acrylate monomer unit, whereby the resin composition is superb in terms of mechanical properties such as surface characteristics, matte properties, and scratch resistance.

Description

Resin composition and method for producing the same

[0001] [Cross-reference with related applications]

[0002] This application claims the benefit of priority to Korean Patent Application No. 2023-0142385, filed October 23, 2023, the entire contents of which are incorporated herein by reference.

[0003]

[0004] [Technical Field]

[0005] The present invention relates to a resin composition and a method for producing the same.

[0006] Acrylonitrile-butadiene-styrene (ABS) copolymers are manufactured by grafting styrene and acrylonitrile onto a rubbery butadiene polymer. ABS copolymers offer a balanced combination of rigidity, chemical resistance, impact resistance, and processability. They also boast excellent impact strength, mechanical properties, surface gloss, and secondary processing characteristics, such as plating, printing, and painting. They also offer the advantage of being able to produce products in a variety of colors.

[0007] Moreover, recently, the demand for plastics with a matte finish has been increasing to improve the appearance of products. To this end, methods are known for manufacturing sheets by coextruding polymethyl methacrylate (PMMA) particles with ABS resin as a substrate layer, extruding sheets using a cross-linked polymer as a matting agent through reactive extrusion, or mixing in crystalline polymers such as syndiotactic polystyrene (sPS) or polyamide (PA). However, when manufacturing using the above-mentioned manufacturing methods, there are problems such as a significant deterioration in the mechanical properties of the resin composition or a decrease in processability.

[0008] [Prior Art Literature]

[0009] [Patent Document]

[0010] (Patent Document 0001) KR 1205204 B1

[0011] The problem to be solved by the present invention is to provide a resin composition having high mechanical properties such as scratch resistance and high surface uniformity while having a matte characteristic.

[0012] Another problem to be solved by the present invention is to provide a method for producing a resin composition having high mechanical properties such as scratch resistance and high surface uniformity while having a matte characteristic.

[0013] (1) The present invention comprises a graft copolymer comprising a conjugated diene polymer, an aromatic vinyl monomer unit, and a vinyl cyan monomer unit; a matrix copolymer; and a crosslinked copolymer comprising a crosslinking moiety formed from an aromatic vinyl monomer unit, a vinyl cyan monomer unit, and a crosslinking functional compound, wherein the particle diameter (D) when the weight-based cumulative percentage on the particle size distribution of the crosslinked copolymer reaches 50% 50 ) is 30 ㎛ or more and 100 ㎛ or less, and the average HW ratio of the crosslinked copolymer satisfies the following mathematical formula 1, and the matrix copolymer comprises: a first matrix copolymer comprising an aromatic vinyl monomer unit, a vinyl cyan monomer unit, and an alkyl (meth)acrylate monomer unit; or, a second matrix copolymer comprising an aromatic vinyl monomer unit and a vinyl cyan monomer unit, and the first matrix copolymer, and when the matrix copolymer comprises the first matrix copolymer and the second matrix copolymer, the content of the first matrix copolymer is greater than the content of the second matrix copolymer.

[0014] [Mathematical Formula 1]

[0015] 0.05≤ Average HW ratio ≤1

[0016] In the above mathematical expression 1, the average HW ratio is the average value of the HW ratio (a / b) calculated for each crosslinked copolymer observed when the surface of the resin composition is observed with an optical microscope,

[0017] The above a is ½ the value of the shortest axis length of each cross-linked copolymer observed when observed with an optical microscope,

[0018] The above b is the longest axis length of each crosslinked copolymer observed when observed with an optical microscope.

[0019] (2) The present invention provides a resin composition in which, in the above (1), the crosslinking functional compound is a compound containing a vinyl functional group.

[0020] (3) The present invention provides a resin composition in which, in the above (1) or (2), the crosslinking functional compound is allyl methacrylate.

[0021] (4) The present invention is characterized in that, in any one of the above (1) to (3), the D of the crosslinked copolymer 50 Provided is a resin composition having a particle size of 30 ㎛ or more and 70 ㎛ or less.

[0022] (5) The present invention provides a resin composition in which, in any one of the above (1) to (4), when the matrix copolymer includes the first matrix copolymer and the second matrix copolymer, the first matrix copolymer is included in an amount of 60 wt% or more based on the total of the first matrix copolymer and the second matrix copolymer.

[0023] (6) The present invention provides a resin composition comprising, in any one of the above (1) to (5), 40 parts by weight or more and 70 parts by weight or less of the matrix copolymer relative to 100 parts by weight of the total of the graft copolymer, the matrix copolymer, and the crosslinked copolymer.

[0024] (7) The present invention provides a resin composition comprising, in any one of the above (1) to (6), 10 parts by weight or more and 40 parts by weight or less of the crosslinked copolymer relative to 100 parts by weight of the total of the graft copolymer, the matrix copolymer, and the crosslinked copolymer.

[0025] (8) The present invention provides a resin composition having a pencil hardness of HB or higher as measured by the evaluation method of ASTM D 336 in any one of the above (1) to (7).

[0026] (9) The present invention provides a resin composition having a light reflection variation coefficient calculated by the following mathematical formula 1 of 1.5 or less in any one of the above (1) to (8).

[0027] [Mathematical Formula 1]

[0028] C LR = D L / M L

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

[0030] (10) The present invention provides a resin composition having a glossiness of 20 or less at 60° as measured by a gloss meter according to the evaluation method of ASTM D523 in any one of (1) to (9) above.

[0031] The resin composition according to the present invention has a matte characteristic and excellent mechanical properties such as scratch resistance and surface uniformity.

[0032] The manufacturing method according to the present invention can provide a resin composition having a matte characteristic and excellent mechanical properties such as scratch resistance and surface uniformity.

[0033] Hereinafter, the present invention will be described in more detail to help understand the present invention.

[0034] Terms or words used in this specification and claims should not be interpreted as limited to their usual or dictionary meanings, but should be interpreted as meanings and concepts that conform to the technical idea of ​​the present invention, based on the principle that the inventor can appropriately define the concept of the term to explain his or her own invention in the best way.

[0035]

[0036] The terms and measurement methods used in the present invention may be defined as follows unless otherwise defined.

[0037] The term 'composition' as used in the present invention includes a mixture of materials comprising the composition as well as reaction products and decomposition products formed from the materials of the composition.

[0038] The term 'monomer unit', 'crosslinking unit', or 'crosslinking portion' used in the present invention may mean 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 resulting therefrom, or the material itself.

[0039] The term 'derivative' used in the present invention may refer to a compound having a structure in which at least one of the hydrogen atoms constituting the original compound is substituted with a halogen group, an alkyl group, or a hydroxy group.

[0040]

[0041] Resin composition

[0042] The present invention provides a resin composition.

[0043] The resin composition according to the present invention comprises a graft copolymer comprising a conjugated diene polymer, an aromatic vinyl monomer unit, and a vinyl cyan monomer unit; a matrix copolymer; and a crosslinked copolymer comprising a crosslinking moiety formed from an aromatic vinyl monomer unit, a vinyl cyan monomer unit, and a crosslinking functional compound, wherein the particle diameter (D) when the weight-based cumulative percentage on the particle size distribution of the crosslinked copolymer reaches 50% 50 ) is 30 ㎛ or more and 100 ㎛ or less, and the average HW ratio of the crosslinked copolymer satisfies the following mathematical formula 1, and the matrix copolymer comprises: a first matrix copolymer comprising an aromatic vinyl monomer unit, a vinyl cyan monomer unit, and an alkyl (meth)acrylate monomer unit; or, a second matrix copolymer comprising an aromatic vinyl monomer unit and a vinyl cyan monomer unit, and the first matrix copolymer, and when the matrix copolymer comprises the first matrix copolymer and the second matrix copolymer, the content of the first matrix copolymer is greater than the content of the second matrix copolymer.

[0044] [Mathematical Formula 1]

[0045] 0.05≤ Average HW ratio ≤1

[0046] In the above mathematical expression 1, the average HW ratio is the average value of the HW ratio (a / b) calculated for each crosslinked copolymer observed when the surface of the resin composition is observed with an optical microscope,

[0047] The above a is ½ the value of the shortest axis length of each cross-linked copolymer observed when observed with an optical microscope,

[0048] The above b is the longest axis length of each crosslinked copolymer observed when observed with an optical microscope.

[0049] Conventional matte products typically involve roughening the surface of an injection mold with a corrosion treatment, then injecting resin to create a diffusely reflective surface. However, this method presents challenges in achieving a practical matte finish, and the resulting wear on the injection mold reduces processability, making it unsuitable for mass production.

[0050] Meanwhile, some molded products attempt to achieve a matte finish through post-processing. For example, a film containing a crosslinker is co-extruded and applied to create a pattern on the surface. Another method involves applying a crosslinker to the product and then UV curing it to create a pattern on the surface. However, these methods have limitations in the achievable gloss level and suffer from poor surface uniformity.

[0051] Gloss is a representative value that can express the gloss (high gloss, low gloss) or matte of a resin. In general, commercially available matte molded products have a gloss value exceeding 30, which cannot be considered practically matte. However, when using the resin composition of the present invention, gloss can be implemented at a very low level, making it possible to implement a matte product.

[0052] In addition, according to one embodiment of the present invention, the resin composition has excellent pencil hardness, low gloss, and low coefficient of variation of light reflection, so that it is possible to provide a matte molded product with a uniform surface, and these characteristics are specific D 50 It can be implemented by including an aromatic vinyl-vinyl cyan-acrylic crosslinked copolymer having a range and an average HW ratio and a first matrix copolymer including an aromatic vinyl monomer unit, a vinyl cyan monomer unit and an alkyl (meth)acrylate monomer unit, and the problem of the existing matte molded product can be solved through this crosslinked copolymer.

[0053]

[0054] A resin composition according to one embodiment of the present invention may have a pencil hardness of HB or higher as measured by the evaluation method of ASTM D 336.

[0055]

[0056] According to one embodiment of the present invention, the resin composition may have a glossiness at 60° measured by a gloss meter according to the evaluation method of ASTM D523 of 20 or less, and for specific examples, may be 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, or 6 or less.

[0057]

[0058] Hereinafter, each component included in the above resin composition will be described in detail.

[0059]

[0060] 1. Crosslinked copolymer

[0061] According to one embodiment of the present invention, the crosslinked copolymer imparts surface properties to the resin composition such that light can be diffusely reflected from the surface. Due to crosslinking, the crosslinked copolymer is manufactured in a form with higher strength and can be uniformly distributed within the matrix resin. When the crosslinked copolymer is included in the resin composition, the gloss and light reflection coefficient of variation can be implemented with very low levels, while the impact strength can be improved to an excellent level.

[0062] According to one embodiment of the present invention, the crosslinked copolymer may be included in an amount of 10 parts by weight or more and 35 parts by weight or less, based on 100 parts by weight of the resin composition, and more specifically, it may be included in an amount of 11 parts by weight or more, 12 parts by weight or more, 13 parts by weight or more, 14 parts by weight or more, or 15 parts by weight or more, and further, it may be included in an amount of 34 parts by weight or less, 33 parts by weight or less, 32 parts by weight or less, 31 parts by weight or less, or 30 parts by weight or less. When the crosslinked copolymer is included in the above range, the above effect can be better realized.

[0063]

[0064] According to one embodiment of the present invention, the crosslinked copolymer may include a crosslinking portion formed from a crosslinking functional compound, an aromatic vinyl monomer unit, and a vinyl cyan monomer unit.

[0065] The above crosslinked copolymer may be a random copolymer, and the composition of the aromatic vinyl monomer units and vinyl cyan 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 in the polymer that is polymerized and grows by the polymerization reaction of the monomer is maintained uniformly. As a specific example, as the polymerization progresses, that is, when a portion of the polymer in the reactor is collected according to changes in the polymerization time during the polymerization, the ratio of each monomer unit forming the polymer may be maintained uniformly.

[0066] According to one embodiment of the present invention, the aromatic vinyl monomer unit and the vinyl cyan monomer unit may refer to repeating units formed by the aromatic vinyl monomer and the vinyl cyan monomer participating in a polymerization reaction, respectively. As a specific example, the polymerization reaction may be a radical polymerization reaction, and thus, may refer to repeating units derived from carbon-carbon double bonds present in the aromatic vinyl monomer and the vinyl cyan monomer.

[0067]

[0068] According to one embodiment of the present invention, the crosslinking portion may include a crosslinking functional compound unit formed from a crosslinking functional compound, and the crosslinking functional compound may include at least one selected from the group consisting of an acrylic compound and an allyl compound, and the crosslinking portion may be formed from units derived from these compounds.

[0069] A crosslinked copolymer according to one embodiment of the present invention may have crosslinking units very uniformly distributed therein, and the degree of distribution of the crosslinking units may be appropriate, so that the fluidity between the entire chains is alive.

[0070] According to one embodiment of the present invention, the crosslinking functional compound may include at least one selected from the group consisting of acrylic compounds and aryl compounds as described above, and may include a functional group such as a vinyl group or an acrylic group, and specifically, at least one selected from the group consisting of divinylbenzene, trivinylbenzene, ethylene glycol di(meth)acrylate, allyl (meth)acrylate, diallyl phthalate, diallyl maleate, triallyl isocyanurate, and trialkyl isocyanurate may be applied, and may be divinylbenzene or allyl methacrylate.

[0071] According to one embodiment of the present invention, the crosslinked copolymer may contain the crosslinking unit in an amount of 0.05 parts by weight or more and 5 parts by weight or less, based on 100 parts by weight of the total of the aromatic vinyl monomer unit and the vinyl cyan monomer unit, and more specifically, it may contain 0.055 parts by weight or more, 0.06 parts by weight or more, 0.065 parts by weight or more, 0.07 parts by weight or more, 0.075 parts by weight or more, or 0.08 parts by weight or more, and further, it may contain 4.5 parts by weight or less, 4 parts by weight or less, 3.5 parts by weight or less, 3 parts by weight or less, 2.5 parts by weight or less, or 2 parts by weight or less. When the above range is satisfied, the degree of crosslinking can be implemented at an appropriate level.

[0072]

[0073] According to one embodiment of the present invention, the aromatic vinyl monomer for forming the aromatic vinyl monomer unit included in the crosslinked copolymer may be at least one selected from the group consisting of styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, o-methylstyrene, ot-butylstyrene, bromostyrene, chlorostyrene, trichlorostyrene, and derivatives thereof, and a specific example thereof may be styrene.

[0074] According to one embodiment of the present invention, the crosslinked copolymer may contain 60 parts by weight or more and 85 parts by weight or less of the aromatic vinyl monomer unit, based on 100 parts by weight of the total of the aromatic vinyl monomer unit and the vinyl cyan monomer unit, and for more specific examples, it may contain 62 parts by weight or more, 64 parts by weight or more, 66 parts by weight or more, 68 parts by weight or more, 70 parts by weight or more, or 72 parts by weight or more, and further, it may contain 84 parts by weight or less, 83 parts by weight or less, 82 parts by weight or less, 81 parts by weight or less, 80 parts by weight or less, or 79 parts by weight or less.

[0075]

[0076] According to one embodiment of the present invention, the vinyl cyan monomer for forming the vinyl cyan monomer unit included in the crosslinked copolymer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and derivatives thereof, and a specific example thereof may be acrylonitrile.

[0077] According to one embodiment of the present invention, the crosslinked copolymer may contain 15 parts by weight or more and 40 parts by weight or less of the vinyl cyan monomer unit, based on 100 parts by weight of the total of the aromatic vinyl monomer unit and the vinyl cyan monomer unit, and as a more specific example, it may contain 16 parts by weight or more, 17 parts by weight or more, 18 parts by weight or more, 19 parts by weight or more, 20 parts by weight or more, or 21 parts by weight or more, and further, it may contain 38 parts by weight or less, 36 parts by weight or less, 34 parts by weight or less, 32 parts by weight or less, 30 parts by weight or less, or 28 parts by weight or less.

[0078]

[0079] According to one embodiment of the present invention, the crosslinked copolymer has a particle size (D) when the cumulative percentage based on weight on the particle size distribution reaches 50%. 50 ) may be 30 ㎛ or more and 100 ㎛ or less. In the present invention, D 50 It means the particle size when the cumulative percentage based on weight on the particle size distribution reaches 50%, and it means the particle size when the cumulative weight from the sample with the smallest particle size on the particle size distribution reaches 50%. In the present invention, D of the crosslinked copolymer 50 It can be measured using a laser diffraction measuring device, and as a specific example, it can be measured using a light diffraction particle size analyzer (manufacturer: Sympatec GmbH, product name: HELOS / KR).

[0080] According to one embodiment of the present invention, the crosslinked copolymer has a particle size (D) when the cumulative percentage based on weight on the particle size distribution reaches 50%. 50 ) may be 32 ㎛ or more, 34 ㎛ or more, 36 ㎛ or more, 38 ㎛ or more, or 40 ㎛ or more, and, as a specific example, may be 95 ㎛ or less, 90 ㎛ or less, 85 ㎛ or less, 80 ㎛ or less, 75 ㎛ or less, 70 ㎛, 65 ㎛ or less, 60 ㎛ or less, 55 ㎛ or less, or 50 ㎛ or less. D of the crosslinked copolymer 50When the above range is satisfied, low gloss and excellent surface properties can be realized in the resin composition. If the D of the crosslinked copolymer 50 If it is larger than the above range, when the crosslinked copolymer is dispersed in the matrix, the surface roughness caused by the crosslinked copolymer may increase, which may deteriorate the surface properties and light reflection coefficient of the resin composition. In addition, the D of the crosslinked copolymer 50 If it is smaller than the above range, the surface roughness of the crosslinked copolymer dispersed in the matrix becomes small, so that diffuse reflection does not occur efficiently, and the gloss of the resin composition may increase.

[0081]

[0082] The crosslinked copolymer according to one embodiment of the present invention may have an average HW ratio of 0.05 or more and 1 or less. In the present invention, the average HW ratio of the crosslinked copolymer means the average value of the HW ratio (a / b) of each crosslinked copolymer observed when the surface of the resin composition is observed with an optical microscope. The a is half the value of the shortest axis length of each crosslinked copolymer observed when observed with an optical microscope, and the b is the longest axis length of each crosslinked copolymer observed when observed with an optical microscope.

[0083] Specifically, the crosslinked copolymer can be observed as a plane in an optical microscope image. The plane of the crosslinked copolymer observed in the optical microscope image is referred to as a 'plane', and assuming that the density of the crosslinked copolymer is constant, when the center of gravity of the crosslinked copolymer is within the 'plane', the longest axis of the crosslinked copolymer means the longest distance from the straight lines passing through the center of gravity to the two points where it meets the surface of the plane, and the shortest axis of the crosslinked copolymer means the shortest distance from the straight lines passing through the center of gravity to the two points where it meets the surface of the plane.

[0084] The crosslinked copolymer according to one embodiment of the present invention may have an average HW ratio of 0.052 or more, 0.054 or more, 0.056 or more, 0.058 or more, or 0.6 or more, and may also have an average HW ratio of 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.4 or less, or 0.3 or less. When the average HW ratio of the crosslinked copolymer satisfies the above range, low gloss and excellent surface properties can be implemented in the resin composition.

[0085]

[0086] According to one embodiment of the present invention, the resin composition may have a gloss of 20 or less, and for specific examples, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, or 6 or less. If the resin composition does not contain a crosslinked copolymer, the gloss of the resin composition may exceed the above-described range, and the pencil hardness may be reduced.

[0087]

[0088] Furthermore, the resin composition according to one embodiment of the present invention comprises the crosslinked copolymer, thereby enabling the provision of a nonporous molded article with guaranteed surface uniformity. The coefficient of variation of light reflection is a numerical value that indicates the uniformity of the surface of the molded article and also reflects gloss, indicating whether diffuse reflection occurs equally anywhere on the surface of the molded article while maintaining a matte, uniform surface throughout.

[0089]

[0090] The above light reflection variation coefficient can be measured using Python in the following manner.

[0091] 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 at a distance of 40 cm from the camera and 100 cm from the sample and at an angle of 90°.

[0092] 2) Grayscale conversion of sample image: The sample image is converted to grayscale (0-255) using the Open CV library. At this time, a grayscale value is assigned to each pixel in the sample image, and this grayscale value is used as the luminance.

[0093] 3) Image reconstruction: The image is divided into grids of 200 ㎛ x 200 ㎛ in size, and the image is reconstructed by averaging the luminance values ​​(grayscale values) of the pixels within each grid. At this time, each grid has one averaged luminance value.

[0094] 4) Luminance 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 luminance value of the target grid is derived using the following mathematical expression 2.

[0095] [Equation 2]

[0096]

[0097] In the above mathematical expression 2, L is the luminosity of the grid to be measured, L1 is the luminosity of the grid in the first zone, L21, L22, L23, ..., L28 are the luminosities of each of the eight grids in the second zone, and L31, L32, L33, ..., L316 are the luminosities of each of the 16 grids in the third zone.

[0098] The above correction factor is intended to readjust the brightness in consideration of the visual suppression effect, and may be intended to minimize errors due to an optical illusion in which the brightness of the target grid may be evaluated differently depending on the brightness of the surrounding grids when observed with the naked eye. Specifically, since the judgment by human visual perception is more important when it comes to “matte” when commercialized, the value measured by the device should not only indicate matte, but also be perceived as actually visually matte, and accordingly, the above correction factor may be applied to the measured value so that the measured value derived through the device is at a level equivalent to the actual visual effect that takes the optical illusion into account.

[0099] 5) Derivation of mean and standard deviation: The mean and standard deviation are derived from the corrected luminosity values ​​of each grid, and the coefficient of variation of light reflection is derived using the mean value and standard deviation of the luminosity obtained in this manner using the following mathematical formula 3.

[0100] [Equation 3]

[0101] C LR = D L / M L

[0102] In the above mathematical formula 3, C LR is the coefficient of variation of light reflection, and D L is the standard deviation of luminosity, and M L is the average luminosity.

[0103]

[0104] According to one embodiment of the present invention, the light reflection variation coefficient of the resin composition may be 1.5 or less, and for specific examples, may be 1.45 or less, 1.4 or less, 1.35 or less, 1.3 or less, 1.25 or less, or 1.2 or less. If the light reflection variation coefficient exceeds the above range, the surface appearance quality of the resin composition may deteriorate. If the light reflection variation coefficient exceeds the above range, it may mean that the surface is not uniform and thus diffuse reflection does not occur in any part of the surface.

[0105]

[0106] 2. Matrix copolymer

[0107] According to one embodiment of the present invention, the resin composition may include a matrix copolymer. The copolymer serves as a matrix in the resin composition and can play a fundamental role in realizing excellent physical properties of a resin molded product.

[0108] According to one embodiment of the present invention, the matrix copolymer may be included in an amount of 40 parts by weight or more and 70 parts by weight or less, based on 100 parts by weight of the sum of the crosslinked copolymer, the matrix copolymer, and the graft copolymer, and more specifically, it may be included in an amount of 42 parts by weight or more, 44 parts by weight or more, 46 parts by weight or more, 48 parts by weight or more, or 50 parts by weight or more, and further, it may be included in an amount of 68 parts by weight or less, 66 parts by weight or less, 64 parts by weight or less, 62 parts by weight or less, or 60 parts by weight or less.

[0109]

[0110] According to one embodiment of the present invention, the matrix copolymer may include a first matrix copolymer including an aromatic vinyl monomer unit, a vinyl cyan monomer unit, and an alkyl (meth)acrylate monomer unit, or may include, in addition to the first matrix, a second matrix including an aromatic vinyl monomer unit and a vinyl cyan monomer unit. In other words, the matrix copolymer according to one embodiment of the present invention may include the first matrix copolymer but not the second matrix copolymer, or may include both the first matrix copolymer and the second matrix copolymer.

[0111]

[0112] (1) First matrix copolymer

[0113] According to one embodiment of the present invention, the first matrix copolymer may serve to impart scratch resistance to the resin composition. The first matrix copolymer may include an aromatic vinyl monomer unit, a vinyl cyan monomer unit, and an alkyl (meth)acrylate monomer unit.

[0114] According to one embodiment of the present invention, the aromatic vinyl monomer for forming the aromatic vinyl monomer unit included in the first matrix copolymer may be at least one selected from the group consisting of styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, o-methylstyrene, ot-butylstyrene, bromostyrene, chlorostyrene, trichlorostyrene, and derivatives thereof, and a specific example thereof may be styrene.

[0115] According to one embodiment of the present invention, the vinyl cyan monomer for forming the vinyl cyan monomer unit included in the first matrix copolymer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and derivatives thereof, and a specific example thereof may be acrylonitrile.

[0116] According to one embodiment of the present invention, the alkyl (meth)acrylate monomer for forming the alkyl (meth)acrylate monomer unit included in the first matrix copolymer may be at least one selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, and lauryl (meth)acrylate, and specifically, the alkyl (meth)acrylate monomer may be at least one selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, and butylacrylate.

[0117]

[0118] According to one embodiment of the present invention, when the matrix copolymer includes the first matrix copolymer but does not include the second matrix copolymer, the first matrix copolymer may be included in an amount of 40 parts by weight or more and 70 parts by weight or less, based on 100 parts by weight of the sum of the crosslinked copolymer, the matrix copolymer, and the graft copolymer, and more specifically, may be included in an amount of 42 parts by weight or more, 44 parts by weight or more, 46 parts by weight or more, 48 parts by weight or more, or 50 parts by weight or more, and further may be included in an amount of 68 parts by weight or less, 66 parts by weight or less, 64 parts by weight or less, 62 parts by weight or less, or 60 parts by weight or less. When the above range is satisfied, the scratch resistance of the resin composition may be improved.

[0119]

[0120] (2) Second matrix copolymer

[0121] According to one embodiment of the present invention, the second matrix copolymer may serve as a matrix in a resin composition. The second matrix copolymer may include an aromatic vinyl monomer unit and a vinyl cyan monomer unit.

[0122] According to one embodiment of the present invention, the aromatic vinyl monomer for forming the aromatic vinyl monomer unit included in the second matrix copolymer may be at least one selected from the group consisting of styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, o-methylstyrene, ot-butylstyrene, bromostyrene, chlorostyrene, trichlorostyrene, and derivatives thereof, and a specific example thereof may be styrene.

[0123] According to one embodiment of the present invention, the vinyl cyan monomer for forming the vinyl cyan monomer unit included in the second matrix copolymer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and derivatives thereof, and a specific example thereof may be acrylonitrile.

[0124]

[0125] According to one embodiment of the present invention, when the matrix copolymer includes both the first matrix copolymer and the second matrix copolymer, the content of the first matrix copolymer may be greater than the content of the second matrix copolymer. When the content of the first matrix copolymer is greater than the content of the second matrix copolymer, the scratch resistance of the resin composition may be exhibited.

[0126] According to one embodiment of the present invention, when the matrix copolymer includes both the first matrix copolymer and the second matrix copolymer, the first matrix copolymer may be included in an amount of 60 wt% or more based on the total of the first matrix copolymer and the second matrix copolymer, and for specific examples, the first matrix copolymer may be included in an amount of 62 wt% or more, 64 wt% or more, 66 wt% or more, 68 wt% or more, or 70 wt% or more. When the content of the first matrix copolymer satisfies the above range, the scratch resistance of the resin composition may be improved.

[0127]

[0128] 3. Graft copolymer

[0129] According to one embodiment of the present invention, the graft copolymer can serve to provide excellent moldability and impact resistance to the resin composition.

[0130] According to one embodiment of the present invention, the graft copolymer may include a conjugated diene polymer, an aromatic vinyl monomer unit, and a vinyl cyan monomer unit, and specifically, may be a core-shell structured graft copolymer including a core including a conjugated diene monomer unit; and a shell surrounding the core and including an aromatic vinyl monomer unit and a vinyl cyan monomer unit.

[0131] According to one embodiment of the present invention, the conjugated diene monomer for forming the conjugated diene monomer unit included in the graft copolymer may be at least one 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 a specific example thereof may be 1,3-butadiene.

[0132] According to one embodiment of the present invention, the aromatic vinyl monomer for forming the aromatic vinyl monomer unit included in the graft copolymer may be at least one selected from the group consisting of styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, o-methylstyrene, ot-butylstyrene, bromostyrene, chlorostyrene, trichlorostyrene, and derivatives thereof, and a specific example thereof may be styrene.

[0133] According to one embodiment of the present invention, the vinyl cyan monomer for forming the vinyl cyan monomer unit included in the graft copolymer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and derivatives thereof, and a specific example thereof may be acrylonitrile.

[0134] According to one embodiment of the present invention, the graft copolymer may include a core comprising a conjugated diene monomer unit in an amount of 30 wt% to 70 wt%; and a shell surrounding the core and comprising an aromatic vinyl monomer unit and a vinyl cyan monomer unit in an amount of 30 wt% to 70 wt%. In addition, the shell may include an aromatic vinyl monomer unit and a vinyl cyan monomer unit in a weight ratio of 7:3 to 8:2, in which case the impact resistance, mechanical properties, and moldability of the copolymer may be more excellent.

[0135] According to one embodiment of the present invention, the graft copolymer may be included in an amount of 5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the resin composition, and more specifically, it may be included in an amount of 7 parts by weight or more, 9 parts by weight or more, 11 parts by weight or more, 13 parts by weight or more, or 15 parts by weight or more, and further, it may be included in an amount of 45 parts by weight or less, 40 parts by weight or less, 35 parts by weight or less, 30 parts by weight or less, or 25 parts by weight or less.

[0136]

[0137] 4. Other additives

[0138] The resin composition according to one embodiment of the present invention may further include, if necessary, one or more additives selected from the group consisting of impact modifiers, lubricants, heat stabilizers, anti-drop agents, antioxidants, light stabilizers, ultraviolet ray blockers, pigments, and inorganic fillers, and in this case, the additives may be used in an amount of 5.0 parts by weight or less, or 0.1 to 1.0 parts by weight, based on 100 parts by weight of the copolymer and the thermoplastic resin.

[0139] In addition, the specific material of the additive may be used without particular limitation as long as it is used in a thermoplastic resin composition, but for example, the anti-dripping agent may be at least one selected from the group consisting of Teflon, polyamide, polysilicon, PTFE (polytetrafluoroethylene), and TFE-HFP (tetrafluoroethylene-hexafluoropropylene) copolymer in terms of further improving flame retardancy, and the inorganic filler may be at least one selected from the group consisting of barium sulfate, barium glass filler, and barium oxide.

[0140]

[0141] <Method for producing resin composition>

[0142] The present invention provides a method for producing the above resin composition.

[0143] The method for producing a resin composition according to the present invention is characterized in that the particle size (D) when the cumulative percentage by weight on the particle size distribution reaches at least 50% 50) is 100 ㎛ or less and an average HW ratio satisfies the following mathematical formula 1; and a crosslinked copolymer manufactured in step S1, a conjugated diene monomer; a graft copolymer including an aromatic vinyl monomer unit and a vinyl cyan monomer unit; And a step (S2) of mixing a matrix copolymer, wherein the matrix copolymer comprises a first matrix copolymer including an aromatic vinyl monomer unit, a vinyl cyan monomer unit, and an alkyl (meth)acrylate monomer unit, or, in addition to the first matrix, a second matrix including an aromatic vinyl monomer unit and a vinyl cyan monomer unit, and when the matrix copolymer includes the first matrix copolymer and the second matrix copolymer, the content of the first matrix copolymer is greater than the content of the second matrix copolymer, and the step S1 comprises: a step (S1-1) of introducing an aromatic vinyl monomer, a vinyl cyan monomer, and a polymerization initiator into a reactor to initiate a polymerization reaction; and a step (S1-2) after the step S1, of partially introducing a crosslinking agent including an acrylate compound or an allyl compound into the reactor to polymerize.

[0144] [Mathematical Formula 1]

[0145] 0.05≤ Average HW ratio ≤1

[0146] In the above mathematical expression 1, the average HW ratio is the average value of the HW ratio (a / b) calculated for each crosslinked copolymer observed when the surface of the resin composition is observed with an optical microscope,

[0147] The above a is ½ the value of the shortest axis length of each cross-linked copolymer observed when observed with an optical microscope,

[0148] The above b is the longest axis length of each crosslinked copolymer observed when observed with an optical microscope.

[0149]

[0150] 1. Step of preparing a crosslinked copolymer (S1)

[0151] According to one embodiment of the present invention, the step (S1) is to determine the particle size (D) when the weight-based cumulative percentage on the particle size distribution reaches 50%. 50 ) is 100 ㎛ or less and the average HW ratio satisfies the above mathematical formula 1, the step of initiating a polymerization reaction by introducing an aromatic vinyl monomer, a vinyl cyan monomer and a polymerization initiator into a reactor (S1-1); and after the step (S1-1), the step of introducing a crosslinking agent including an acrylate compound or an allyl compound into the reactor in portions and polymerizing the crosslinking agent may be included (S1-2).

[0152]

[0153] (1) Polymerization reaction initiation step (S1-1)

[0154] According to one embodiment of the present invention, the step (S1-1) is a step for initiating polymerization, and may be a step of introducing a reaction solution into a reactor and then raising the temperature of the reactor to a predetermined temperature. In the step (S1), if the internal temperature of the reactor rises above the predetermined temperature, polymerization proceeds in the presence of a polymerization initiator, and in the 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.

[0155]

[0156] According to one embodiment of the present invention, the step (S1-1) may include introducing an aromatic vinyl monomer, a vinyl cyan monomer, and a polymerization initiator into the reactor.

[0157] According to one embodiment of the present invention, the aromatic vinyl monomer introduced in the step (S1-1) may be at least one selected from the group consisting of styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, o-methylstyrene, ot-butylstyrene, bromostyrene, chlorostyrene, trichlorostyrene, and derivatives thereof, and a specific example thereof may be styrene.

[0158] The aromatic vinyl monomer may be added in an amount of 60 to 95 parts by weight, 64 to 90 parts by weight, 68 to 85 parts by weight, or 72 to 80 parts by weight, based on 100 parts by weight of the vinyl cyan monomer and the aromatic vinyl monomer added in the step (S1-1), 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 can be a key factor in implementing a matte finish, and has an excellent compatibility effect.

[0159] According to one embodiment of the present invention, the vinyl cyan monomer introduced in the step (S1-1) may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and derivatives thereof, and a specific example thereof may be acrylonitrile.

[0160] In addition, according to one embodiment of the present invention, the vinyl cyan monomer may be introduced in an amount of 5 to 40 parts by weight, 10 to 36 parts by weight, 15 to 32 parts by weight, or 20 to 28 parts by weight, based on 100 parts by weight of the aromatic vinyl monomer and the vinyl cyan monomer introduced in the step (S1-1), and within this range, a copolymer can be obtained with a high polymerization conversion rate, and the copolymer has excellent compatibility while maintaining mechanical properties.

[0161]

[0162] According to one embodiment of the present invention, the method for producing the crosslinked copolymer may be carried out by a suspension polymerization method, and may further include one or more additives selected from the group consisting of a polymerization initiator, a dispersant, a dispersing aid, and a molecular weight regulator as a solvent for carrying out polymerization in the step (S1-1), and may be carried out in the presence of these.

[0163] According to one embodiment of the present invention, the polymerization initiator is not particularly limited as long as it does not adversely affect the polymerization and is used to easily initiate the polymerization, and 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-butylperoxy isopropyl carbonate, t-butyl peroxy-3,5,5-trimethyl-hexanoate, It may be at least one 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), 1,1'-azobis(cyclohexane-1-cyclonitrile) and azobisisobutyronitrile, and specifically, one selected from the group consisting of dicumyl peroxide, 1,1-di(t-butyl peroxy)cyclohexane, 1,1'-azobis(cyclohexanecarbonitrile) and azobisisobutyronitrile. It could be strange.

[0164] In addition, the polymerization initiator may 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 0.3 parts by weight, based on 100 parts by weight of the aromatic vinyl monomer and the vinyl cyan monomer introduced in the step (S1-1). When used in the above range, the polymerization reaction can be performed more easily, thereby increasing the polymerization conversion rate.

[0165] According to one embodiment of the present invention, the dispersant may be at least one selected from the group consisting of water-soluble polyvinyl alcohol, partially saponified polyvinyl alcohol, polyacrylic acid, a 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 thereof may be tricalcium phosphate.

[0166] According to one embodiment of the present invention, the dispersant may be used in an amount of 1.0 to 3.0 parts by weight, 1.5 to 2.5 parts by weight, or 1.5 to 2.0 parts by weight, based on 100 parts by weight of the aromatic vinyl monomer and the vinyl cyan monomer introduced in the step (S1-1), and within this range, the dispersion stability of the monomers in the polymerization system can be increased, thereby producing a copolymer having more uniform particles.

[0167] In addition, according to one embodiment of the present invention, the method for producing the crosslinked copolymer can be carried out by further including a dispersing aid during polymerization, and as a specific example, the dispersing aid can be a polyoxyethylene-based dispersing aid, and as a more specific example, it can be polyoxyethylene alkyl ether phosphate, and in this case, excellent polymerization stability is achieved.

[0168] According to one embodiment of the present invention, the molecular weight modifier may be at least one selected from the group consisting of, for example, α-methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, octyl mercaptan, carbon tetrachloride, methylene chloride, methylene bromide, tetraethyl thiuram disulfide, dipentamethylene thiuram disulfide, and diisopropylxanthogen disulfide, and a specific example may be t-dodecyl mercaptan.

[0169] According to one embodiment of the present invention, the molecular weight regulator introduced in the step (S1-1) may be used in an amount of 0.01 to 0.40 parts by weight, 0.05 to 0.30 parts by weight, or 0.10 to 0.25 parts by weight, based on 100 parts by weight of the aromatic vinyl monomer and the vinyl cyan monomer introduced in the step (S1-1), and a copolymer having an appropriate weight average molecular weight can be prepared within this range.

[0170]

[0171] (2) Polymerization step (S1-2)

[0172] According to one embodiment of the present invention, the step (S1-2) is a step of dividing and introducing a crosslinking agent including the above-described crosslinking functional compound, and the crosslinking agent may be divided and introduced two or more times, or three or more times. In addition, the crosslinking functional compound may include at least one selected from the group consisting of acrylic compounds and aryl compounds, as described above, and may include a functional group such as a vinyl group or an acrylic group.

[0173]

[0174] If the crosslinking agent is added only at the early stage of polymerization, the crosslinking effect may be relatively low. Since the concentration of the crosslinking agent is high at the early stage of polymerization, the possibility of side reactions in which crosslinking agents bond with each other may increase. In addition, since the concentration of the crosslinking agent decreases toward the later stage of polymerization, it is difficult for the crosslinking moiety to be uniformly distributed within the copolymer chain, and the formation of the crosslinked copolymer may not be smooth, so the yield of the crosslinked copolymer may be significantly reduced. These problems ultimately lead to an increase in the gloss and the coefficient of variation of light reflection, and the non-uniformity may even lead to a decrease in the impact strength.

[0175] According to one embodiment of the present invention, the crosslinking functional compound is introduced in step (S1-2), and can be introduced starting immediately after step (S1-1), and can be introduced in two or more portions during polymerization, and preferably can be introduced in three or more portions.

[0176] According to one embodiment of the present invention, the time difference between the divided injections when the crosslinking functional compound is injected in step (S1-2) may be 1% to 30% of the total polymerization time. When the time difference between the divided injections is provided, the degree of crosslinking within the entire copolymer chain of the crosslinked copolymer can be achieved at a uniform and appropriate level, and the crosslinking density can also be excellent, which may play an important role in performing the function of imparting diffuse reflection to the surface of the resin molded product. In addition, the divided injection of the crosslinking agent may be performed for a time period of 20% to 70% of the total polymerization time, and it may be desirable to start and end the divided injection within this time range in order to impart a sufficient crosslinking effect.

[0177] According to one embodiment of the present invention, the crosslinking functional compound that is dividedly introduced during the polymerization in the step (S1-2) may be introduced in an amount of 0.05 to 0.30 parts by weight, preferably 0.05 to 0.20 parts by weight, and more preferably 0.05 to 0.15 parts by weight, based on 100 parts by weight of the aromatic vinyl monomer and the vinyl cyan monomer introduced in the step (S1-1).

[0178] In addition, according to one embodiment of the present invention, the crosslinking functional compound may be injected in the same or different amounts for each split injection, and it is preferable to control the amount so that the deviation between the amounts injected is not large.

[0179]

[0180] According to one embodiment of the present invention, in the step (S1-2), at least one of a molecular weight regulator and a polymerization initiator may be further added to the crosslinking agent and then divided and added.

[0181] In this way, when a molecular weight regulator and / or a polymerization initiator are included in the step (S1-2) and are dividedly introduced together with a crosslinking functional compound, control of the reactivity between monomers, the reactivity between the polymer chain and the crosslinking agent, etc. can be more easily achieved, and thus, control of the degree of crosslinking can be easily achieved, and accordingly, impact strength and heat resistance are maintained at excellent levels, and at the same time, a uniform and matte molded product can be obtained with a low coefficient of variation in gloss and light reflection.

[0182]

[0183] Meanwhile, according to one embodiment of the present invention, the polymerization in step (S1-2) may be performed at a temperature range of 50°C to 150°C, preferably 60°C to 130°C, and more preferably 65°C to 120°C. When polymerization is performed in the above-described temperature range, it may be preferable for obtaining the final polymerization conversion rate and other polymer properties.

[0184]

[0185] Meanwhile, the steps (S1-1) and (S1-2) according to one embodiment of the present invention may be performed under stirring. If the steps (S1-1) and (S1-2) according to one embodiment of the present invention are performed under stirring at 500 rpm or more, even if the crushing step (S1-3) described below is omitted, the particle size (D) when the cumulative percentage by weight of the crosslinked copolymer produced reaches 50% on the target particle size distribution 50 ) and can have an average HW ratio.

[0186] Specifically, the steps (S1-1) and (S1-2) according to one embodiment of the present invention may be performed under stirring at 550 rpm or more, 600 rpm or more, 700 rpm or more, 750 rpm or more, or 800 rpm or more, and in this case, even if the pulverization step (S1-3) described later is omitted, the particle size (D) when the weight-based cumulative percentage of the crosslinked copolymer produced reaches 50% on the target particle size distribution 50 ) and can have an average HW ratio.

[0187]

[0188] (3) Crushing stage (S1-3)

[0189] According to one embodiment of the present invention, the step (S1) may further include a step (S1-3) of grinding the resultant product of the step (S1-2) when the steps (S1-1) and (S1-2) are performed without stirring or under stirring at less than 500 rpm. The step (S1-3) may further include a step (D) of grinding the resultant product of the step (S1-2) when the weight-based cumulative percentage of the crosslinked copolymer reaches 50% on the desired particle size distribution. 50 ) and may be a process for processing to have an average HW ratio.

[0190] According to one embodiment of the present invention, the step (S1-3) may be performed using one or more of an air jet mill, a rotary mill, a cutting mill, a ball mill, or a hammer mill.

[0191]

[0192] 2. Step of mixing crosslinked copolymer, matrix copolymer and graft copolymer (S2)

[0193] According to one embodiment of the present invention, the step (S2) may be to prepare a resin composition by mixing a crosslinked copolymer, a matrix copolymer, and a graft copolymer manufactured by the manufacturing method described above.

[0194]

[0195] According to one embodiment of the present invention, the first matrix copolymer and the second matrix copolymer can be generally applied as commercially available resins and can be obtained through a commercially available method. Since the contents of the first matrix copolymer and the second matrix copolymer have been described above, a detailed description thereof will be omitted below.

[0196]

[0197] According to one embodiment of the present invention, the graft copolymer can generally apply a commercially available resin and can be obtained through a commercially available method. For example, the graft copolymer can be manufactured by emulsion polymerizing a conjugated diene monomer to produce a rubbery polymer core (or seed), adding a vinyl cyanide monomer and an aromatic vinyl monomer to the core, and then emulsion graft polymerizing the core.

[0198]

[0199] <Molded product>

[0200] The present invention provides a molded article comprising the resin composition. For example, the molded article can be applied to various industrial fields such as various electrical and electronic products and automobile parts. As a molding method, general molding methods such as extrusion, injection, and casting can be applied. For example, in injection molding, compared to a product that aims to provide a matte molded article by corroding the surface of the mold, the molded article according to the present invention does not require corroding the surface of the mold, and even without post-processing the molded article, it is possible to provide a molded article having a matte and uniform surface in the injection-molded state.

[0201]

[0202] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement them. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

[0203]

[0204] Examples and Comparative Examples

[0205] The materials used in the examples and comparative examples are as follows.

[0206]

[0207] (1) Crosslinked copolymer: The crosslinked copolymer prepared in Manufacturing Examples 1 to 3 below was used.

[0208]

[0209] Manufacturing Example 1

[0210] To 100 parts by weight of a mixture composed of 77 parts by weight of styrene monomer and 23 parts by weight of acrylonitrile, 0.2 parts by weight of azobisisobutyronitrile (AIBN), 0.3 parts by weight of t-dodecyl mercaptan (TDDM), and 2.0 parts by weight of tricalcium phosphate were added while stirring at 200 rpm, and after heating to 70°C, 0.2 parts by weight of t-dodecyl mercaptan (TDDM) and 0.1 parts by weight of allyl methacrylate as a crosslinking agent were added in three portions at one-hour intervals, while performing suspension polymerization for 5 hours. Thereafter, the resultant was washed and dehydrated, and dried at 85°C for 90 minutes in a fluidized bed dryer to obtain a copolymer having an average particle size of 250 μm, and the copolymer was pulverized to obtain a crosslinked copolymer A in powder form.

[0211]

[0212] Manufacturing Example 2

[0213] A crosslinked copolymer was prepared in the same manner as in Manufacturing Example 1, except that stirring was performed at 600 rpm and a separate grinding process was not performed, thereby obtaining a crosslinked copolymer B in powder form.

[0214]

[0215] Manufacturing Example 3

[0216] A crosslinked copolymer was prepared in the same manner as in Manufacturing Example 1, except that stirring was performed at 1000 rpm and a separate grinding process was not performed, thereby obtaining a crosslinked copolymer C in powder form.

[0217]

[0218] (2) First matrix copolymer: manufactured by LG Chemical, product name XT510

[0219]

[0220] (3) Second matrix copolymer: manufactured by LG Chemical, product name 97HC

[0221]

[0222] (4) Graft copolymer: manufactured by LG Chemical, product name DP270

[0223]

[0224] Experimental Example 1 - Measurement of the physical properties of crosslinked copolymers

[0225] * D 50 : D of the crosslinked copolymers manufactured in Manufacturing Examples 1 to 7 was measured using a light diffraction particle size analyzer (manufactured by Sympatec GmbH, product name: HELOS / KR). 50 The results were measured and recorded in Tables 1 and 2 below.

[0226] * HW ratio (a / b): The crosslinked copolymer, matrix copolymer, and graft copolymer manufactured in Manufacturing Examples 1 to 3 were added in the contents described in Tables 1 and 2 below, and 0.2 parts by weight of a heat stabilizer and 1 part by weight of a lubricant were mixed for 100 parts by weight of the total of the crosslinked copolymer, matrix copolymer, and graft copolymer to manufacture the resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3.

[0227] The resin compositions manufactured in the above-described examples and comparative examples were put into an extrusion mixer (processing temperature: 220°C), extruded, and then injected to manufacture samples. When the surface of the manufactured samples was observed with an optical microscope (manufactured by Olympus, product name: OLS4000), the HW ratio (a / b) was calculated for each crosslinked copolymer observed in the optical microscope image by setting a as 1 / 2 of the shortest axis length and b as the length of the longest axis, and the average value of the HW ratio (a / b) calculated for each crosslinked copolymer is shown in Tables 1 and 2.

[0228]

[0229] Experimental Example 2 - Measurement of physical properties of resin compositions

[0230] The crosslinked copolymer, matrix copolymer and graft copolymer manufactured in Manufacturing Examples 1 to 3 were introduced in the contents described in Tables 1 and 2 below, and 0.2 parts by weight of a heat stabilizer and 1 part by weight of a lubricant were mixed with respect to 100 parts by weight of the total of the crosslinked copolymer, matrix copolymer and graft copolymer to manufacture the resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3.

[0231] The resin compositions manufactured in the above-described examples and comparative examples were put into an extrusion mixer (processing temperature: 220°C), extruded, and then injected to manufacture samples. The properties of the resin compositions of the manufactured samples were measured using the following methods, and are shown in Tables 1 and 2 below.

[0232]

[0233] * Gloss: For a 0.4 mm thick sample, the surface gloss was measured at a 60° angle using a gloss meter according to the evaluation method specified in ASTM D523. In the present invention, if the gloss was 6 or less, the matte properties were evaluated as excellent.

[0234]

[0235] * Izod impact strength: Measured according to ASTM 256 for 1 / 4 inch thick samples. In the present invention, when the Izod impact strength is 19 kg·cm / cm or more, the impact resistance is evaluated as excellent.

[0236]

[0237] * Flow Index: Measured under 220℃ / 10kg conditions according to the evaluation method specified in ASTM D1238. In the present invention, a flow index of 10 g / 10 min or higher was evaluated as excellent.

[0238]

[0239] * Coefficient of Variation to Light Reflection: Measured using Phyton for a 0.4 mm thick sample using the following method.

[0240] 1) Sample imaging: Using a DSLR camera (Canon 750D) and a 200 mm x 200 mm sized surface light (White LED, Collimated Backlight LTS-3PFT), the prepared sample was photographed and imaged at a distance of 40 cm from the camera and sample, a distance of 100 cm from the sample and a 90° angle.

[0241] 2) Grayscale conversion of sample images: The sample images were converted to grayscale (0-255) using the Open CV library. At this time, a grayscale value was assigned to each pixel in the sample image, and this grayscale value was used as luminosity.

[0242] 3) Image reconstruction: The image was divided into grids of 200 ㎛ x 200 ㎛ in size, and the image was reconstructed by averaging the luminance values ​​(grayscale values) of the pixels within each grid. At this time, each grid has one averaged luminance value.

[0243] 4) Luminance correction: The target grid was 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 luminance value of the target grid was derived using the following mathematical expression 2.

[0244] [Equation 2]

[0245]

[0246] In the above mathematical expression 2, L is the corrected luminance value of the target grid, and L 1 is the luminosity of the first zone grid, L2 1, L 2 2, L 2 3, ..., L 2 8 is the luminosity of each of the eight 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 the third zone.

[0247] 5) Derivation of average and standard deviation: The average and standard deviation were derived from the corrected luminosity values ​​of each grid, and the average value and standard deviation of the luminosity thus obtained were used to derive the coefficient of variation of light reflection using the following mathematical formula 3.

[0248] [Equation 3]

[0249] C LR = D L / M L

[0250] C above LR is the coefficient of variation of light reflection, and D L is the standard deviation of luminosity, and M L is the average luminosity.

[0251]

[0252] * Surface appearance quality: The number of pinholes was measured within a sample with a unit area of ​​10 cm x 10 cm. If no pinholes were observed, it was evaluated as ○, if 1 to 7 pinholes were observed, it was evaluated as △, and if 8 or more were observed, it was evaluated as X.

[0253]

[0254] * Pencil hardness: According to the evaluation method specified in ASTM D 336, a MITSU-BISHI pencil was placed at a 45° angle to the surface of the coating, pressed with a load of 750 g, and pressed horizontally at a speed of 0.5 mm / s for a distance of at least 7 mm to observe whether a scar was formed on the pencil lead. The hardness of the hardest pencil that did not form a scar was determined as the pencil hardness. (9H > 8H > 7H > 6H > 5H > 4H > 3H > 2H > H > F > HB > B > 2B > 3B > 4B > 5B > 6B > 7B > 8B > 9B)

[0255]

[0256] Example 123456 Crosslinked copolymer type AAAABCD 50 (㎛)404040407040Average HW ratio0.10.10.10.10.080.11Content (parts by weight)203020303030First matrix copolymer (parts by weight)605042355050Second matrix copolymer (parts by weight)--1815--Graft copolymer (parts by weight)20202020202020Gloss656585Pencil hardnessFFFFFFFlow index (g / 10 min)424222Impact strength (kg·cm / cm)201919191920Coefficient of variation of light reflection1.21.11.11.11.41.1Surface appearance quality○○○○○○

[0257] Comparative Example 123 Crosslinked Copolymer Type AA-D 50 (㎛)4040-Average HW ratio0.10.1-Content (parts by weight)3020-First matrix copolymer(parts by weight)-3080Second matrix copolymer(parts by weight)5030-Graft copolymer(parts by weight)202020Gloss5690Pencil hardnessBBBFlow index (g / 10 min)245Impact strength (kg·cm / cm)201925Coefficient of variation of light reflection1.11.11.0Surface appearance quality○○○

[0258] Referring to Table 1 and Table 2, D 50It was confirmed that the resin compositions of Examples 1 to 6, which include a crosslinked copolymer having a particle size of 100 ㎛ or less and an average HW ratio satisfying a preferred range, and an appropriate amount of a first matrix copolymer and / or a second matrix copolymer, are all excellent in gloss, flow index, impact strength, surface appearance quality, and pencil hardness.

[0259]

[0260] Comparative Example 1, which does not include the first matrix copolymer, was confirmed to have a lower pencil hardness compared to Examples 1 to 6.

[0261]

[0262] Comparative Example 2, in which the matrix copolymer includes a first matrix copolymer and a second matrix copolymer, but the content of the first matrix copolymer is the same as the content of the second matrix copolymer, showed a decrease in pencil hardness compared to Examples 1 to 6.

[0263]

[0264] Comparative Example 3, which does not include a crosslinked copolymer, secured superior surface appearance quality compared to Examples 1 to 6, but it was confirmed that the gloss and pencil hardness were significantly reduced.

Claims

1. A graft copolymer comprising a conjugated diene polymer, an aromatic vinyl monomer unit, and a vinyl cyan monomer unit; matrix copolymer; and A crosslinked copolymer comprising a crosslinking portion formed from an aromatic vinyl monomer unit, a vinyl cyan monomer unit, and a crosslinking functional compound, The particle size (D) when the cumulative percentage based on weight in the particle size distribution diagram of the above crosslinked copolymer reaches 50% 50 ) is 30 ㎛ or more and 100 ㎛ or less, The average HW ratio of the above crosslinked copolymer satisfies the following mathematical formula 1, The above matrix copolymer: A first matrix copolymer comprising an aromatic vinyl monomer unit, a vinyl cyan monomer unit, and an alkyl (meth)acrylate monomer unit; or, A second matrix copolymer comprising an aromatic vinyl monomer unit and a vinyl cyan monomer unit and the first matrix copolymer, A resin composition wherein, when the matrix copolymer includes the first matrix copolymer and the second matrix copolymer, the content of the first matrix copolymer is greater than the content of the second matrix copolymer. [Mathematical Formula 1] 0.05≤ Average HW ratio ≤1 In the above mathematical expression 1, the average HW ratio is the average value of the HW ratio (a / b) calculated for each crosslinked copolymer observed when the surface of the resin composition is observed with an optical microscope, The above a is ½ the value of the shortest axis length of each cross-linked copolymer observed when observed with an optical microscope, The above b is the longest axis length of each crosslinked copolymer observed when observed with an optical microscope.

2. In paragraph 1, A resin composition wherein the above crosslinking functional compound is a compound containing a vinyl functional group.

3. In paragraph 1, A resin composition wherein the crosslinking functional compound is allyl methacrylate.

4. In paragraph 1, D of the above cross-linked copolymer 50 A resin composition having a particle size of 30 ㎛ or more and 70 ㎛ or less.

5. In paragraph 1, When the matrix copolymer comprises the first matrix copolymer and the second matrix copolymer, A resin composition comprising 60 wt% or more of the first matrix copolymer and the second matrix copolymer.

6. In paragraph 1, For 100 parts by weight of the total of the graft copolymer, the matrix copolymer and the crosslinked copolymer, A resin composition comprising 40 parts by weight or more and 70 parts by weight or less of the above matrix copolymer.

7. In paragraph 1, For 100 parts by weight of the total of the graft copolymer, the matrix copolymer and the crosslinked copolymer, A resin composition comprising 10 parts by weight or more and 40 parts by weight or less of the above crosslinked copolymer.

8. In paragraph 1, A resin composition having a pencil hardness of HB or higher as measured by the evaluation method of ASTM D 336.

9. In paragraph 1, A resin composition having a light reflection variation coefficient calculated by the following mathematical formula 1 of 1.5 or less. [Mathematical Formula 1] C LR = D L / M L C above LR is the coefficient of variation of light reflection, and D L is the standard deviation of luminosity, and M L is the average luminosity.

10. In paragraph 1, A resin composition having a gloss of 20 or less at 60° as measured by a gloss meter according to the evaluation method of ASTM D523.

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