Resin composition

Abstract

A resin composition, according to one embodiment of the present invention, comprises: a rubber polymer comprising a first aromatic vinyl-based monomer unit and a conjugated diene-based monomer unit; a (meth)acrylate-based monomer unit; and a second aromatic vinyl-based monomer unit, wherein the transparency (haze) measured for the resin composition according to ASTM D1003 is 2.5% or less, and when the resin composition is observed using a TEM image, the number average particle diameter of the rubber polymer that is observed is 210 nm to 350 nm, and the standard deviation of the number average particle diameter may be 110 nm or smaller.

Description

Resin composition

[0001] [Cross-reference with related applications]

[0002] This application claims the benefit of priority based on Korean patent application 10-2025-0023820 filed February 24, 2025, 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.

[0006] Recently, as industries advance and lifestyles become more diverse, extensive research is being conducted to impart high functionality to materials for product differentiation. For example, research is being intensively focused on transparent materials, such as washing machine covers that allow viewing of laundry contents, vacuum cleaner dust collectors that check dust accumulation, game console housings, transparent windows for home appliances, and transparent windows for office equipment.

[0007] However, the diene graft copolymer prepared by graft polymerizing styrene monomers and acrylonitrile monomers onto the diene rubbery polymers used in these parts has excellent impact resistance, chemical resistance, processability, and surface gloss, but does not have excellent transparency.

[0008] Meanwhile, polycarbonate, polymethyl methacrylate, polystyrene, and polyacrylonitrile-styrene are commonly used as transparent materials. However, while polycarbonate has excellent impact strength and transparency, its poor processability makes it difficult to manufacture complex products, and it does not have excellent chemical resistance. Polymethyl methacrylate has excellent optical properties, but it does not have excellent impact resistance or chemical resistance. In addition, polystyrene and polyacrylonitrile-styrene also do not have excellent impact resistance or chemical resistance. Furthermore, diene-based graft polymers offer a balance of excellent impact resistance and processability, but they do not have excellent transparency.

[0009] Therefore, there is a need to develop materials that are excellent in transparency, impact resistance, chemical resistance, and processability.

[0010] [Prior Art Literature]

[0011] [Patent Literature]

[0012] (Patent Document 1) KR 10-2016-0081497

[0013] The problem to be solved by the present invention is to provide a resin composition that has excellent transparency, chemical resistance, and processability.

[0014] (1) The present invention provides a resin composition comprising a rubbery polymer comprising a first aromatic vinyl monomer unit and a conjugated diene monomer unit; a (meth)acrylate monomer unit; and a second aromatic vinyl monomer unit, wherein the haze measured according to ASTM D1003 for the resin composition is 2.5% or less, and when the resin composition is observed by TEM image, the number average particle size of the rubbery polymer observed is 210 nm or more and 350 nm or less, and the standard deviation of the number average particle size is 110 nm or less.

[0015] (2) The present invention provides a resin composition in which, when the resin composition is observed with a TEM image, the number average particle size of the observed rubbery polymer is 235 nm or more and 300 nm or less.

[0016] (3) The present invention provides a resin composition in which, in (1) or (2), when the resin composition is observed with a TEM image, the standard deviation of the observed rubbery polymer particle size is 100 nm or less.

[0017] (4) The present invention provides a resin composition in any one of (1) to (3) wherein the rubbery polymer is included in an amount of 9% or more and 25% or less, (meth)acrylate monomer units are included in an amount of 30% or more and 60% or less, and the second aromatic vinyl monomer units are included in an amount of 22% or more and 47% or less.

[0018] (5) The present invention provides a resin composition in which, in any one of (1) to (4), the average particle size of the rubbery polymer is 240 nm or more and 350 nm or less.

[0019] (6) The present invention provides a resin composition in which, in any one of (1) to (5), the average particle size of the rubbery polymer is 260 nm or more and 330 nm or less.

[0020] (7) The present invention provides a resin composition in which, in any one of (1) to (6), the full width at half maximum (FWHM) of the particle size measured by CHDF (Capillary Hydro Dynamic Fractionation) of the rubbery polymer is 30 nm or more and 70 nm or less.

[0021] (8) The present invention provides a resin composition in which, in any one of (1) to (7), the full width at half maximum (FWHM) of the particle size measured by CHDF (Capillary Hydro Dynamic Fractionation) of the rubbery polymer is 40 nm or more and 60 nm or less.

[0022] (9) The present invention provides a resin composition comprising, in any one of (1) to (8), a graft copolymer comprising a rubbery polymer, a (meth)acrylate-based monomer unit grafted onto the rubbery polymer, and a second aromatic vinyl-based monomer unit grafted onto the rubbery polymer; and a matrix copolymer comprising a (meth)acrylate-based monomer unit not grafted onto the rubbery polymer, and a second aromatic vinyl-based monomer unit not grafted onto the rubbery polymer, wherein the difference between the refractive index of the graft copolymer and the refractive index of the matrix copolymer is 0.005 or less.

[0023] (10) The present invention provides a resin composition in which, in any one of (1) to (9), the graft copolymer is included in an amount of 15 parts by weight or more and 65 parts by weight or less, and the matrix copolymer is included in an amount of 35 parts by weight or more and 85 parts by weight or less, with respect to 100 parts by weight of the total amount of the graft copolymer and the matrix copolymer.

[0024] (11) The present invention provides a resin composition in any one of (1) to (10), wherein the resin composition further comprises vinyl cyanide monomer units, the vinyl cyanide monomer units include vinyl cyanide monomer units grafted onto the rubbery polymer and vinyl cyanide monomer units not grafted onto the rubbery polymer, the graft copolymer further comprises vinyl cyanide monomer units grafted onto the rubbery polymer, and the matrix copolymer further comprises vinyl cyanide monomer units not grafted onto the rubbery polymer.

[0025] (12) The present invention provides a resin composition in which, in any one of (1) to (11), the graft copolymer comprises: 35% by weight or more and 65% by weight or less of the rubbery polymer, 14% by weight or more and 45% by weight or less of (meth)acrylate monomer units grafted onto the rubbery polymer, 12% by weight or more and 34% by weight or less of a second aromatic vinyl monomer unit grafted onto the rubbery polymer, and 7% by weight or less of a vinyl cyanide monomer unit grafted onto the rubbery polymer.

[0026] (13) The present invention provides a resin composition in which, in any one of (1) to (12), the matrix copolymer comprises 39% by weight or more and 66% by weight or less of (meth)acrylate monomer units not grafted onto the rubbery polymer, 33% by weight or more and 52% by weight or less of second aromatic vinyl monomer units not grafted onto the rubbery polymer, and 12% by weight or less of vinyl cyanide monomer units not grafted onto the rubbery polymer.

[0027] (14) The present invention provides a resin composition in which, in any one of (1) to (10), the rubbery polymer comprises 15% by weight or more and 40% by weight or less of a first aromatic vinyl monomer unit.

[0028] A resin composition according to one embodiment of the present invention has excellent transparency, chemical resistance, and processability.

[0029] Figure 1 is a TEM image of a resin composition according to Example 1 of the present invention.

[0030] Figure 2 is a TEM image of a resin composition according to Example 2 of the present invention.

[0031] Figure 3 is a TEM image of a resin composition according to Comparative Example 1 of the present invention.

[0032] Hereinafter, the present invention will be described in more detail to aid in understanding the invention.

[0033] Terms and words used in this specification and claims should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted in a meaning and concept consistent with the technical spirit of the invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0034] In the present invention, the average particle size can be measured using the dynamic light scattering method, and specifically, it may refer to the arithmetic mean particle size in the particle size distribution measured by the dynamic light scattering method, that is, the scattering intensity average particle size. The average particle size can be measured using the Nicomp 380 equipment of Particle Sizing Systems.

[0035] In the present invention, the refractive index refers to the absolute refractive index of a material, and the refractive index can be recognized as the ratio of the velocity of electromagnetic radiation in free space to the velocity of radiation within the material. In this case, the radiation may be visible light with a wavelength of 450.0 nm to 680.0 nm, and specifically, may be visible light with a wavelength of 589.3 nm. The refractive index can be measured by a known method, namely an Abbe refractometer.

[0036] In the present invention, the term 'monomer unit' may refer to a component, structure, or the material itself derived from a monomer, and as a specific example, may refer to a repeating unit formed within a polymer by a monomer introduced during the polymerization of a polymer and participating in the polymerization reaction.

[0037] 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.

[0038]

[0039] <Resin Composition>

[0040] The present invention provides a resin composition.

[0041] A resin composition according to one embodiment of the present invention comprises at least a rubbery polymer comprising a first aromatic vinyl monomer unit and a conjugated diene monomer unit; a (meth)acrylate monomer unit; and a second aromatic vinyl monomer unit, wherein the haze measured according to ASTM D1003 for the resin composition is 2.5% or less, and when the resin composition is observed by TEM image, the number average particle size of the observed rubbery polymer is 210 nm or more and 350 nm or less, and the standard deviation of the number average particle size is 110 nm or less.

[0042]

[0043] Generally, when using large-diameter rubbery polymers with an average particle size of 240 nm or more in transparent acrylonitrile-butadiene-styrene (hereinafter referred to as ABS) resin, there was a problem with the transparency of the resin composition decreasing. Accordingly, methods to increase the transparency of transparent ABS resin include lowering the rubber content of the rubbery polymer or using small-diameter rubbery polymers with an average particle size of 100 nm or less. However, when the rubber content is lowered, the impact strength of the resin composition decreases rapidly, and when small-diameter rubbery polymers are used, there was a problem with the fluidity of the resin composition decreasing.

[0044] The inventors have discovered that when a rubbery polymer included as a core of a graft copolymer in a resin composition has a particle size half-width in a desirable range, excellent transparency is exhibited in the resin composition even if the rubbery polymer is a large-diameter rubbery polymer with an average particle size of 240 nm or more, and at the same time, excellent impact strength and fluidity are secured, and thus have completed the present invention.

[0045]

[0046] A resin composition according to one embodiment of the present invention may include a rubbery polymer comprising a first aromatic vinyl monomer unit and a conjugated diene monomer unit, a (meth)acrylate monomer unit, and a second aromatic vinyl monomer unit.

[0047] According to one embodiment of the present invention, the first aromatic vinyl monomer unit refers to an aromatic vinyl monomer unit included in the rubbery polymer, and the second aromatic vinyl monomer unit may refer to an aromatic vinyl monomer unit included in the resin composition but not included in the rubbery polymer.

[0048] A resin composition according to one embodiment of the present invention may comprise a graft copolymer comprising the rubbery polymer, a (meth)acrylate-based monomer unit grafted onto the rubbery polymer, and a second aromatic vinyl-based monomer unit grafted onto the rubbery polymer; and a matrix copolymer comprising a (meth)acrylate-based monomer unit not grafted onto the rubbery polymer, and a second aromatic vinyl-based monomer unit not grafted onto the rubbery polymer.

[0049] In addition, a resin composition according to one embodiment of the present invention may further include a vinyl cyanide monomer, and in this case, the graft copolymer may further include a vinyl cyanide monomer unit grafted onto the rubbery polymer, and the matrix copolymer may further include a vinyl cyanide monomer unit not grafted onto the rubbery polymer.

[0050] Hereinafter, each component constituting the resin composition will be described in detail.

[0051]

[0052] Graft copolymer

[0053] According to one embodiment of the present invention, the graft copolymer may serve to impart impact resistance to the resin composition and may include a rubbery polymer comprising a first aromatic vinyl monomer unit and a conjugated diene monomer unit, a meth)acrylate monomer unit grafted onto the rubbery polymer, and a second aromatic vinyl monomer unit grafted onto the rubbery polymer.

[0054]

[0055] According to one embodiment of the present invention, the rubbery polymer includes not only conjugated diene monomer units but also the first aromatic vinyl monomer units, so the refractive index of the rubbery polymer itself can be increased. As a result, even if the difference in refractive index between the graft copolymer and the matrix copolymer of the resin composition is non-existent or minimized, the matrix copolymer can include a small amount of (meth)acrylate monomer units. Accordingly, the decrease in chemical resistance and the increase in manufacturing costs caused by (meth)acrylate monomer units can be minimized.

[0056] According to one embodiment of the present invention, the first aromatic vinyl monomer for forming the first aromatic vinyl monomer unit of the rubbery polymer may be one or more selected from the group consisting of styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene, and as a specific example, it may be styrene.

[0057] According to one embodiment of the present invention, the conjugated diene monomer for forming the conjugated diene monomer unit of the rubbery polymer may be one or more selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, and 2-phenyl-1,3-butadiene, and more specifically, 1,3-butadiene may be used.

[0058] According to one embodiment of the present invention, the rubbery polymer may contain the first aromatic vinyl monomer unit in an amount of 15% by weight or more and 40% by weight or less. Specifically, it may contain 16% by weight or more, 17% by weight or more, 18% by weight or more, 19% by weight or more, or 20% by weight or more, and may also contain 38% by weight or less, 36% by weight or less, 34% by weight or less, 32% by weight or less, or 30% by weight or less. When the above-described ranges are satisfied, the physical properties of the resin composition may be further improved.

[0059] According to one embodiment of the present invention, the refractive index of the rubbery polymer may be 1.523 to 1.542, and preferably 1.53 to 1.54. If the above-described range is satisfied, the transparency of the graft copolymer may be further improved.

[0060] According to one embodiment of the present invention, the rubbery polymer may have an average particle size of 240 nm or more and 350 nm or less, and as a specific example, may have an average particle size of 245 nm or more, 250 nm or more, 255 nm or more, or 260 nm or more, and may also have an average particle size of 345 nm or less, 340 nm or less, 335 nm or less, or 330 nm or less. When satisfying the above-described ranges, excellent transparency, impact resistance, and fluidity can be imparted to the resin composition.

[0061] According to one embodiment of the present invention, the rubbery polymer may have a full width at half maximum (FWHM) of 30 nm or more and 70 nm or less as measured by CHDF (Capillary Hydro Dynamic Fractionation). Specifically, it may be 32 nm or more, 34 nm or more, 36 nm or more, 38 nm or more, or 40 nm or more, and may also be 68 nm or less, 66 nm or less, 64 nm or less, 62 nm or less, or 60 nm or less. When the above-described ranges are satisfied, excellent transparency, impact resistance, and fluidity can be imparted to the resin composition.

[0062]

[0063] According to one embodiment of the present invention, the graft copolymer may be formed by graft polymerizing a (meth)acrylate-based monomer unit and a second aromatic vinyl-based monomer unit onto the rubbery polymer. Accordingly, the graft copolymer may comprise the rubbery polymer and the (meth)acrylate-based monomer unit and the second aromatic vinyl-based monomer unit grafted onto the rubbery polymer, and may also comprise the (meth)acrylate-based monomer unit and the second aromatic vinyl-based monomer unit not grafted onto the rubbery polymer in the portion where the graft layer of the graft copolymer is formed according to the graft polymerization conditions. In this case, the graft polymerization may be carried out by emulsion polymerization or bulk polymerization.

[0064] According to one embodiment of the present invention, the (meth)acrylate monomer for forming the (meth)acrylate monomer unit of the graft copolymer is C1 to C 10 It may be an alkyl (meth)acrylate monomer, and C1 to C 10The alkyl (meth)acrylate monomer may be one or more selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, heptyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and decyl (meth)acrylate, and specifically may be methyl methacrylate.

[0065] According to one embodiment of the present invention, the second aromatic vinyl monomer for forming the second aromatic vinyl monomer unit of the graft copolymer may be one or more selected from the group consisting of styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene, and as a specific example, it may be styrene.

[0066] A graft copolymer according to one embodiment of the present invention may further include vinyl cyanide monomer units. In this case, the graft copolymer may be formed by graft polymerizing (meth)acrylate monomer units, second aromatic vinyl monomer units, and vinyl cyanide monomer units onto the rubbery polymer. Accordingly, the graft copolymer may comprise the rubbery polymer and (meth)acrylate monomer units, second aromatic vinyl monomer units, and vinyl cyanide monomer units grafted onto the rubbery polymer, and may also comprise (meth)acrylate monomer units, second aromatic vinyl monomer units, and vinyl cyanide monomer units that are not grafted onto the rubbery polymer in the portion where the graft layer of the graft copolymer is formed according to the graft polymerization conditions.

[0067] 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, phenylacrylonitrile, and α-chloroacrylonitrile, and as a specific example, it may be acrylonitrile.

[0068] According to one embodiment of the present invention, the graft copolymer may comprise the rubbery polymer in an amount of 35% by weight or more and 65% by weight or less, (meth)acrylate-based monomer units grafted onto the rubbery polymer in an amount of 14% by weight or more and 45% by weight or less, second aromatic vinyl-based monomer units grafted onto the rubbery polymer in an amount of 12% by weight or more and 34% by weight or less, and vinyl cyanide-based monomer units grafted onto the rubbery polymer in an amount of 0% by weight or more and 7% by weight or less. When the above-described ranges are satisfied, the physical properties of the resin composition may be further improved.

[0069] According to one embodiment of the present invention, the graft copolymer may contain the rubbery polymer in an amount of 36 wt% or more, 37 wt% or more, 38 wt% or more, 39 wt% or more, or 40 wt% or more, and may also contain 64 wt% or less, 63 wt% or less, 62 wt% or less, 61 wt% or less, or 60 wt% or less. When the above-described ranges are satisfied, the physical properties of the resin composition may be further improved.

[0070] According to one embodiment of the present invention, the graft copolymer may contain (meth)acrylate-based monomer units grafted onto the rubbery polymer in an amount of 15 wt% or more, 16 wt% or more, 17 wt% or more, 18 wt% or more, 19 wt% or more, or 20 wt% or more, and may also contain 44 wt% or less, 43 wt% or less, 42 wt% or less, 41 wt% or less, or 40 wt% or less. When the above-described ranges are satisfied, the physical properties of the resin composition may be further improved.

[0071] According to one embodiment of the present invention, the graft copolymer may contain a second aromatic vinyl monomer unit grafted to the rubbery polymer in an amount of 13 wt% or more, 14 wt% or more, 16 wt% or more, 18 wt% or more, or 20 wt% or more, and may contain 33 wt% or less, 32 wt% or less, 31 wt% or less, or 30 wt% or less. When the above-described ranges are satisfied, the physical properties of the resin composition may be further improved.

[0072] According to one embodiment of the present invention, the graft copolymer may contain vinyl cyanide monomer units grafted onto the rubbery polymer in an amount of 1 wt% or more, 1.5 wt% or more, 2 wt% or more, 2.5 wt% or more, or 3 wt% or more, and may also contain 6.5 wt% or less, 6 wt% or less, 5.5 wt% or less, or 5 wt% or less. When the above-described ranges are satisfied, the physical properties of the resin composition may be further improved.

[0073] According to one embodiment of the present invention, the refractive index of the graft copolymer may be 1.523 to 1.542, and preferably 1.53 to 1.54. If the above-described range is satisfied, the refractive index matches or is similar to that of the rubbery polymer described above, so the transparency of the graft copolymer can be further improved.

[0074]

[0075] A resin composition according to one embodiment of the present invention may contain 15 parts by weight or more and 65 parts by weight or less of the graft copolymer with respect to 100 parts by weight of the total sum of the graft copolymer and the matrix copolymer. Specifically, it may contain 16 parts by weight or more, 18 parts by weight or more, 20 parts by weight or more, 22 parts by weight or more, 24 parts by weight or more, 26 parts by weight or more, 28 parts by weight or more, or 30 parts by weight or more, and may also contain 60 parts by weight or less, 55 parts by weight or less, 50 parts by weight or less, 45 parts by weight or less, or 40 parts by weight or less. When the above-described ranges are satisfied, the physical properties of the resin composition may be further improved.

[0076]

[0077] Matrix copolymer

[0078] According to one embodiment of the present invention, the matrix copolymer may comprise a (meth)acrylate-based monomer unit and a second aromatic vinyl-based monomer unit as a resin for imparting basic physical properties to a resin composition.

[0079]

[0080] It may include a (meth)acrylate-based monomer unit not grafted onto the above rubbery polymer, and a second aromatic vinyl-based monomer unit not grafted onto the above rubbery polymer.

[0081] According to one embodiment of the present invention, the (meth)acrylate monomer unit of the matrix copolymer may be a (meth)acrylate monomer unit that is not grafted onto the rubbery polymer, and the (meth)acrylate monomer for forming the same may be C1 to C 10 It may be an alkyl (meth)acrylate monomer, and C1 to C 10The alkyl (meth)acrylate monomer may be one or more selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, heptyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and decyl (meth)acrylate, and specifically may be methyl methacrylate.

[0082] According to one embodiment of the present invention, the second aromatic vinyl monomer unit of the matrix copolymer may be a second aromatic vinyl monomer unit that is not grafted onto the rubbery polymer, and the second aromatic vinyl monomer for forming the same may be one or more selected from the group consisting of styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene, and as a specific example, it may be styrene.

[0083] A matrix copolymer according to one embodiment of the present invention may further include vinyl cyanide monomer units. In this case, the matrix copolymer may include (meth)acrylate monomer units, second aromatic vinyl monomer units, and vinyl cyanide monomer units that are not grafted onto the rubbery polymer.

[0084] 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, phenylacrylonitrile, and α-chloroacrylonitrile, and as a specific example, it may be acrylonitrile.

[0085] According to one embodiment of the present invention, the matrix copolymer may comprise (meth)acrylate-based monomer units not grafted onto the rubbery polymer in an amount of 39% by weight or more and 66% by weight or less, second aromatic vinyl-based monomer units not grafted onto the rubbery polymer in an amount of 33% by weight or more and 52% by weight or less, and vinyl cyanide-based monomer units not grafted onto the rubbery polymer in an amount of 0% by weight or more and 12% by weight or less. When the above-described ranges are satisfied, the physical properties of the resin composition may be further improved.

[0086] According to one embodiment of the present invention, the matrix copolymer may contain (meth)acrylate-based monomer units not grafted onto the rubbery polymer in an amount of 40 wt% or more, 41 wt% or more, 42 wt% or more, 43 wt% or more, 44 wt% or more, or 45 wt% or more, and may also contain 65 wt% or less, 64 wt% or less, 63 wt% or less, 62 wt% or less, 61 wt% or less, or 60 wt% or less. When the above-described ranges are satisfied, the physical properties of the resin composition may be further improved.

[0087] According to one embodiment of the present invention, the matrix copolymer may contain a second aromatic vinyl monomer unit not grafted onto the rubbery polymer in an amount of 34 wt% or more, 35 wt% or more, 36 wt% or more, 38 wt% or more, or 40 wt% or more, and may contain 51 wt% or less, 50 wt% or less, 48 ​​wt% or less, or 46 wt% or less. When the above-described ranges are satisfied, the physical properties of the resin composition may be further improved.

[0088] According to one embodiment of the present invention, the matrix copolymer may contain vinyl cyanide monomer units not grafted onto the rubbery polymer in an amount of 1 wt% or more, 1.5 wt% or more, 2 wt% or more, 2.5 wt% or more, or 3 wt% or more, and may also contain 11 wt% or less, 10 wt% or less, 9 wt% or less, or 8 wt% or less. When the above-described ranges are satisfied, the physical properties of the resin composition may be further improved.

[0089] According to one embodiment of the present invention, the refractive index of the matrix copolymer may be 1.523 to 1.542, and preferably 1.53 to 1.54. If the above-described range is satisfied, the refractive index of the matrix copolymer is matched or similar to that of the above-described matrix copolymer, so the transparency of the resin composition can be further improved.

[0090]

[0091] A resin composition according to one embodiment of the present invention may include the matrix copolymer in an amount of 35 parts by weight or more and 85 parts by weight or less, based on 100 parts by weight of the total amount of the graft copolymer and the matrix copolymer. Specifically, it may include 36 parts by weight or more, 38 parts by weight or more, 40 parts by weight or more, 42 parts by weight or more, 44 parts by weight or more, 46 parts by weight or more, 48 parts by weight or more, or 50 parts by weight or more, and may also include 80 parts by weight or less, 75 parts by weight or less, 70 parts by weight or less, 65 parts by weight or less, or 60 parts by weight or less. When the above-described ranges are satisfied, the physical properties of the resin composition may be further improved.

[0092]

[0093] Other additives

[0094] A resin composition according to one embodiment of the present invention may further include additives. The additives may be one or more selected from the group consisting of lubricants, flame retardants, flame retardant aids, antioxidants, light stabilizers, hydrolysis stabilizers, release agents, pigments, antistatic agents, conductivity imparters, 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. The 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.

[0095] According to one embodiment of the present invention, the additive may be included in an amount of 0.2 parts by weight or more and 2 parts by weight or less per 100 parts by weight of the total content of the graft copolymer and the matrix copolymer. If the above-described range is satisfied, the physical properties of the resin composition may not be impaired.

[0096]

[0097] Resin composition

[0098] In the present invention, the weight of the rubbery polymer, conjugated diene monomer unit, (meth)acrylate monomer unit, first aromatic vinyl monomer unit, and second aromatic vinyl monomer unit included in the resin composition can be measured by infrared spectroscopy on the resin composition.

[0099] According to one embodiment of the present invention, the rubbery polymer measured by infrared spectroscopy on the resin composition may be derived from the graft copolymer. Since the detailed description of the rubbery polymer is as described above, a detailed description thereof will be omitted.

[0100] According to one embodiment of the present invention, the (meth)acrylate monomer unit measured by infrared spectroscopy on the resin composition may include both the (meth)acrylate monomer unit included in the graft copolymer that is 'a (meth)acrylate monomer unit grafted onto the rubbery polymer' and the (meth)acrylate monomer unit included in the matrix copolymer that is 'a (meth)acrylate monomer unit not grafted onto the rubbery polymer'.

[0101] According to one embodiment of the present invention, the second aromatic vinyl monomer unit measured by infrared spectroscopy on the resin composition may include both the second aromatic vinyl monomer unit included in the graft copolymer, which is 'the second aromatic vinyl monomer unit grafted into the graft copolymer' and the second aromatic vinyl monomer unit included in the matrix copolymer, which is 'the second aromatic vinyl monomer unit not grafted into the graft copolymer'.

[0102] A resin composition according to one embodiment of the present invention may further include vinyl cyanide monomer units. In this case, the vinyl cyanide monomer units measured by infrared spectroscopy on the resin composition may include both 'vinyl cyanide monomer units grafted onto the graft copolymer' as vinyl cyanide monomer units included in the graft copolymer and 'vinyl cyanide monomer units not grafted onto the graft copolymer' as vinyl cyanide monomer units included in the matrix copolymer.

[0103] In a resin composition according to one embodiment of the present invention, the rubbery polymer measured by infrared spectroscopy may be 9 wt% or more and 25 wt% or less, the (meth)acrylate-based monomer unit may be 30 wt% or more and 60 wt% or less, the second aromatic vinyl-based monomer unit may be 22 wt% or more and 47 wt% or less, and the vinyl cyanide-based monomer unit may be 0 wt% or more and 10 wt% or less. In other words, regarding the entire resin composition according to one embodiment of the present invention, the rubbery polymer may be included in an amount of 9 wt% or more and 25 wt% or less, the (meth)acrylate-based monomer unit may be included in an amount of 30 wt% or more and 60 wt% or less, the second aromatic vinyl-based monomer unit may be included in an amount of 22 wt% or more and 47 wt% or less, and the vinyl cyanide-based monomer unit may be included in an amount of 0 wt% or more and 10 wt% or less.

[0104] The rubbery polymer measured by infrared spectroscopy on a resin composition according to one embodiment of the present invention may specifically be 10 wt% or more, 11 wt% or more, 12 wt% or more, 13 wt% or more, 14 wt% or more, or 15 wt% or more, and may also be 24 wt% or less, 23 wt% or less, 22 wt% or less, 21 wt% or less, or 20 wt% or less.

[0105] Specifically, the (meth)acrylate-based monomer unit measured by infrared spectroscopy in the resin composition according to one embodiment of the present invention may be 32 wt% or more, 34 wt% or more, 36 wt% or more, 38 wt% or more, or 40 wt% or more, and may also be 58 wt% or less, 56 wt% or less, 54 wt% or less, 52 wt% or less, or 50 wt% or less.

[0106] Specifically, the second aromatic vinyl monomer unit measured by infrared spectroscopy on the resin composition according to one embodiment of the present invention may be 23 wt% or more, 24 wt% or more, 25 wt% or more, 26 wt% or more, or 27 wt% or more, and may also be 46 wt% or less, 45 wt% or less, 44 wt% or less, 43 wt% or less, or 42 wt% or less.

[0107] Specifically, the vinyl cyanide monomer unit in the resin composition according to one embodiment of the present invention may be 1 wt% or more, 1.5 wt% or more, 2 wt% or more, 2.5 wt% or more, or 3 wt% or more, and may also be 9 wt% or less, 8 wt% or less, 7 wt% or less, 6 wt% or less, or 5 wt% or less.

[0108]

[0109] In a resin composition according to one embodiment of the present invention, when observed with a TEM image, the number average particle size of the observed rubbery polymer may be 210 nm or more and 350 nm or less. Specifically, it may be 215 nm or more, 220 nm or more, 225 nm or more, 230 nm or more, or 235 nm or more, and may also be 340 nm or less, 330 nm or less, 320 nm or less, 310 nm or less, or 300 nm or less. When the above-described ranges are satisfied, the transparency, impact strength, and fluidity of the resin composition may all be excellent. If the number average particle size of the rubbery polymer exceeds the above-described range, the transparency of the resin composition may decrease, and if it is below the above-described range, the impact strength of the resin composition may decrease.

[0110] In the present invention, the number average particle size can be calculated by recognizing rubbery polymer particles within a TEM image, separating them by individual, and measuring the area of ​​each particle (the diameter of a circle having the same area as the particle observed in the TEM image) and the number of particles within the image. Specifically, it may be calculated by dividing the sum of the particle sizes of rubbery polymer particles within the TEM image by the total number of particles.

[0111] In a resin composition according to one embodiment of the present invention, when observed with a TEM image, the standard deviation of the number average particle size of the observed rubbery polymer may be 110 nm or less. Specifically, it may be 105 nm or less, 100 nm or less, 95 nm or less, 95 nm or less, or 90 nm or less, and may also be 40 nm or more, 45 nm or more, 50 nm or more, 55 nm or more, or 60 nm or more. When the above-described ranges are satisfied, the transparency, impact strength, and fluidity of the resin composition may all be excellent. If the standard deviation of the number average particle size of the rubbery polymer exceeds the above-described range, rubbery polymers with small particle sizes exist in excess of what is necessary, making it difficult to control polymerization during graft polymerization, and as a result, the transparency of the resin composition may be reduced.

[0112] In a resin composition according to one embodiment of the present invention, when observed with a TEM image, the ratio of the number of rubbery polymers with a number average particle size of 100 nm or less to the total number of rubbery polymers (number of rubbery polymers with a number average particle size of 100 nm or less / total number of rubbery polymers) may be 15% or less, and specifically, as an example, 14% or less, 13% or less, 11% or less, or 10% or less. When the above range is satisfied, the transparency, impact strength, and fluidity of the resin composition may be even better.

[0113] Meanwhile, the number average particle size and standard deviation of the particle size within the range described above can be achieved by controlling the particle size of the rubbery polymer introduced when manufacturing the resin composition, that is, the average particle size and / or particle size half-width range as described above.

[0114]

[0115] A resin composition according to one embodiment of the present invention may have a haze of 2.5% or less as measured according to ASTM D1003, and specifically, as an example, may be 2.4% or less, 2.3% or less, 2.2% or less, 2.1% or less, 2.0% or less, 1.9% or less, 1.8% or less, 1.7% or less, 1.6% or less, or 1.5% or less. If the above-described range is satisfied, the resin composition can be evaluated as having excellent transparency.

[0116] Meanwhile, transparency within the range described above can be achieved when the refractive index of the graft copolymer included in the resin composition and the refractive index of the matrix copolymer are the same. In the present invention, the refractive index being the same means that the difference in refractive index is 0.005 or less, 0.004 or less, 0.003 or less, 0.002 or less, or 0.001 or less, or that the refractive index is completely identical.

[0117]

[0118] Molded product

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

[0120] According to one embodiment of the present invention, the molded article may be extruded and injection-molded from the resin composition and may be applied to a product family requiring a transparent plastic that exhibits a matte finish, and as a specific example, may be a part such as a washing machine transparent window or an office equipment transparent window.

[0121]

[0122] Hereinafter, embodiments of the present invention are described in detail so that those skilled in the art can easily implement the invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

[0123]

[0124] Preparation Example 1: Preparation of Graft Copolymer A-1

[0125] Manufacture of rubber latex

[0126] 1.3 parts by weight of potassium rosinate, 1.0 parts by weight of potassium oleate, 1.5 parts by weight of potassium carbonate, and 100 parts by weight of water were filled into a pressure vessel equipped with a stirrer, and after purging with nitrogen, the temperature was raised to 50°C. Subsequently, 75 parts by weight of butadiene, 25 parts by weight of styrene, 0.2 parts by weight of tertiary-dodecyl mercaptan, and 0.3 parts by weight of potassium persulfate were added to the pressure vessel, and polymerization was performed by raising the temperature to 80°C over 2 hours and maintaining the temperature for 30 hours, thereby obtaining an SBR rubber latex (S1) with a conversion rate of 93%, an average particle size of 3050 Å, and a full width at half maximum (FWHM) of 740 Å.

[0127] The average particle size of the SBR rubber latex (S1) was measured as an intensity value in Gaussian mode using a particle size analyzer with a Nicomp 380 instrument from Particle Sizing Systems, which is the arithmetic mean particle size in the particle size distribution measured by dynamic light scattering. Specifically, 0.1g of SBR rubber latex (S1) was prepared by diluting it with distilled water so as not to deviate significantly from the Intensity Setpoint of 300kHz and placing it in a glass tube. It was then auto-diluted and measured using a flow cell. The measurement mode was set to dynamic light scattering / Intensity 300KHz / Intensity-weight Gaussian Analysis, and the setting values ​​were set to a temperature of 23℃, a measurement wavelength of 632.8nm, and a channel width of 10μsec.

[0128] In addition, the full width at half maximum (FWHM) of the SBR rubber latex (S1) was measured using the CHDF (Capillary Hydrodynamic Fractionation) method with MATEC CHDF 400. Here, the full width at half maximum (FWHM) refers to the difference between particle sizes corresponding to half of the maximum particle size (fmax) in the particle size distribution map measured by the CHDF method.

[0129] <Preparation of Graft Copolymers>

[0130] 100 parts by weight of ion-exchanged water, 1.0 parts by weight of sodium oleate emulsifier, 23.9 parts by weight of methyl methacrylate, 21.1 parts by weight of styrene, 5 parts by weight of acrylonitrile, 0.3 parts by weight of tertiary dodecyl mercaptan, 0.05 parts by weight of ethylenediaminetetraacetic acid, 0.1 parts by weight of sodium formaldehyde sulfoxylate, 0.001 parts by weight of ferrous sulfide, and 0.2 parts by weight of cumene hydroperoxide were continuously added to 50 parts by weight of manufactured SBR rubber latex (S1) at 75°C for 5 hours and reacted. After the reaction, the temperature was raised to 80°C, aged for 1 hour, and the reaction was terminated. 2 parts by weight of calcium chloride was added as a coagulant to the reaction product, and graft copolymer powder was obtained through dehydration and drying. The refractive index of the obtained graft copolymer (A-1) was 1.535.

[0131] The refractive index of the graft copolymer (A-1) was measured using an Abbe refractometer with visible light having a wavelength of 589.3 nm at 25°C after spreading the graft copolymer (A-1) to a thickness of 0.2 mm.

[0132]

[0133] Preparation Example 2: Preparation of Graft Copolymer A-2

[0134] Manufacture of rubber latex

[0135] 1.3 parts by weight of potassium rosinate, 1.0 parts by weight of potassium oleate, 1.5 parts by weight of potassium carbonate, and 100 parts by weight of water were filled into a pressure vessel equipped with a stirrer, and after purging with nitrogen, the temperature was raised to 50°C. Subsequently, 50 parts by weight of butadiene, 25 parts by weight of styrene, 0.2 parts by weight of tertiary-dodecyl mercaptan, and 0.4 parts by weight of potassium persulfate were added to the pressure vessel, and the temperature was raised to 80°C over 2 hours and maintained for 30 hours to perform polymerization. From 3 hours after the polymerization began, 25 parts by weight of butadiene were added for 20 hours to continue the polymerization, thereby obtaining an SBR rubber latex (S2) with a conversion rate of 95%, an average particle size of 2900 Å, and a FWHM of 540 Å.

[0136] The average particle size and FWHM of the SBR rubber latex (S2) were measured in the same way as described in Preparation Example 1 above.

[0137]

[0138] <Preparation of Graft Copolymers>

[0139] 100 parts by weight of ion-exchanged water, 1.0 parts by weight of sodium oleate emulsifier, 23.9 parts by weight of methyl methacrylate, 21.1 parts by weight of styrene, 5 parts by weight of acrylonitrile, 0.3 parts by weight of tertiary dodecyl mercaptan, 0.05 parts by weight of ethylenediaminetetraacetic acid, 0.1 parts by weight of sodium formaldehyde sulfoxylate, 0.001 parts by weight of ferrous sulfide, and 0.2 parts by weight of cumene hydroperoxide were continuously added to 50 parts by weight of manufactured SBR rubber latex (S2) at 75°C for 5 hours and reacted. After the reaction, the temperature was raised to 80°C, aged for 1 hour, and the reaction was terminated. 2 parts by weight of calcium chloride was added as a coagulant to the reaction product, and graft copolymer powder was obtained through dehydration and drying. The refractive index of the obtained graft copolymer (A-2) was 1.535.

[0140] The refractive index of the graft copolymer (A-2) was measured in the same manner as described in Preparation Example 1 above.

[0141]

[0142] Preparation Example 3: Preparation of Graft Copolymer A-3

[0143] Manufacture of rubber latex

[0144] 0.5 parts by weight of potassium rosinate, 2.5 parts by weight of potassium oleate, 1.0 parts by weight of potassium carbonate, 0.005 parts by weight of ferrous sulfate, 0.008 parts by weight of disodium ethylenediaminetetraacetate, 0.05 parts by weight of sodium formaldehyde sulfoxylate, and 200 parts by weight of water were filled into a pressure vessel equipped with a stirrer, and after purging with nitrogen, the temperature was raised to 50°C. Subsequently, 75 parts by weight of butadiene, 25 parts by weight of styrene, and 0.3 parts by weight of t-butyl hydroperoxide were added to the pressure vessel, and the temperature was raised to 70°C over 2 hours. Afterward, polymerization was carried out by maintaining the temperature for 20 hours, and an SBR rubber latex (S3) with a conversion rate of 98%, an average particle size of 950 Å, and a FWHM of 480 Å was obtained.

[0145] The average particle size and FWHM of the SBR rubber latex (S3) were measured in the same way as described in Preparation Example 1 above.

[0146]

[0147] <Preparation of Graft Copolymers>

[0148] 50 parts by weight of manufactured SBR rubber latex (S3) were continuously added to 100 parts by weight of ion-exchanged water, 1.0 parts by weight of sodium oleate emulsifier, 23.9 parts by weight of methyl methacrylate, 21.1 parts by weight of styrene, 5 parts by weight of acrylonitrile, 0.3 parts by weight of tertiary dodecyl mercaptan, 0.05 parts by weight of ethylenediaminetetraacetic acid, 0.1 parts by weight of sodium formaldehyde sulfoxylate, 0.001 parts by weight of ferrous sulfide, and 0.2 parts by weight of cumene hydroperoxide at 75°C for 5 hours and reacted. After the reaction, the temperature was raised to 80°C, aged for 1 hour, and the reaction was terminated. 2 parts by weight of calcium chloride was added as a coagulant to the reaction product, and graft copolymer powder was obtained through dehydration and drying. The refractive index of the obtained graft copolymer (A-3) was 1.535.

[0149] The refractive index of the graft copolymer (A-3) was measured in the same manner as described in Preparation Example 1 above.

[0150]

[0151] Preparation Example 4: Preparation of Graft Copolymer A-4

[0152] Manufacture of rubber latex

[0153] 100 parts by weight of the above SBR rubber latex (S3) were added to a reaction vessel, and the stirring speed was adjusted to 10 rpm and the temperature to 30°C. Then, 2.0 parts by weight of a 5% aqueous acetic acid solution were slowly added over 1 hour, after which stirring was stopped and the mixture was left for 30 minutes to produce an SBR rubber latex (S4) with an average particle size of 3200 Å and an FWHM of 1380 Å.

[0154] The average particle size and FWHM of the SBR rubber latex (S4) were measured in the same way as described in Preparation Example 1 above.

[0155]

[0156] <Preparation of Graft Copolymers>

[0157] 50 parts by weight of manufactured SBR rubber latex (S4) were continuously added to 100 parts by weight of ion-exchanged water, 1.0 parts by weight of sodium oleate emulsifier, 23.9 parts by weight of methyl methacrylate, 21.1 parts by weight of styrene, 5 parts by weight of acrylonitrile, 0.3 parts by weight of tertiary dodecyl mercaptan, 0.05 parts by weight of ethylenediaminetetraacetic acid, 0.1 parts by weight of sodium formaldehyde sulfoxylate, 0.001 parts by weight of ferrous sulfide, and 0.2 parts by weight of cumene hydroperoxide at 75°C for 5 hours and reacted. After the reaction, the temperature was raised to 80°C, aged for 1 hour, and the reaction was terminated. 2 parts by weight of calcium chloride was added as a coagulant to the reaction product, and graft copolymer powder was obtained through dehydration and drying. The refractive index of the obtained graft copolymer (A-4) was 1.535.

[0158] The refractive index of the graft copolymer (A-4) was measured in the same manner as described in Preparation Example 1 above.

[0159]

[0160] Preparation Example 5: Preparation of Matrix Copolymer (B-1)

[0161] A raw material mixture comprising 48.5 parts by weight of methyl methacrylate, 42.5 parts by weight of styrene, and 9 parts by weight of acrylonitrile, 30 parts by weight of toluene as a solvent, and 0.3 parts by weight of normal octyl mercaptan as a molecular weight regulator was continuously fed into a reaction vessel for an average reaction time of 3 hours, and the reaction temperature was maintained at 148°C. The polymer solution discharged from the reaction vessel was heated in a preheating tank, unreacted monomers were evaporated in a volatilization tank, and the temperature of the polymer was maintained at 210°C. The copolymer resin was then processed into pellet form using a polymer transfer pump extruder. The refractive index of the prepared matrix copolymer was 1.535.

[0162] The refractive index of the matrix copolymer (B-1) was measured in the same manner as described in Preparation Example 1 above.

[0163]

[0164] Preparation Example 6: Preparation of Matrix Copolymer (B-2)

[0165] A raw material mixture comprising 70.4 parts by weight of methyl methacrylate, 24.6 parts by weight of styrene, and 5 parts by weight of acrylonitrile, 30 parts by weight of toluene as a solvent, and 0.3 parts by weight of normal octyl mercaptan as a molecular weight regulator was continuously fed into a reaction vessel for an average reaction time of 3 hours, and the reaction temperature was maintained at 148°C. The polymer solution discharged from the reaction vessel was heated in a preheating tank, unreacted monomers were evaporated in a volatilization tank, and the temperature of the polymer was maintained at 210°C. The copolymer resin was then processed into pellet form using a polymer transfer pump extruder. The refractive index of the prepared matrix copolymer was 1.516.

[0166] The refractive index of the matrix copolymer (B-2) was measured in the same manner as described in Preparation Example 1 above.

[0167]

[0168] Examples and Comparative Examples

[0169] The graft copolymer and matrix copolymer prepared in Preparation Examples 1 to 6 above were mixed in the weight ratios shown in Table 1 below, and 0.5 parts by weight of ethylenebisstearamide as a lubricant and 0.2 parts by weight of IR 1076 as an antioxidant were added, and the mixture was prepared in the form of pellets using a twin-screw extrusion kneader at a cylinder temperature of 220°C.

[0170]

[0171] Experimental Example

[0172] Specimens were prepared by injecting the pellets prepared in the above examples and comparative examples, and physical properties were measured in the following manner, and the results are listed in Table 1 below.

[0173]

[0174] * Transparency (Haze; %): Transparency was measured according to ASTM D1003.

[0175]

[0176] * Melt flow index (g / 10min): Measured according to ASTM D1238 under conditions of 220℃ and 10kg.

[0177]

[0178] * Impact strength (kgf·cm / cm, 1 / 4 inch): Measured at 23℃ according to ASTM D256.

[0179]

[0180] * Number average particle size and standard deviation of rubbery polymer: For each specimen, TEM images (magnification 25,000x) were taken at an acceleration voltage of 120kV using a Leica EM UC7 / FC7 and an OsO4 staining at a thickness of 90nm or less. The diameter of a circle having the same area as each rubbery polymer particle observed in the TEM image was defined as the particle size of the rubbery polymer particle, and the number average particle size was calculated by adding the individual particle sizes and dividing the result by the total number of rubbery polymer particles. Additionally, the difference between each particle size and the number average particle size was defined as the deviation, and the standard deviation of the number average particle size was calculated by taking the square root of the variance value obtained by dividing the sum of the squares of these deviations by the total number of rubbery polymer particles.

[0181] TEM images of resin composition specimens according to Examples 1 and 2 are shown in FIG. 1 and 2, respectively, and TEM images of resin composition specimens according to Comparative Example 1 are shown in FIG. 3.

[0182]

[0183] Example Comparative Example 1 2 1 2 3 4 Graft copolymer type A-2 A-2 A-1 A-3 A-4 A-2 Average particle size (nm) (of rubbery polymer) 290 290 30 59 53 20 290 FWHM (nm) (of rubbery polymer) 54 54 74 48 13 8 5 4 Refractive index 1.535 1.535 1.535 1.535 1.535 1.535 1.535 1.535 1.535 1.535 1.535 1.535 1.535 1.535 1.535 1.535 1.535 1.535 1.535 1.535 1.535 1.516 1.535 1.535 1.535 1.535 1.535 1.516 1.535 72 67 67 6767 67 7 Resin composition (of rubbery polymer) Number average particle size (nm) 250 23 82 11 90 24 12 3 8 (rubber Polymer) Particle Size Standard Deviation (nm) 8 1 6 9 1 3 6 3 6 1 1 2 6 9 Haze (%) 1.3 1.5 3.1 0.9 4.7 9 9 Excess Flow Index (g / 10 min) 28 2 4 2 5 1 5 2 4 2 4 Impact Strength (Kgf·cm / cm) 10.1 1 4.2 1 5.7 2.5 1 5.4 1 3.7

[0184] Referring to Table 1 above, it was confirmed that the resin compositions according to Examples 1 and 2 satisfied the number average particle size and standard deviation of the graft copolymer within the desired range, and that transparency, fluidity, and impact strength were all excellent.

[0185] In the case of Comparative Example 1, where the full half-width of the graft copolymer exceeds the desirable range, and Comparative Example 3, where it is less than the desirable range, it was confirmed that the number average particle size and standard deviation of the graft copolymer observed in the resin composition did not satisfy the desirable range, and the transparency decreased.

[0186] In the case of Comparative Example 2, where the average particle size of the graft copolymer is below the desirable range, it was confirmed that the number average particle size and standard deviation of the graft copolymer observed in the resin composition did not satisfy the desirable range, and that the impact strength and fluidity were reduced.

[0187] In the case of Comparative Example 4, where the difference in refractive index between the graft copolymer and the matrix copolymer exceeded 0.005, it was confirmed that the transparency decreased.

Claims

1. A rubbery polymer comprising a first aromatic vinyl monomer unit and a conjugated diene monomer unit; (Met)acrylate-based monomer units; and A resin composition comprising a second aromatic vinyl monomer unit, The transparency (Haze) of the above resin composition, measured according to ASTM D1003, is 2.5% or less, and A resin composition in which, when the resin composition is observed by a TEM image, the number average particle size of the observed rubbery polymer is 210 nm or more and 350 nm or less, and the standard deviation of the number average particle size is 110 nm or less.

2. In Paragraph 1, A resin composition in which, when the resin composition is observed by a TEM image, the number average particle size of the observed rubbery polymer is 235 nm or more and 300 nm or less.

3. In Paragraph 1, A resin composition in which, when the resin composition is observed by a TEM image, the standard deviation of the observed rubbery polymer particle size is 100 nm or less.

4. In Paragraph 1, The above rubbery polymer is included in an amount of 9% by weight or more and 25% by weight or less, and It contains (meth)acrylate-based monomer units in an amount of 30% by weight or more and 60% by weight or less, A resin composition comprising 22% by weight or more and 47% by weight or less of the above-mentioned second aromatic vinyl monomer unit.

5. In Paragraph 1, A resin composition having an average particle size of 240 nm or more and 350 nm or less of the above rubbery polymer.

6. In Paragraph 1, A resin composition having an average particle size of 260 nm or more and 330 nm or less of the above rubbery polymer.

7. In Paragraph 1, A resin composition having a full width at half maximum (FWHM) of the above-mentioned rubbery polymer measured by CHDF (Capillary Hydro Dynamic Fractionation) of 30 nm or more and 70 nm or less.

8. In Paragraph 1, A resin composition having a full width at half maximum (FWHM) of the above-mentioned rubbery polymer measured by CHDF (Capillary Hydro Dynamic Fractionation) of 40 nm or more and 60 nm or less.

9. In Paragraph 1, A graft copolymer comprising the above rubbery polymer, a (meth)acrylate-based monomer unit grafted onto the above rubbery polymer, and a second aromatic vinyl-based monomer unit grafted onto the above rubbery polymer; and A matrix copolymer comprising a (meth)acrylate-based monomer unit not grafted onto the rubbery polymer, and a second aromatic vinyl-based monomer unit not grafted onto the rubbery polymer, A resin composition in which the difference between the refractive index of the graft copolymer and the refractive index of the matrix copolymer is 0.005 or less.

10. In Paragraph 9, With respect to 100 parts by weight of the total sum of the graft copolymer and the matrix copolymer, The above graft copolymer is included in an amount of 15 parts by weight or more and 65 parts by weight or less, and A resin composition comprising 35 parts by weight or more and 85 parts by weight or less of the above matrix copolymer.

11. In Paragraph 9, The above resin composition further comprises vinyl cyanide monomer units, and The vinyl cyanide monomer unit comprises a vinyl cyanide monomer unit grafted onto the rubbery polymer and a vinyl cyanide monomer unit not grafted onto the rubbery polymer, and The above graft copolymer further comprises vinyl cyanide monomer units grafted onto the above rubbery polymer, and A resin composition in which the matrix copolymer further comprises vinyl cyanide monomer units that are not grafted onto the rubbery polymer.

12. In Paragraph 11, The above graft copolymer is: The above rubbery polymer is included in an amount of 35% by weight or more and 65% by weight or less, and The above rubbery polymer contains (meth)acrylate-based monomer units grafted thereon in an amount of 14% by weight or more and 45% by weight or less, The above rubbery polymer comprises a second aromatic vinyl monomer unit grafted thereon in an amount of 12% by weight or more and 34% by weight or less, and A resin composition comprising 7 weight% or less of vinyl cyanide monomer units grafted onto the above rubbery polymer.

13. In Paragraph 11, The above matrix copolymer is, The above rubbery polymer contains (meth)acrylate-based monomer units not grafted thereon in an amount of 39% by weight or more and 66% by weight or less, and The above rubbery polymer contains a second aromatic vinyl monomer unit that is not grafted in an amount of 33% by weight or more and 52% by weight or less, A resin composition comprising 12 weight percent or less of vinyl cyanide monomer units not grafted into the above rubbery polymer.

14. In Paragraph 1, The above rubbery polymer is a resin composition comprising 15% by weight or more and 40% by weight or less of a first aromatic vinyl monomer unit.

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