KR102268403B1 - Thermoplastic resin composition - Google Patents

Abstract

The present invention relates to a graft copolymer comprising an alkyl (meth)acrylate-based rubber-derived unit, an aromatic vinyl-based monomer-derived unit and a vinyl cyan-based monomer-derived unit; a first matrix copolymer comprising a unit derived from an alkyl (meth)acrylate monomer, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyanide monomer; and a second matrix copolymer including units derived from an alkyl (meth)acrylate-based monomer, units derived from an aromatic vinyl-based monomer, and units derived from a maleimide-based monomer.

Description

Thermoplastic resin composition {THERMOPLASTIC RESIN COMPOSITION}

The present invention relates to a thermoplastic resin composition, and more particularly, to provide a thermoplastic resin composition excellent in colorability and heat resistance.

ASA copolymer is an acrylonitrile-styrene-acrylate terpolymer, and has excellent weather resistance and aging resistance, so it is used in various fields such as automobiles, ships, leisure products, building materials, and horticulture. There is a problem that it is difficult to apply to this required product. As a method for improving the colorability of the ASA copolymer, there is a method of providing a thermoplastic resin composition by mixing an ASA copolymer and a methyl methacrylate polymer, but there is a problem in that the surface glossiness and heat resistance are reduced.

On the other hand, in U.S. Patent No. 4,224,419, in the thermoplastic resin excellent in colorability, the first graft copolymer prepared by graft polymerization of styrene and acrylonitrile to an acrylate rubber polymer having an average particle diameter of 50 to 150 nm, an average particle diameter of 200 A second graft copolymer comprising an acrylonitrile-styrene-acrylate copolymer prepared by graft polymerization of styrene and acrylonitrile to an acrylate polymer having a thickness of 500 nm, acrylonitrile and styrene or acrylonitrile and styrene and A mixture comprising a rigid copolymer made of α-methyl styrene is disclosed. However, due to the large-diameter acrylonitrile-styrene-acrylate copolymer, an article made of the mixture has a disadvantage in that colorability is poor.

Therefore, although research on a thermoplastic resin composition having excellent colorability and heat resistance and excellent surface gloss is continued, it is still insufficient.

KR2012-0009864A

An object of the present invention is to provide a thermoplastic resin composition excellent in colorability and heat resistance.

In order to solve the above problems, the present invention is a graft copolymer comprising an alkyl (meth) acrylate-based rubber-derived unit, an aromatic vinyl-based monomer-derived unit and a vinyl cyan-based monomer-derived unit; a first matrix copolymer comprising a unit derived from an alkyl (meth)acrylate monomer, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyanide monomer; and an alkyl (meth)acrylate-based monomer-derived unit, an aromatic vinyl-based monomer-derived unit, and a maleimide-based monomer-derived unit.

The thermoplastic resin composition according to the present invention is excellent in colorability, heat resistance, mechanical strength and melt index.

Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.

The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. It should be interpreted as meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

In the present invention, the average particle size may be defined as a particle size corresponding to 50% of the volume or cumulative amount in the particle size distribution curve of the particles.

In the present invention, the average particle diameter of the alkyl (meth)acrylate-based rubber of the graft copolymer can be measured after dissolving a certain amount of the graft copolymer in a solvent. Specifically, after dissolving 0.5 g of the graft copolymer in 100 ml of methyl ethyl ketone, it can be measured using a Coulter counter (trade name: LS230, manufacturer: Beckman Coulter).

In addition, in the present invention, it can be measured with a Particle Size Analyzer (NICOM™ 80) of the alkyl (meth)acrylate-based rubber of the graft copolymer.

The thermoplastic resin composition according to an embodiment of the present invention includes (1) a graft copolymer comprising an alkyl (meth)acrylate-based rubber-derived unit, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit; (2) a first matrix copolymer including units derived from an alkyl (meth)acrylate-based monomer, units derived from an aromatic vinyl-based monomer, and units derived from a vinyl cyanide-based monomer; and (3) a second matrix copolymer including units derived from an alkyl (meth)acrylate-based monomer, units derived from an aromatic vinyl-based monomer, and units derived from a maleimide-based monomer.

Hereinafter, each component of the thermoplastic resin composition of the present invention will be described in detail.

(One) graft copolymer

The graft copolymer is included to improve weather resistance and aging resistance of the thermoplastic resin composition according to an embodiment of the present invention.

The graft copolymer includes an alkyl (meth)acrylate-based rubber-derived unit, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit.

The alkyl (meth) acrylate-based rubber-derived unit is an alkyl (meth) acrylate-based polymer polymerized with an alkyl (meth) acrylate-based monomer is modified by graft polymerization with the aromatic vinyl-based monomer and a vinyl cyanide-based monomer. It may be a (meth)acrylate-based polymer.

The alkyl (meth) acrylate-based monomer may be C ₁ to C ₁₀ alkyl (meth) acrylate, and the C ₁ to C ₁₀ alkyl (meth) acrylate is methyl acrylate, ethyl acrylate, butyl acryl It may be at least one selected from the group consisting of acrylate and ethylhexyl acrylate, of which butyl acrylate is preferable.

The alkyl (meth)acrylate-based rubber-derived unit may be included in an amount of 30 to 60% by weight, 35 to 55% by weight, or 40 to 50% by weight, of which 40 to 50% by weight, based on the total weight of the graft copolymer. It is preferably included in weight %. When the above-described range is satisfied, the impact resistance and weather resistance of the graft copolymer may be further improved.

The aromatic vinyl-based monomer-derived unit may be at least one derived unit selected from the group consisting of styrene, α-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene, and vinyl toluene, among which styrene-derived units is preferable

The aromatic vinyl-based monomer-derived unit may be included in 35 to 65% by weight, 40 to 60% by weight, or 45 to 55% by weight, of which 45 to 55% by weight, based on the total weight of the graft copolymer. It is preferable to be When the above-described range is satisfied, the impact resistance and weather resistance of the graft copolymer may be further improved.

The vinyl cyan-based monomer-derived unit may be at least one derived unit selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile, and among these, an acrylonitrile-derived unit is preferable.

The vinyl cyan-based monomer-derived unit may be included in an amount of 1 to 25% by weight, 3 to 20% by weight, or 5 to 15% by weight, of which 5 to 15% by weight, based on the total weight of the graft copolymer. It is preferable to be When the above-described range is satisfied, the impact resistance and weather resistance of the graft copolymer may be further improved.

The graft copolymer may be included in an amount of 20 to 50 parts by weight, 25 to 45 parts by weight, or 30 to 40 parts by weight in the thermoplastic resin composition, of which 30 to 40 parts by weight is preferable. When the above-described range is satisfied, the impact resistance and weather resistance of the graft copolymer may be further improved.

The graft copolymer may include two or more types of graft copolymers having different average particle diameters. Specifically, the graft copolymer may include a small-diameter graft copolymer and a large-diameter graft copolymer.

The alkyl (meth)acrylate-based rubber-derived unit included in the small-diameter graft copolymer may have an average particle diameter of 80 to 200 nm, 90 to 180 nm, or 100 to 160 nm, of which 100 to 160 nm it is preferable When the above-mentioned range is satisfied, there is an effect that the surface glossiness and colorability of the thermoplastic resin composition become more excellent. In addition, impact strength, tensile strength, thermal stability and colorability of the alkyl (meth)acrylate-based rubber may be further improved.

The alkyl (meth)acrylate-based rubber-derived unit included in the large-diameter graft copolymer may have an average particle diameter of 350 to 600 nm, 370 to 550 nm, or 400 to 500 nm, of which 400 to 500 nm desirable. When the above-mentioned range is satisfied, there is an effect that the surface glossiness and colorability of the thermoplastic resin composition become more excellent. In addition, impact strength, tensile strength, thermal stability and colorability of the alkyl (meth)acrylate-based rubber may be further improved.

The weight ratio of the small-diameter graft copolymer and the large-diameter graft copolymer may be 1: 4 to 1: 9, 1: 5 to 1: 8, or 1: 6 to 1: 7, of which 1: 6 to 1 : 7 is preferable. When the above-mentioned range is satisfied, it is possible to provide a thermoplastic resin composition excellent in colorability, surface glossiness, and mechanical properties.

The graft copolymer may be prepared by at least one polymerization method from the group consisting of suspension polymerization, emulsion polymerization, and bulk polymerization, and among them, it is preferably prepared by emulsion polymerization.

(2) first matrix copolymer

The first matrix copolymer is included to improve colorability and heat resistance of the thermoplastic resin composition according to an embodiment of the present invention.

The first matrix copolymer includes an alkyl (meth)acrylate-based monomer-derived unit, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit.

The alkyl (meth) acrylate-based monomer-derived unit is methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, ethylhexyl acrylate and ethylhexyl methacrylate. It may be one or more types of derived units selected from the group consisting of, among them, methyl methacrylate-derived units are preferred.

The alkyl (meth) acrylate-based monomer-derived unit may be included in an amount of 50 to 90% by weight, 55 to 85% by weight, or 60 to 80% by weight, of which 60 to 80% by weight, based on the total weight of the first matrix copolymer. It is preferably included in weight %. When the above-described range is satisfied, there is an advantage in that colorability is increased and blackness is secured.

Specific examples of the aromatic vinyl-based monomer-derived unit are as described in '(1) Graft copolymer'.

The aromatic vinyl-based monomer-derived unit may be included in an amount of 5 to 40 wt%, 10 to 35 wt%, or 15 to 30 wt%, based on the total weight of the first matrix copolymer, of which 15 to 30 wt% It is preferable to be When the above-mentioned range is satisfied, there is an advantage in that the workability becomes excellent.

Specific examples of the vinyl cyan-based monomer-derived unit are as described in '(1) graft copolymer'.

The vinyl cyan-based monomer-derived unit may be included in an amount of 1 to 20 wt%, 3 to 17 wt%, or 5 to 15 wt%, based on the total weight of the first matrix copolymer, of which 5 to 15 wt% It is preferable to be When the above-described range is satisfied, there is an advantage in that impact resistance and chemical resistance are increased.

The first matrix copolymer may have a weight average molecular weight of 60,000 to 190,000 g/mol, 70,000 to 180,000 g/mol, or 80,000 to 170,000 g/mol, of which 80,000 to 170,000 g/mol is preferable. When the above-described range is satisfied, the refractive index of the first matrix copolymer may be improved, and thus the colorability of the thermoplastic resin composition may be further improved.

The weight average molecular weight of the first matrix copolymer may be measured as a relative value with respect to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent.

The first matrix copolymer may have a refractive index of 1.55 or less, 1.45 to 1.55, or 1.47 to 1.54, of which it is preferable that it is 1.50 to 1.53. When the above-mentioned range is satisfied, the colorability can be further improved.

The refractive index of the first matrix copolymer may be measured at 25 using an Abbe refractometer according to ASTM D542.

The first matrix copolymer may be included in the thermoplastic resin composition in an amount of 10 to 60 parts by weight, 15 to 55 parts by weight, or 20 to 50 parts by weight, of which 20 to 50 parts by weight is preferable. When the above-described range is satisfied, the refractive index of the first matrix copolymer may be improved, and thus the colorability of the thermoplastic resin composition may be improved.

The first matrix copolymer may be prepared by at least one polymerization method from the group consisting of suspension polymerization, emulsion polymerization, and bulk polymerization, and among them, it is preferably prepared by emulsion polymerization.

(3) second matrix copolymer

The second matrix copolymer is included to improve colorability and heat resistance of the thermoplastic resin composition according to an embodiment of the present invention.

The second matrix copolymer includes an alkyl (meth)acrylate-based monomer-derived unit, an aromatic vinyl-based monomer-derived unit, and a maleimide-based monomer-derived unit.

Specific examples of the alkyl (meth) acrylate-based monomer-derived unit are as described in '(2) First Matrix Copolymer'.

The alkyl (meth) acrylate-based monomer-derived unit may be included in an amount of 50 to 90% by weight, 55 to 85% by weight, or 60 to 80% by weight, of which 60 to 80% by weight, based on the total weight of the second matrix copolymer. It is preferably included in weight %. When the above-mentioned range is satisfied, there is an advantage in that colorability is increased and blackness is easily secured.

Specific examples of the aromatic vinyl-based monomer-derived unit are as described in '(1) Graft copolymer'.

The aromatic vinyl-based monomer-derived unit may be included in 1 to 20 wt%, 2 to 17 wt%, or 3 to 15 wt%, based on the total weight of the second matrix copolymer, of which 3 to 15 wt% It is preferable to be When the above-mentioned range is satisfied, there is an advantage in that the workability becomes excellent.

The maleimide-based monomer-derived unit is maleimide, N-methyl maleimide, N-ethyl maleimide, N-propyl maleimide, N-isopropyl maleimide, N-butyl maleimide, N-isobutyl maleimide, Nt -Butyl maleimide, N-lauryl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, N-(4-chlorophenyl) maleimide, 2-methyl-N-phenyl maleimide, N-(4 -Bromophenyl) maleimide, N-(4-nitrophenyl) maleimide, N-(4-hydroxyphenyl) maleimide, N-(4-methoxyphenyl) maleimide, N-(4-carboxyphenyl) ) may be at least one unit selected from the group consisting of maleimide and N-benzyl maleimide, and among them, a unit derived from N-phenylmaleimide is preferable.

The maleimide-based monomer-derived unit may be included in an amount of 5 to 45 wt%, 10 to 40 wt%, or 15 to 35 wt%, of which 15 to 35 wt%, based on the total weight of the second matrix copolymer. It is preferable to be When the above-described range is satisfied, there is an advantage in securing heat resistance.

The second matrix copolymer may have a weight average molecular weight of 110,000 to 290,000 g/mol, 130,000) to 270,000 g/mol, or 150,000 to 250,000 g/mol, of which 150,000 to 250,000 g/mol is preferable. When the above-described range is satisfied, the heat resistance of the thermoplastic resin composition may be improved.

The weight average molecular weight of the second matrix copolymer may be measured as a relative value with respect to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent.

The second matrix copolymer may have a refractive index of 1.55 or less, 1.47 to 1.55, or 1.48 to 1.54, of which 1.49 to 1.53 is preferable. When the above-mentioned range is satisfied, the colorability can be further improved.

The refractive index of the second matrix copolymer may be measured at 25 using an Abbe refractometer according to ASTM D542.

The second matrix copolymer may be included in the thermoplastic composition in an amount of 10 to 50 parts by weight, 15 to 45 parts by weight, or 20 to 40 parts by weight, of which 20 to 40 parts by weight is preferable. When the above-described range is satisfied, the refractive index of the first matrix copolymer may be improved, and thus the colorability of the thermoplastic resin composition may be further improved.

The total sum of the graft copolymer, the first matrix copolymer, and the second matrix copolymer may be 100 parts by weight.

The second matrix copolymer may be prepared by one or more polymerization methods from the group consisting of suspension polymerization, emulsion polymerization, and bulk polymerization, and among them, it is preferably prepared by emulsion polymerization.

The second matrix copolymer may be prepared directly or a commercially available material may be used. In the case of using a commercially available material, PML203 manufactured by NIPPON SHOKUBAI may be used.

Meanwhile, the thermoplastic resin composition according to an embodiment of the present invention may further include an additive. The additive may be at least one selected from the group consisting of anti-drip agents, flame retardants, antibacterial agents, antistatic agents, stabilizers, release agents, heat stabilizers, ultraviolet stabilizers, inorganic additives, lubricants, antioxidants, light stabilizers, pigments, dyes and inorganic fillers. Among them, at least one selected from the group consisting of lubricants, antioxidants, weathering stabilizers and dyes is preferable.

The lubricant may be at least one selected from the group consisting of ethylene bis stearamide, polyethylene oxide wax, and magnesium stearate.

The lubricant may be included in an amount of 0.1 parts by weight to 5 parts by weight or 0.5 parts by weight to 2 parts by weight based on 100 parts by weight of the total of the graft copolymer, the first matrix copolymer, and the second matrix copolymer, of which 0.5 It is preferably included in an amount of 2 parts by weight to 2 parts by weight.

The antioxidant may be a phenol-based antioxidant or a phosphate-based antioxidant, preferably stearyl-beta-(3,5-di-t-butyl-4-hydroxyphenyl)propionate.

The antioxidant may be included in an amount of 0.5 to 2 parts by weight based on 100 parts by weight of the total of the graft copolymer, the first matrix copolymer, and the second matrix copolymer.

The weathering stabilizer may be 2(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chloro benzotriazole.

The weathering stabilizer may be included in an amount of 0.05 parts by weight to 3 parts by weight or 0.2 parts by weight to 1 part by weight, based on 100 parts by weight of the total of the graft copolymer, the first matrix copolymer, and the second matrix copolymer, of which It is preferably included in an amount of 0.2 to 1 part by weight.

The black dye may have an average particle diameter of 5 to 100 nm or 7 to 60 nm, of which 7 to 60 nm is preferable.

The average particle diameter of the black dye may be measured by a TEM analysis method.

The black dye may be prepared as carbon black/SAN masterbatch, and the weight ratio of carbon black and SAN may be 30:70 to 70:30.

The thermoplastic resin composition according to an embodiment of the present invention may be used for one or more purposes selected from the group consisting of automobile parts, electric/electronic parts, and building materials, among which those used for automobile parts desirable.

The thermoplastic resin composition according to an embodiment of the present invention may have a colorability (L) of 25.2 or less or 25.1 or less, of which 25.1 or less is preferable. When the above-mentioned range is satisfied, excellent colorability can be ensured.

The colorability may be measured using a Colormeter device.

The thermoplastic resin composition according to an embodiment of the present invention may have a heat deflection temperature (°C) of 87°C or more, 90°C or more, or 90.5°C or more, of which 90.5°C or more is preferable. If the above-described range is satisfied within the range, the heat resistance may be further improved.

The heat deflection temperature may be measured using an HDT device.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

Example One

5 parts by weight of small-diameter graft copolymer (average particle diameter: 100 nm, core: butyl acrylate rubber-derived unit 40% by weight, shell: styrene-derived unit 48% by weight, acrylnitrile-derived unit 12% by weight) 5 parts by weight, large-diameter graft copolymer (Average particle diameter: 450 nm, core: butyl acrylate rubber-derived unit 40 wt%, shell: styrene-derived unit 48 wt%, acrylnitrile-derived unit 12 wt%) 32 parts by weight, first matrix copolymer (weight average molecular weight: 148,000) g/mol, methyl methacrylate-derived unit 70% by weight, styrene-derived unit 23% by weight, acrylonitrile-derived unit 7% by weight, refractive index: 1.52) 43 parts by weight, second matrix copolymer (manufacturer: NIPPON SHOKUBAI, trade name) : PML203, weight average molecular weight: 200,000 g/mol, refractive index: 1.52) 20 parts by weight, 1.0 parts by weight of lubricant, 0.8 parts by weight of antioxidant, 0.8 parts by weight of weathering stabilizer and 3.0 parts by weight of black dye to prepare a thermoplastic resin composition .

The thermoplastic resin composition was put into an extrusion kneader, and it was made into pellets under the condition of a cylinder temperature of 230° C., and a specimen was prepared by injection.

Example 2

A specimen was prepared in the same manner as in Example 1, except that 33 parts by weight of the first matrix copolymer and 30 parts by weight of the second matrix copolymer were added.

Example 3

A specimen was prepared in the same manner as in Example 1, except that 23 parts by weight of the first matrix copolymer and 40 parts by weight of the second matrix copolymer were added.

comparative example One

A low molecular weight copolymer as the first matrix copolymer (weight average molecular weight: 95,000 g/mol, methyl methacrylate-derived units 70 wt%, styrene-derived units 23 wt%, acrylonitrile-derived units 7 wt%, refractive index: 1.52) 10 parts by weight and a high molecular weight copolymer (weight average molecular weight: 148,000 g/mol, methyl methacrylate-derived unit 70% by weight, styrene-derived unit 23% by weight, acrylonitrile-derived unit 7% by weight, refractive index: 1.52) 53 weight A specimen was prepared in the same manner as in Example 1, except that parts were added and the second matrix copolymer was not added.

comparative example 2

28 parts by weight of the first matrix copolymer and 35 parts by weight of the AMS-SAN copolymer (weight average molecular weight: 95,000 g/mol, α-methylstyrene-derived units 72 wt%, acrylonitrile-derived units 28 wt%, refractive index: 1.57) A specimen was prepared in the same manner as in Example 1 except that the second matrix copolymer was not added.

comparative example 3

41 parts by weight of the first matrix copolymer and PMI-SM-MAH copolymer (manufacturer: DENKA, trade name: MS-NB, weight average molecular weight: 138,000 g/mol, unit derived from N-phenylmaleimide: 52 wt%, derived from styrene Unit 46% by weight, maleic anhydride 2% by weight, refractive index: 1.59) 22 parts by weight) was added, and a specimen was prepared in the same manner as in Example 1, except that the second matrix copolymer was not added.

The compositions of the specimens of Examples 1 to 3 and Comparative Examples 1 to 3 were summarized and described in Tables 1 and 2 below.

division Example 1
(parts by weight) Example 2
(parts by weight) Example 3
(parts by weight) small diameter graft copolymer 5 5 5 large diameter
graft copolymer 32 32 32 First matrix copolymer (high molecular weight) 43 33 23 second matrix copolymer 20 30 40

division Comparative Example 1
(parts by weight) Comparative Example 2
(parts by weight) Comparative Example 3
(parts by weight) small diameter graft copolymer 5 5 5 large diameter
graft copolymer 32 32 32 First matrix copolymer (low molecular weight) 10 - - First matrix copolymer (high molecular weight) 53 28 41 AMS-SAN copolymer - 35 - PMI-SM-MAH copolymer - - 22

test example

The properties of the specimens of Examples 1 to 2 and Comparative Examples 1 to 3 were measured in the following manner, and the results are shown in Tables 3 and 4 below.

※ Heat deflection temperature: In accordance with ASTM D648, the heat deflection temperature was measured with Auto HDT Tester 6A-2 (brand name, manufacturer: TOYOSEIKI).

※ Coloring property: L value was measured in SCI mode using Color-Eye 7000A (brand name, manufacturer: GRETAGMACBETH).

※ Tensile strength (kgf/cm2): Measured with a UTM Z010 (brand name, manufacturer: ZWICK ROELL) device in accordance with ASTM D638.

※ Melt index: In accordance with ASTM D1238, the weight was measured for 10 minutes at a temperature of 220° C. and a load of 10 kg with a MI-4 (brand name, manufacturer: GOTTFERT) instrument.

division Example 1 Example 2 Example 3 Heat deflection temperature (℃) 87.4 90.9 93.4 Colorability (L) 25.2 25.1 25.1 Tensile strength (kg/㎠) 537 556 559 Melt index (g/10min) 4.4 3.0 2.3

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Heat deflection temperature (℃) 82.6 91.5 90.3 Colorability (L) 25.1 25.7 25.5 Tensile strength (kg/㎠) 520 535 544 Melt index (g/10min) 9.3 7.5 2.4

Referring to Tables 3 and 4, it was confirmed that the specimens of Examples 1 to 3 were excellent in both heat resistance and colorability because the heat deflection temperature was high and the colorability was low. However, in the case of Comparative Example 3, although the colorability was excellent, the heat resistance was not excellent because the heat deformation temperature was low. In Comparative Examples 4 and 5, the heat resistance was excellent because the heat deformation temperature was low, but the colorability was not excellent because the refractive indices of the AMS-AN copolymer and the PMI-SM-MAH copolymer were high.

Claims (15)

a graft copolymer comprising an alkyl (meth)acrylate-based rubber-derived unit, an aromatic vinyl-based monomer-derived unit and a vinyl cyan-based monomer-derived unit;
a first matrix copolymer comprising a unit derived from an alkyl (meth)acrylate monomer, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyanide monomer; and
A second matrix copolymer comprising a unit derived from an alkyl (meth) acrylate monomer, a unit derived from an aromatic vinyl monomer, and a unit derived from a maleimide monomer,
The maleimide-based monomer-derived unit is included in an amount of 15 to 35% by weight based on the total weight of the second matrix copolymer,
The second matrix copolymer is included in an amount of 15 to 45 parts by weight based on 100 parts by weight of the total of the graft copolymer, the first matrix copolymer and the second matrix copolymer,
The refractive index of the first matrix copolymer is 1.50 to 1.53,
The refractive index of the second matrix copolymer is 1.49 to 1.53 of the thermoplastic resin composition.
The method according to claim 1,
The thermoplastic resin composition is
20 to 50 parts by weight of the graft copolymer; and
The thermoplastic resin composition comprising 10 to 60 parts by weight of the first matrix copolymer.
delete The method according to claim 1,
The graft copolymer is
about total weight
30 to 60 wt% of the alkyl (meth)acrylate-based rubber-derived unit;
35 to 65% by weight of the aromatic vinyl-based monomer-derived unit; and
The thermoplastic resin composition comprising 1 to 25% by weight of the vinyl cyan-based monomer-derived unit.
The method according to claim 1,
The graft copolymer is a thermoplastic resin composition comprising two or more types of graft copolymers having different average particle diameters.
The method according to claim 1,
The graft copolymer is a thermoplastic resin composition comprising a small-diameter graft copolymer having an average particle diameter of 80 to 200 nm and a large-diameter graft copolymer having an average particle diameter of 350 to 500 nm.
7. The method of claim 6,
The weight ratio of the small-diameter graft copolymer to the large-diameter graft copolymer is 1: 4 to 1: 9 of the thermoplastic resin composition.
The method according to claim 1,
The first matrix copolymer is
with respect to the total weight,
50 to 90 wt% of units derived from the alkyl (meth)acrylate-based monomer;
5 to 40% by weight of the aromatic vinyl-based monomer-derived unit; and
The thermoplastic resin composition comprising 1 to 20% by weight of the vinyl cyan-based monomer-derived unit.
The method according to claim 1,
The first matrix copolymer has a weight average molecular weight of 60,000 to 190,000 g/mol of the thermoplastic resin composition.
delete The method according to claim 1,
The second matrix copolymer is
with respect to the total weight,
50 to 90 wt% of units derived from the alkyl (meth)acrylate-based monomer;
1 to 20% by weight of the aromatic vinyl-based monomer-derived unit; and
The thermoplastic resin composition comprising 5 to 45% by weight of the maleimide-based monomer-derived unit.
The method according to claim 1,
The second matrix copolymer has a weight average molecular weight of 110,000 to 290,000 g / mol of the thermoplastic resin composition.
delete The method according to claim 1,
The thermoplastic resin composition has a colorability (L) of 25.2 or less of the thermoplastic resin composition.
The method according to claim 1,
The thermal deformation temperature of the thermoplastic resin composition is 87 ℃ or more thermoplastic resin composition.