WO2020091371A1 - Thermoplastic resin composition - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition, comprising: a first graft polymer comprising a C₄-C₁₀ alkyl (meth)acrylate-based monomer unit, an aromatic vinyl-based monomer unit, and a vinyl cyan-based monomer unit; a second graft copolymer comprising a C₄-C₁₀ alkyl (meth)acrylate-based monomer unit, an aromatic vinyl-based monomer unit, and a vinyl cyan-based monomer unit; and a first styrene-based copolymer which is a copolymer of a monomer mixture comprising a C₁-C₃ alkyl-substituted styrene-based monomer, a vinyl cyan-based monomer, and a C₁-C₃ alkyl (meth)acrylate-based monomer, wherein the first graft copolymer and the second graft copolymer are different in terms of average core diameter. The thermoplastic resin composition has excellent colorability, weather resistance, tensile strength, flexural strength, and impact strength.

Description

Thermoplastic resin composition

[Mutual citations with related applications]

The present invention claims the benefit of priority based on Korean Patent Application Nos. 10-2018-0132192, filed on October 31, 2018 and Korean Patent Application No. 10-2019-0134501, filed on October 28, 2019, and claims the interests of priority All content disclosed in the literature of the application is included as part of the present specification.

[Technical field]

The present invention relates to a thermoplastic resin composition, and relates to a thermoplastic resin composition excellent in colorability, weather resistance, tensile strength, flexural strength and impact strength.

 The thermoplastic resin composition comprising a diene-based graft copolymer obtained by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyan-based monomer on a diene-based rubbery polymer has excellent impact resistance, stiffness, chemical resistance, and processability, and provides electrical, electronic, and construction , Used in various fields such as automobiles. However, it is not suitable as an outdoor material due to its weak weather resistance.

Accordingly, a thermoplastic resin composition having excellent weather resistance and aging resistance, and an acrylic graft copolymer obtained by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyan-based monomer on an acrylic rubbery polymer has been spotlighted as an alternative. However, the thermoplastic resin composition containing the acrylic graft copolymer is difficult to be applied to products requiring high quality due to poor colorability.

Accordingly, research into developing a thermoplastic resin composition having excellent weatherability as well as coloring properties is continuing.

An object of the present invention is to provide a thermoplastic resin composition excellent in weather resistance, colorability, tensile strength, flexural strength and impact strength.

In order to solve the above problems, the present invention is a first graft copolymer comprising a C ₄ to C ₁₀ alkyl (meth) acrylate monomer units, aromatic vinyl monomer units and vinyl cyan monomer units; A second graft copolymer comprising C ₄ to C ₁₀ alkyl (meth) acrylate monomer units, aromatic vinyl monomer units, and vinyl cyan monomer units; And a first styrenic copolymer that is a copolymer of a monomer mixture comprising a C ₁ to C ₃ alkyl substituted styrene monomer, a vinyl cyan monomer, and a C ₁ to C ₃ alkyl (meth) acrylate monomer, The first graft copolymer and the second graft copolymer provide a thermoplastic resin composition having different average particle diameters of the core.

The thermoplastic resin composition according to the present invention is excellent in mechanical properties such as tensile strength, flexural strength, impact strength, etc., while also significantly improving colorability and weatherability. Specifically, the thermoplastic resin composition according to the present invention is a copolymer of a monomer mixture comprising a C ₁ to C ₃ alkyl-substituted styrene-based monomer, a vinyl cyan-based monomer, and a C ₁ to C ₃ alkyl (meth) acrylate-based monomer. By using the first styrene-based copolymer, excellent colorability and weatherability can be realized without deteriorating mechanical properties.

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

The terms or words used in the present specification and claims should not be interpreted as being limited to ordinary or lexical meanings, and the inventor can appropriately define the concept of terms in order to best describe his or her invention. Based on the principle that it should be interpreted as meanings and concepts consistent with the technical spirit of the present invention.

In the present invention, the average particle diameter of the first and second graft copolymers can be measured using a dynamic light scattering method, and specifically, measured using Nicomp 380 HPL equipment (product name, manufacturer: Nicomp). can do.

In the present specification, it is preferable to measure the arithmetic mean particle size in the particle size distribution measured by the dynamic light scattering method, that is, the average particle size of the scattering intensity.

In the present invention, the graft ratio of the first and second graft copolymers can be calculated by the following equation.

Graft ratio (%): weight of grafted monomer (g) / weight of crosslinked polymer (g) × 100

Weight of grafted monomer (g): weight of insoluble material (gel) after dissolving 1 g of graft copolymer in 30 g of acetone and centrifuging

Weight of crosslinked polymer (g): The weight of C ₄ to C ₁₀ alkyl (meth) acrylate monomers theoretically added in the graft copolymer powder

In the present invention, the weight average molecular weight of the first styrene-based copolymer, the second styrene-based copolymer, and the (meth) acrylic-based polymer is tetrahydrofuran as an eluent, and is subjected to a standard PS (standard polystyrene) sample through gel permeation chromatography. It can be measured as a relative value for.

In the present invention, the polymer should be understood as a concept including both a homopolymer formed by polymerizing one monomer and a copolymer formed by polymerizing two or more monomers.

1. Thermoplastic resin composition

The thermoplastic resin composition according to an embodiment of the present invention is 1) C ₄ to C ₁₀ alkyl (meth) acrylate monomer unit, an aromatic vinyl-based monomer unit and a first graft copolymer comprising a vinyl cyan-based monomer unit ; 2) a second graft copolymer comprising C ₄ to C ₁₀ alkyl (meth) acrylate monomer units, aromatic vinyl monomer units, and vinyl cyan monomer units; And 3) a first styrenic copolymer that is a copolymer of a monomer mixture comprising a C ₁ to C ₃ alkyl substituted styrene monomer, a vinyl cyan monomer, and a C ₁ to C ₃ alkyl (meth) acrylate monomer. And, the first graft copolymer and the second graft copolymer have different average particle diameters of the core.

Since the average particle diameters of the cores of the first graft copolymer and the second graft copolymer are different from each other, the thermoplastic resin composition according to an embodiment of the present invention can realize both excellent weather resistance and mechanical properties.

In addition, the thermoplastic resin composition according to an embodiment of the present invention may further include a second styrene copolymer that is a copolymer of a monomer mixture comprising 4) an aromatic vinyl monomer and a vinyl cyan monomer.

In addition, the thermoplastic resin composition according to an embodiment of the present invention may further include a (meth) acrylic polymer comprising 5) C ₁ to C ₃ alkyl (meth) acrylate monomer units.

Hereinafter, the components of the thermoplastic resin composition according to an embodiment of the present invention will be described in detail.

1) First Graft  Copolymer

The first graft copolymer includes C ₄ to C ₁₀ alkyl (meth) acrylate monomer units, aromatic vinyl monomer units, and vinyl cyan monomer units.

The first graft copolymer may impart excellent weather resistance, tensile strength, flexural strength, and impact strength to the thermoplastic resin composition. Specifically, the C ₄ to C ₁₀ alkyl (meth) acrylate-based monomer unit may impart excellent weather resistance to the thermoplastic resin composition. In addition, the average particle diameter of the first graft copolymer may impart excellent tensile strength, flexural strength and impact strength to the thermoplastic resin composition.

The first graft copolymer may be a graft copolymer obtained by graft polymerization of an aromatic vinyl monomer and a vinyl cyan monomer on an acrylic rubber polymer that is a crosslinked polymer of C ₄ to C ₁₀ alkyl (meth) acrylate monomers. have.

Here, the acrylic rubber polymer may mean a core.

The first graft copolymer has an average particle diameter of the core of 350 to 600 nm, 370 to 550 nm, or 400 to 500 nm, of which 400 to 500 nm is preferred. If the above-described range is satisfied, mechanical properties such as tensile strength, flexural strength, and impact strength of the thermoplastic resin composition may be further improved. In addition, the coloring property of the thermoplastic resin composition can be remarkably improved.

The C ₄ to C ₁₀ alkyl (meth) acrylate monomer units are butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylic It may be a unit derived from at least one monomer selected from the group consisting of acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate and decyl (meth) acrylate, , Of these, units derived from butyl acrylate are preferred.

The C ₄ to C ₁₀ alkyl (meth) acrylate-based monomer unit may be included in an amount of 30 to 70% by weight, or 40 to 60% by weight, based on the total weight of the first graft copolymer, 40 of which It is preferably included to 60% by weight. If the above-described range is satisfied, weather resistance and mechanical properties of the first graft copolymer can be further improved.

The aromatic vinyl-based monomer unit may be a unit derived from at least one monomer selected from the group consisting of styrene, α-methyl styrene, p-methyl styrene, and 2,4-dimethyl styrene, of which an alkyl unsubstituted styrene The unit derived from styrene which is a system monomer is preferred.

The aromatic vinyl-based monomer unit may be included in 5 to 25% by weight, or 10 to 20% by weight, based on the total weight of the first graft copolymer, and is preferably included in 10 to 20% by weight. . If the above-described range is satisfied, the processability of the first graft copolymer can be further improved.

The vinyl cyan monomer unit may be a unit derived from one or more monomers selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile, of which units derived from acrylonitrile are preferred. .

The vinyl cyan monomer unit may be included in 15 to 55% by weight, or 25 to 45% by weight relative to the total weight of the first graft copolymer, and is preferably included in 25 to 45% by weight. . If the above-described range is satisfied, chemical resistance and rigidity of the first graft copolymer can be further improved.

The first graft copolymer may have a graft ratio of 10 to 50% or 20 to 40%, of which 20 to 40% is preferred. If the above-described range is satisfied, mechanical properties of the first graft copolymer, that is, tensile strength, flexural strength, and impact strength may be further improved.

The first graft copolymer may be included in 1 to 20% by weight or 5 to 15% by weight based on the total weight of the thermoplastic resin composition, and preferably 5 to 15% by weight. If the above-described range is satisfied, excellent mechanical properties of the thermoplastic resin composition can be realized.

2) Second Graft  Copolymer

The second graft copolymer includes C ₄ to C ₁₀ alkyl (meth) acrylate monomer units, aromatic vinyl monomer units, and vinyl cyan monomer units.

The second graft copolymer may impart excellent weather resistance to the thermoplastic resin composition. Specifically, due to the C ₄ to C ₁₀ alkyl (meth) acrylate-based monomer unit and the above-described average particle diameter, excellent weatherability can be imparted to the thermoplastic resin composition.

The second graft copolymer may be a graft copolymer obtained by graft polymerization of an aromatic vinyl monomer and a vinyl cyan monomer on an acrylic rubber polymer that is a crosslinked polymer of C ₄ to C ₁₀ alkyl (meth) acrylate monomers. have.

Here, the acrylic rubber polymer may mean a core.

The second graft copolymer has a core having an average particle diameter of 30 to 200 nm or 50 to 150 nm, of which 30 to 200 nm is preferred. If the above-mentioned range is satisfied, the specific surface area of the second graft copolymer is widened, so that weatherability can be remarkably improved.

The types of the C ₄ to C ₁₀ alkyl (meth) acrylate monomer units are as described above.

The C ₄ to C ₁₀ alkyl (meth) acrylate-based monomer unit may be included in 30 to 70% by weight, or 40 to 60% by weight, based on the total weight of the second graft copolymer, 40 of which It is preferably included to 60% by weight. If the above-described range is satisfied, weatherability and mechanical properties of the second graft copolymer can be further improved.

The types of the aromatic vinyl monomer units are as described above.

The aromatic vinyl-based monomer unit may be included in 5 to 25% by weight, or 10 to 20% by weight, based on the total weight of the second graft copolymer, and is preferably included in 10 to 20% by weight. . If the above-described range is satisfied, the processability of the second graft copolymer can be further improved.

The type of the vinyl cyan monomer unit is as described above.

The vinyl cyan monomer unit may be included in an amount of 15 to 55% by weight, or 25 to 45% by weight, and preferably 25 to 45% by weight, based on the total weight of the second graft copolymer. . If the above-described range is satisfied, chemical resistance and rigidity of the second graft copolymer may be further improved.

The second graft copolymer may have a graft ratio of 10 to 50% or 20 to 40%, of which 20 to 40% is preferred. If the above-described range is satisfied, mechanical properties of the first graft copolymer, that is, tensile strength, flexural strength, and impact strength may be further improved.

The second graft copolymer may be included in an amount of 20 to 45% by weight or 25 to 40% by weight, and preferably 25 to 40% by weight, based on the total weight of the thermoplastic resin composition. If the above-mentioned ranges are satisfied, excellent weatherability and coloring properties of the thermoplastic resin composition can be realized.

3) First styrenic copolymer

The first styrene copolymer is a copolymer of a monomer mixture comprising a C ₁ to C ₃ alkyl substituted styrene monomer, a vinyl cyan monomer, and a C ₁ to C ₃ alkyl (meth) acrylate monomer.

The first styrene-based copolymer may impart remarkably excellent weather resistance, heat resistance, and colorability to the thermoplastic resin composition.

Specifically, the C ₁ to C ₃ alkyl-substituted styrene-based monomers introduced during the preparation of the first styrene-based copolymer may impart remarkably excellent weather resistance and heat resistance to the thermoplastic resin composition. In addition, the C ₁ to C ₃ alkyl (meth) acrylate-based monomers introduced during the preparation of the first styrene-based copolymer may impart remarkably excellent coloring properties to the thermoplastic resin composition.

The C ₁ to C ₃ alkyl-substituted styrene-based monomers may be at least one selected from the group consisting of α-methyl styrene, p-methyl styrene, and 2,4-dimethyl styrene, of which α-methyl styrene is preferred. Do.

The C ₁ to C ₃ alkyl-substituted styrene-based monomer may be included in an amount of 50 to 75% by weight, 55 to 70% by weight, or 60 to 65% by weight, based on the total weight of the monomer mixture, of which 60 to 65% by weight It is preferred to be included in%. When included in the above-described range, it is possible to impart remarkably excellent weather resistance and heat resistance to the thermoplastic resin composition.

The type of the vinyl cyan monomer is as described above.

The vinyl cyan monomer may be included in an amount of 15 to 40% by weight, 20 to 35% by weight, or 25 to 30% by weight, and preferably 25 to 30% by weight, based on the total weight of the monomer mixture. . When included in the above-described range, it can give excellent chemical resistance and rigidity to the thermoplastic resin composition.

The C ₁ to C ₃ alkyl (meth) acrylate-based monomers may be at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate and propyl (meth) acrylate, of which Methyl methacrylate is preferred.

The alkyl (meth) acrylate-based monomer of C ₁ to C ₃ may be included in 1 to 20% by weight, 5 to 15% by weight, or 9 to 13% by weight based on the total weight of the monomer mixture, of which 9 It is preferably included at 13% by weight. When included in the above-described range, it is possible to impart remarkably excellent coloring properties to the thermoplastic resin composition without lowering the impact strength.

The first styrene-based copolymer may have a weight average molecular weight of 80,000 to 105,000 g / mol, 85,000 to 100,000 g / mol, or 90,000 to 95,000 g / mol, of which 90,000 to 95,000 g / mol is preferred. If the above-described range is satisfied, the processability of the thermoplastic resin composition can be further improved.

The first styrene-based copolymer, based on the total weight of the thermoplastic resin composition, may be included in 40 to 70% by weight or 45 to 65% by weight, preferably 45 to 60% by weight. If the above-mentioned ranges are satisfied, excellent weatherability and coloring properties of the thermoplastic resin composition can be realized.

4) Second styrenic copolymer

The second styrene-based copolymer may be a copolymer of a monomer mixture comprising an aromatic vinyl monomer and a vinyl cyan monomer.

The second styrene-based copolymer may impart excellent processability, chemical resistance, rigidity, and heat resistance to the thermoplastic resin composition.

The monomer mixture may include the aromatic vinyl-based monomer and the vinyl cyan-based monomer in a weight ratio of 55:45 to 80:20 or 60:40 to 75:25, of which in a weight ratio of 60:40 to 75:25 It is preferred to include. If the above-mentioned range is satisfied, the second styrene-based copolymer can balance workability, chemical resistance, rigidity, and heat resistance.

The type of the aromatic vinyl-based monomer is as described above, and among them, one or more selected from the group consisting of styrene and α-methyl styrene is preferable.

The type of the vinyl cyan monomer is as described above, and acrylonitrile is preferable.

The second styrene-based copolymer may be at least one selected from the group consisting of styrene-acrylonitrile copolymer and α-methyl styrene-acrylonitrile copolymer, in order to further improve the processability of the thermoplastic resin composition, styrene -Acrylonitrile copolymers are preferred.

The second styrene-based copolymer may be included in 1 to 20% by weight or 5 to 15% by weight, and preferably 5 to 15% by weight, based on the total weight of the thermoplastic resin composition. If the above-mentioned range is satisfied, the processability of the thermoplastic resin composition can be further improved.

5) ( Met ) Acrylic polymer

The (meth) acrylic polymer may include C ₁ to C ₃ alkyl (meth) acrylate monomer units.

The (meth) acrylic polymer may impart excellent weather resistance and colorability to the thermoplastic resin composition.

The types of the C ₁ to C ₃ alkyl (meth) acrylate monomers are as described above.

The (meth) acrylic polymer may have a weight average molecular weight of 80,000 to 100,000 g / mol or 85,000 to 95,000 g / mol, of which 85,000 to 95,000 g / mol is preferred. When the above-described conditions are satisfied, the coloring property of the thermoplastic resin composition may be further improved.

Meanwhile, the (meth) acrylic polymer further includes at least one selected from the group consisting of aromatic vinyl monomer units and vinyl cyan monomer units in addition to C ₁ to C ₃ alkyl (meth) acrylate monomer units ( It may be a metha) acrylic copolymer.

In this case, the (meth) acrylic copolymer is a copolymer of an alkyl (meth) acrylate monomer of C ₁ to C ₃ and at least one monomer mixture selected from the group consisting of an aromatic vinyl monomer and a vinyl cyan monomer. Can be.

The monomer mixture is 30 to 55 parts by weight of one or more selected from the group consisting of aromatic vinyl monomers and vinyl cyan monomers, based on 100 parts by weight of the alkyl (meth) acrylate monomers of C ₁ to C ₃ or It may include 35 to 50 parts by weight, and it is preferable to include 35 to 55 parts by weight. When the above-described range is satisfied, compatibility with the first and second styrene-based copolymers may be further improved.

The (meth) acrylic polymer, based on the total weight of the thermoplastic resin composition, may be included in 1 to 10 or 2 to 7% by weight, preferably 2 to 7% by weight. If the above-described range is satisfied, weatherability and colorability of the thermoplastic resin composition may be further improved.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art to which the present invention pertains can easily practice. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein.

Manufacturing example  One

95 parts by weight of a monomer mixture containing 60% by weight of α-methyl styrene, 30% by weight of acrylonitrile and 10% by weight of methyl methacrylate, 5 parts by weight of toluene as a reaction solvent, and 1,1-bis (t-butyl) as an initiator. A polymerization solution was prepared by adding 0.075 parts by weight of peroxy) cyclohexane and 0.195 parts by weight of polyether poly-t-butylperoxy carbonate. The polymerization solution was continuously added to a reactor at a temperature of 110 ° C. to perform a polymerization reaction. The prepared polymerization product was transferred to a devolatilization tank, and unreacted monomers and reaction solvents were recovered and removed under a temperature of 235 ° C. and a pressure of 20.6 torr to prepare a pellet-type heat-resistant styrene resin.

Example  And Comparative example

The specifications of the components used in Examples and Comparative Examples are as follows.

(A-1) 1st graft copolymer: SA927 (a graft copolymer obtained by graft polymerization of styrene and acrylonitrile on a butyl acrylate rubbery polymer having an average particle diameter of 450 nm) was used.

(A-2) 2nd graft copolymer: SA100 of LG Chemical (graft copolymer obtained by graft polymerization of styrene and acrylonitrile on a butyl acrylate rubber polymer having an average particle diameter of 100 nm) was used.

(B) First styrenic copolymer: The copolymer prepared in Preparation Example 1 was used.

(C) Second styrenic copolymer:

(C-1) Heat-resistant SAN copolymer: 200 UH (copolymer of α-methyl styrene and acrylonitrile) from LG Chemical was used.

(C-2) SAN copolymer: 95RF (a copolymer of styrene and acrylonitrile) of LG Chemical was used.

(D) (meth) acrylic polymer:

(D-1) Poly (methyl methacrylate): IH830 from LG PMMA was used.

(D-2) (meth) acrylic-based copolymer: XT510 (a copolymer of methyl methacrylate, styrene and acrylonitrile) manufactured by LG Chemical was used.

The above-mentioned components were mixed and stirred according to the contents described in [Table 1] to prepare a thermoplastic resin composition.

Experimental example  One

The thermoplastic resin compositions of Examples and Comparative Examples were put into an extrusion kneader (cylinder temperature: 240 ° C.) and extruded to prepare pellets, and physical properties were evaluated by the methods described below, and the results are shown in [Table 1].

(1) Flow index (g / 10min, 220 ° C, 10 kg): Measured according to ISO 1133.

Experimental example  2

The pellets prepared in Experimental Example 1 were injected to prepare specimens, evaluated by the methods described below, and the results are shown in Table 1 below.

(2) Vicat Softening Temperature (℃): measured according to ISO 306.

(3) Tensile strength (㎫): Measured according to ISO 527.

(4) Flexural strength (㎫): Measured according to ISO 178.

(5) Charpy impact strength (KJ / m 2, Notched): Measured according to ISO 179.

(6) Colorability: L value was measured in SCI mode using Color-Eye 7000A of GRETAGMACBETH.

(7) Weatherability: Tested under PV3929 condition among VW weatherability standards using Ci4000 Weather-O meter (trade name, manufacturer: Atlas). Weatherability was visually evaluated for the degree of discoloration of the specimen before and after the test based on the gray scale.

◎: No change in color of the specimen after weather resistance test

○: After the weather resistance test, the color of the specimen changed slightly.

△: After the weather resistance test, the color of the specimen changed significantly.

division		Example				Comparative example
		One	2	3	4	One	2	3	4	5
(A-1) First graft copolymer (% by weight)		10	10	10	10	10	10	10	10	10
(A-2) Second graft copolymer (% by weight)		30	30	30	30	30	30	30	30	30
(B) First styrene-based copolymer (% by weight)		60	55	45	45	-	-	-	-	-
(C) Second styrene-based copolymer (% by weight)	(C-1)	-	-	-	-	60	55	45	45	-
	(C-2)	-	-	10	10	-	-	10	10	-
(D) (meth) acrylic polymer (% by weight)	(D-1)	-	5	5	-	-	5	5	-	-
	(D-2)	-	-	-	5	-	-	-	5	60
Flow index		5	5	7	7	5	5	7	7	9
Softening temperature		104	105	102	101	105	104	103	103	88
The tensile strength		50	50	48	48	49	49	48	49	46
Flexural strength		74	74	74	74	74	73	73	74	69
Charpy impact strength		11	11	10	10	11	11	10	10	9
Coloring		26.7	26.6	26.5	26.5	27.0	26.9	26.8	26.8	25.3
Weatherability		◎	◎	◎	◎	◎	◎	○	○	△
(A-1) 1st graft copolymer: SA927 of LG Chem (graft copolymer obtained by graft polymerization of styrene and acrylonitrile on a butyl acrylate rubbery polymer having an average particle diameter of 450 nm) (A-2) 2nd graft copolymer: SA100 of LG Chemical (graft copolymer obtained by graft polymerization of styrene and acrylonitrile on a butyl acrylate rubbery polymer having an average particle diameter of 100 nm) (B) 1st styrenic copolymer: Copolymer (C-1) heat - resistant SAN copolymer: a copolymer of a monomer mixture containing 60% by weight of α-methyl styrene, 30% by weight of acrylonitrile, and 10% by weight of methyl methacrylate: 200UH of LG Chem (α- Copolymer of methyl styrene and acrylonitrile) (C-2) SAN copolymer: 95RF (polymer of styrene and acrylonitrile) manufactured by LG Chem. (C-3) MSAN copolymer: 60% by weight of styrene, acrylic 30% by weight of nitrile and methyl methacrylate 10% by weight of monomers copolymerized is water the copolymer (D-1) a mixture comprising a poly (methyl methacrylate): LG PMMA社of IH830 (D-2) (meth) acrylic copolymer of: LG Chemical社XT510 (methyl Copolymers of methacrylate, styrene and acrylonitrile)

Referring to Table 1, it was confirmed that Examples 1 to 4 were excellent in basic physical properties and also excellent in colorability and weatherability. Example 1 and Comparative Example 1, Example 1 and Comparative Example 5, Example 2 and comparison When each of Example 2, Example 3 and Comparative Example 3, Example 4 and Comparative Example 4 were compared, the L value differed by 0.3 or more, and thus it was confirmed that the coloring property was significantly improved.

In addition, when each of Example 3 and Comparative Example 3, Example 4 and Comparative Example 4 were compared, it was confirmed that the effect of improving not only coloration but also weather resistance was large.

Claims (10)

1. A first graft copolymer comprising C ₄ to C ₁₀ alkyl (meth) acrylate monomer units, aromatic vinyl monomer units, and vinyl cyan monomer units;

   A second graft copolymer comprising C ₄ to C ₁₀ alkyl (meth) acrylate monomer units, aromatic vinyl monomer units, and vinyl cyan monomer units; And

   A first styrenic copolymer that is a copolymer of a monomer mixture comprising a C ₁ to C ₃ alkyl-substituted styrene-based monomer, a vinyl cyanide monomer and a C ₁ to C ₃ alkyl (meth) acrylate-based monomer,

   The first graft copolymer and the second graft copolymer are thermoplastic resin compositions having different average particle diameters of the core.
2. The method according to claim 1,

   The monomer mixture,

   50 to 75% by weight of the C ₁ to C ₃ alkyl substituted styrene monomer;

   15 to 40% by weight of the vinyl cyan monomer; And

   The thermoplastic resin composition comprising 1 to 20% by weight of the C ₁ to C ₃ alkyl (meth) acrylate-based monomer.
3. The method according to claim 1,

   The first graft copolymer is a thermoplastic resin composition having an average particle diameter of 350 to 600 nm of the core.
4. The method according to claim 1,

   The second graft copolymer is a thermoplastic resin composition having an average particle diameter of 30 to 200 nm of the core.
5. The method according to claim 1,

   The first graft copolymer and the second graft copolymer are acrylonitrile-styrene-alkyl acrylate copolymers, respectively.
6. The method according to claim 1,

   The thermoplastic resin composition

   1 to 20% by weight of the first graft copolymer;

   20 to 45% by weight of the second graft copolymer; And

   A thermoplastic resin composition comprising 40 to 70% by weight of the first styrene-based copolymer.
7. The method according to claim 1,

   The thermoplastic resin composition further comprises a second styrene-based copolymer,

   The second styrene-based copolymer is a thermoplastic resin composition that is a copolymer of a monomer mixture containing an aromatic vinyl monomer and a vinyl cyan monomer.
8. The method according to claim 7,

   The thermoplastic resin composition

   A thermoplastic resin composition comprising 1 to 20% by weight of the second styrene-based copolymer.
9. The method according to any one of claims 1 to 8,

   The thermoplastic resin composition further comprises a (meth) acrylic polymer,

   The (meth) acrylic polymer is a thermoplastic resin composition comprising a C ₁ to C ₃ alkyl (meth) acrylate monomer units.
10. The method according to claim 9,

    The thermoplastic resin composition

    A thermoplastic resin composition comprising 1 to 10% by weight of the (meth) acrylic polymer.