WO2013077492A1

WO2013077492A1 - Thermoplastic resin composition, and molded product using same

Info

Publication number: WO2013077492A1
Application number: PCT/KR2011/010010
Authority: WO
Inventors: 김인철; 홍창민; 박지은; 정택웅
Original assignee: 제일모직 주식회사
Priority date: 2011-11-24
Filing date: 2011-12-22
Publication date: 2013-05-30
Also published as: DE112011105875T5; JP2014533763A; CN103958599A; DE112011105875B4; KR101531613B1; JP2016196656A; KR20130057795A; CN103958599B; JP6263234B2

Abstract

One embodiment of the present invention provides a thermoplastic resin composition comprising: (A) a grafted acrylic copolymer; (B) an aromatic vinyl-cyanovinyl copolymer; and (C) a polyalkyl (meth)acrylate resin. The aromatic vinyl-cyanovinyl copolymer (B) can comprise 5-25 wt% of a monomer derived from a cyanovinyl compound.

Description

Thermoplastic resin composition and molded article using same

A thermoplastic resin composition and a molded article using the same.

Acrylonitrile-butadiene-styrene (ABS) resins are widely used in electrical and electronic parts and office equipment because of their excellent impact resistance and workability, and good mechanical strength, heat deformation temperature, and glossiness. However, when used in high-end consumer housings, such as LCD, PDP TV, audio, etc., there is a problem that the product value is low due to the easy generation of scratches during injection molding or use and difficult to express the color of the high-quality texture.

In order to solve this problem, the surface of the injection molded product of ABS resin has been coated with urethane, UV coating treatment or acrylic resin having excellent scratch characteristics. However, such work is accompanied by the problem of productivity degradation such as the complexity of the work and the increase of the defective rate by the addition of additional post-processing process and the environmental pollution problem due to the painting.

ASA resin with excellent weather resistance is a general-purpose resin used for various materials such as building materials and automotive exteriors, and does not have excellent scratch resistance, and has a limit of colorability due to the characteristics of an opaque resin.

ABS / PMMA resin, on the other hand, has excellent transparency, high color, high gloss color, and high scratch resistance according to PMMA prescription.

One embodiment of the present invention is to provide a transparent thermoplastic resin composition excellent in excellent weather resistance and scratch resistance.

Another embodiment of the present invention is to provide a molded article using the thermoplastic resin composition.

One embodiment of the invention graft acrylic copolymer (A); Aromatic vinyl-vinyl cyanide copolymer (B); And a polyalkyl (meth) acrylate resin (C), wherein the aromatic vinyl-vinyl cyanide copolymer (B) provides a thermoplastic resin composition comprising units derived from 5 to 25 wt% of a vinyl cyanide compound. .

The thermoplastic resin composition may include 50 to 200 parts by weight of the aromatic vinyl-vinyl cyanide copolymer (B) based on 100 parts by weight of the graft acrylic copolymer (A).

The thermoplastic resin composition may include 50 to 300 parts by weight of the polyalkyl (meth) acrylate (C) based on 100 parts by weight of the graft acrylic copolymer (A).

The content ratio of the aromatic vinyl-vinyl cyanide copolymer (B) and the polyalkyl (meth) acrylate (C) may be in the range of 6: 4 to 3: 7.

The graft acrylic copolymer (A) is a copolymer in which an acrylic rubber-like polymer is copolymerized with the aromatic vinyl monomer, the monomer copolymerizable with the aromatic vinyl monomer, or a combination thereof, graft or two or more thereof. May be a combination.

The monomer copolymerizable with the aromatic vinyl monomer may include a vinyl cyanide compound, and may include a content of 20 to 30 wt% of the total amount of the monomer graft-polymerized to the acrylic rubber polymer.

The aromatic vinyl cyanide copolymer (B) may be a copolymer of styrene and acrylonitrile, a copolymer of α-methylstyrene and acrylonitrile, or a copolymer of styrene, α-methylstyrene and acrylonitrile. have.

The polyalkyl (meth) acrylate resin (C) is an alkyl (meth) acrylate having an alkyl group of C1 to C10, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, It may be a polymer of glycidyl (meth) acrylate, hydroxyethyl (meth) acrylate or a combination thereof.

The thermoplastic resin composition may further include an additive including a dye, a pigment, a flame retardant, a filler, a stabilizer, a lubricant, an antibacterial agent, a release agent, or a combination thereof.

Another embodiment of the present invention provides a molded article manufactured using the thermoplastic resin composition.

The molded article may have a haze value of 5 to 20 according to ASTM D1003 standard.

Other details of aspects of the invention are included in the following detailed description.

The thermoplastic resin composition may implement high transparent properties while having excellent weather resistance and scratch resistance.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless stated otherwise in the present specification, "substituted" means that the hydrogen atom in the compound is a halogen atom (F, Cl, Br, I), hydroxy group, nitro group, cyano group, amino group, azido group, amidino group, hydrazino group, Hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkoxy Substituted with a substituent of a C1 to C20 alkoxy group, C6 to C30 aryl group, C6 to C30 aryloxy group, C3 to C30 cycloalkyl group, C3 to C30 cycloalkenyl group, C3 to C30 cycloalkynyl group, or a combination thereof Means that.

Unless otherwise specified herein, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible. Also, "(meth) acrylic acid alkyl ester" means that both "acrylic acid alkyl ester" and "methacrylic acid alkyl ester" are possible, and "(meth) acrylic acid ester" means both "acrylic acid ester" and "methacrylic acid ester". It means everything is possible.

The thermoplastic resin composition according to one embodiment of the present invention includes (A) graft acrylic copolymer, (B) aromatic vinyl-vinyl cyanide copolymer, and (C) polyalkyl (meth) acrylate resin. The thermoplastic resin composition is a general-purpose resin composition including a graft acrylic copolymer, and is easily applied to various applications such as building materials, automotive exterior applications, etc., while securing transparency and improving scratch resistance. Hereinafter, each component included in the thermoplastic resin composition will be described in detail.

(A) Graft Acrylic Copolymer

The graft acrylic copolymer (A) is a copolymer obtained by graft polymerization of an acrylic vinyl polymer with an aromatic vinyl monomer and / or a monomer copolymerizable with the aromatic vinyl monomer. Preferably, the acrylic rubber-like polymer forms a core, and the monomer copolymerizable with the aromatic vinyl monomer and / or the aromatic vinyl monomer may form a shell while graft polymerization on the core, thereby forming the graft. The acrylic copolymer (A) may form a core-shell structure.

The acrylic rubber polymer may be polymerized, including a (meth) acrylic acid alkyl ester, a (meth) acrylic acid ester, or a combination thereof. The alkyl may be C1 to C10 alkyl. Examples of the (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and the like. Examples of the (meth) acrylic acid esters include (meth) acrylate. Acrylic monomers, such as these, are mentioned, It is not limited to this.

The acrylic rubber polymer may have a core structure including a single layer, a double layer, or a combination thereof depending on the physical properties to be implemented. Specifically, the acrylic rubber polymer may include a single layer rubber core including the acrylic monomer. Alternatively, the acrylic rubber polymer may include a double layer rubber core including an inner layer including the acrylic monomer and an aromatic vinyl compound, and an outer layer including the acrylic monomer. By using the rubber core of the double layer, it is possible to further improve the coloring and gloss while maintaining weather resistance and impact resistance. For example, in order to obtain an excellent effect in terms of optical properties, an inner layer containing an acrylic monomer and a vinyl compound may be used. An acrylic rubber-like polymer including a double layer rubber core may be used.

As described above, the rubber core of the bilayer may be composed of an inner layer and an outer layer, for example, the inner layer includes an acrylic acid alkyl ester compound and an aromatic vinyl compound, and the outer layer is an acrylic acid alkyl ester compound. It includes.

The acrylic acid alkyl ester compound may be C1 to C10 alkyl acrylate, for example, methyl acrylate, butyl acrylate or the like or a combination thereof may be used.

As the aromatic vinyl compound, styrene, C1 to C10 alkyl substituted styrene, halogen substituted styrene, or the like, or a combination thereof may be used. Examples of the alkyl substituted styrenes include o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, α-methyl styrene, and the like, but are not limited thereto.

Specifically, the inner layer may be a copolymer of the acrylic acid alkyl ester compound and the aromatic vinyl compound. When the weight ratio of the acrylic acid alkyl ester compound and the aromatic vinyl compound of the inner layer may be from 5: 5 to 90:20, and included in the weight ratio of this range, weather resistance, impact resistance, gloss and colorability suitable for use as a predetermined use A combination of aspects can be obtained.

In another embodiment, the weight ratio of the inner layer and outer layer may be 20:80 Pa to 70: 300. When composed of the weight ratio of the above range it is possible to obtain a physical property balance suitable for use as a predetermined use.

The acrylic rubber polymer may be used by mixing an acrylic copolymer including the rubber core of the single layer and an acrylic copolymer including the rubber core of the double layer. For example, the acrylic copolymer including the rubber core of the single layer and the acrylic copolymer including the rubber core of the double layer may be mixed in a weight ratio of 20:80 to 90:20, specifically, 25:75 To 75:25 by weight. When mixed in the ratio range, the coloring properties of the acrylic thermoplastic resin composition are excellent.

The monomer graft-polymerized to the acrylic rubber polymer includes an aromatic vinyl monomer and / or a monomer copolymerizable with the aromatic vinyl monomer. As described above, the monomer copolymerizable with the aromatic vinyl monomer and / or the aromatic vinyl monomer may be graft polymerized to the acrylic rubber polymer to form a shell.

As the aromatic vinyl monomer, styrene, C1 to C10 alkyl substituted styrene, halogen substituted styrene, or the like, or a combination thereof may be used. Examples of the alkyl substituted styrenes include o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, α-methyl styrene, and the like.

As the monomer copolymerizable with the aromatic vinyl monomer, a vinyl cyanide compound, a heterocyclic compound, or the like can be used.

As the vinyl cyanide compound, acrylonitrile, methacrylonitrile, ethacrylonitrile, or the like or a combination thereof may be used.

As the heterocyclic compound, maleic anhydride, alkyl or phenyl N-substituted maleimide, or the like, or a combination thereof may be used.

As the monomer copolymerizable with the aromatic vinyl monomer and / or the aromatic vinyl monomer, an aromatic vinyl compound, a vinyl cyanide compound, a heterocyclic compound, or the like or a combination thereof may be used, and among these, preferably an aromatic vinyl compound And mixtures or copolymers of vinyl cyanide compounds. The aromatic vinyl compound and the vinyl cyanide compound may be composed of 6 to 90 wt% and 10 to 40 wt%. For example, the content of the vinyl cyanide compound in the total amount of the monomer graft polymerized to the acrylic rubber-like polymer may be 20 to 30% by weight.

The graft acrylic copolymer (A) may include 70 to 300 wt% of an acrylic rubbery polymer capable of forming a core structure and 30 to 70 wt% of a graft polymerizable polymer capable of forming a shell structure. Specifically, it may be a graft acrylic copolymer (A) comprising a rubber core of 60 to 40 wt% and a shell of 40 to 60 wt%. When the graft acrylic copolymer (A) is made within the content range, the colorability of the thermoplastic resin composition may be excellent.

The average particle diameter of the rubber may be from 0.07 to um. The acrylic rubber polymer may be used in a bi-modal form in which an acrylic rubber polymer having a different average particle diameter of rubber is mixed. For example, an acrylic rubber polymer having a large particle size of 0.4 to 0.7 µm of rubber and an acrylic rubber polymer having a small particle size of 0.1 to 0.3 µm of rubber may be used in combination. Thus, when used in a bi-modal form in which an acrylic rubber polymer having a large particle size / small particle size is mixed, the large particle rubber particles directly absorb the impact, and the small particle rubber particles are substituted. The role of dispersing the impact between the hard rubber, can improve the practical impact compared to the uni-modal (-) type that uses only one type of rubber particle diameter.

The graft acrylic copolymer (A) may be prepared by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization.

(B) Aromatic vinyl-vinyl cyanide copolymer

The aromatic vinyl cyanide copolymer (B) is a copolymer of an aromatic vinyl compound and a vinyl cyanide compound.

As the aromatic vinyl compound, styrene, C1 to C10 alkyl substituted styrene, halogen substituted styrene, vinyl toluene, vinyl naphthalene or a combination thereof may be used. Specific examples of the alkyl substituted styrene include α-methyl styrene, p-methyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, p-t-butyl styrene, 2,4-dimethyl styrene, and the like.

As the vinyl cyanide compound, acrylonitrile, methacrylonitrile, ethacrylonitrile or a combination thereof may be used.

Specific examples of the aromatic vinyl cyanide copolymer (B) include a copolymer of styrene and acrylonitrile; copolymers of α-methylstyrene and acrylonitrile; Or copolymers of styrene, α-methylstyrene and acrylonitrile, and preferably copolymers of styrene and acrylonitrile.

The aromatic vinyl cyanide copolymer (B) may be polymerized by further including (meth) acrylic acid alkyl ester together with the aromatic vinyl compound and the vinyl cyanide compound.

It is preferable that the said (meth) acrylic-acid alkylester is the (meth) acrylic-acid alkylester which has a C1-C10 alkyl group. For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, methyl acrylate, ethyl acryl Laterate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, ethyl hexyl acrylate, and the like or a combination thereof may be used, but is not necessarily limited thereto.

Although the content of the unit derived from the vinyl cyanide compound included in the aromatic vinyl-vinyl cyanide copolymer (B) may be relatively low, transparency characteristics may be realized, but complementary relations with other physical aspects such as chemical resistance (trade -off), it should be included in the appropriate content range. The aromatic vinyl cyanide copolymer (B) may include a unit derived from 5 to 25 wt% of vinyl cyanide compound. For example, the aromatic vinyl-vinyl cyanide copolymer may include a unit derived from 15 to 20% by weight of a vinyl cyanide compound. The thermoplastic resin composition including the unit derived from the vinyl cyanide compound satisfying the above range may ensure transparency characteristics by including a relatively low content of the unit derived from the vinyl cyanide compound from the total content. For example, the thermoplastic resin composition comprising an aromatic vinyl-vinyl cyanide copolymer (B) including a unit derived from a vinyl cyanide compound having a content satisfying the above range may have a haze value of 5 to 20. Can be implemented.

The aromatic vinyl cyanide copolymer (B) may have a weight average molecular weight in the range of 60,000 to 150,000.

The thermoplastic resin composition may include an aromatic vinyl-vinyl cyanide copolymer (B) in an amount of 50 to 200 parts by weight based on 100 parts by weight of the graft acrylic copolymer (A).

(C) polyalkyl (meth) acrylate resin

The polyalkyl (meth) acrylate resin (C) is resistant to hydrolysis and can improve scratch resistance of the thermoplastic resin composition.

The polyalkyl (meth) acrylate resin (C) may be obtained by polymerizing a raw material monomer containing an alkyl (meth) acrylate by a known polymerization method such as suspension polymerization, bulk polymerization, emulsion polymerization, or the like. .

Alkyl (meth) acrylate which is a monomer of the said polyalkyl (meth) acrylate resin (C) has C1-C10 alkyl group, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acryl The rate, glycidyl (meth) acrylate, hydroxyethyl (meth) acrylate, etc. are mentioned.

At this time, the alkyl (meth) acrylate may be included in more than 50% by weight relative to the total amount of the polyalkyl (meth) acrylate resin (C), specifically, it may be included in 80 to 99% by weight. When included in the content, the heat resistance of the obtained molded article is improved, and because the intermolecular interaction with the graft acrylic copolymer (A) and the aromatic vinyl-vinyl cyanide copolymer (B) described above is increased, the affinity is improved. , Hydrolysis resistance and scratch resistance are improved.

The raw material monomer may further include a vinyl monomer in addition to the alkyl (meth) acrylate. As said vinylic monomer, Aromatic vinyl monomers, such as styrene, (alpha) -methylstyrene, (rho) -methylstyrene; Unsaturated nitrile monomers, such as acrylonitrile and methacrylonitrile, etc. can be used, These can be used individually or in mixture.

The polyalkyl (meth) acrylate resin (C) may have a weight average molecular weight in the range of 10,000 to 200,000 g / mol, specifically, may have a range of 15,000 to 150,000 g / mol. When the weight average molecular weight of polyalkyl (meth) acrylate resin (C) is in the said range, it is excellent in compatibility with the graft acrylic copolymer (A) and aromatic vinyl-vinyl cyanide copolymer (B) mentioned above, It has excellent degradability, scratch resistance and workability.

The polyalkyl (meth) acrylate resin (C) may adjust the content ratio with the aromatic vinyl-vinyl cyanide copolymer (B) to adjust the balance between scratch resistance and weather resistance while maintaining transparency characteristics of the thermoplastic resin composition. have. For example, in the thermoplastic resin composition, the weight ratio of the aromatic vinyl-vinyl cyanide copolymer (B) and the polyalkyl (meth) acrylate resin (C) may be 6: 4 to 3: 7, preferably 6: 4 to 4: 6.

The thermoplastic resin composition may include a polyalkyl (meth) acrylate resin in an amount of 50 to 300 parts by weight based on 100 parts by weight of the graft acrylic copolymer (A). When the polyalkyl (meth) acrylate resin is used within the above range, the processability, hydrolysis resistance, scratch resistance and the like are excellent.

(D) other additives

The thermoplastic resin composition may further include additional additives (D) in order to further impart injection moldability and physical property balance.

For example, the thermoplastic resin composition may further include additives such as dyes, pigments, flame retardants, fillers, stabilizers, lubricants, antibacterial agents, and release agents, and these may be used alone or in combination of two or more thereof.

The additive (D) may be suitably included within the range of not impairing the physical properties of the thermoplastic resin composition, specifically, may be included in 40 parts by weight or less relative to 100 parts by weight of the graft acrylic copolymer (A), More specifically, it may be included in 0.1 to 30 parts by weight.

As described above, each component contained in the thermoplastic resin composition has been described, and exemplary contents of each component have been described, but inherent inherent characteristics of each component are considered in accordance with the properties of the thermoplastic resin composition to be finally implemented. By using a properly added content can be implemented a thermoplastic resin composition.

The said thermoplastic resin composition can be manufactured by a well-known method of manufacturing a resin composition. For example, the components and other additives according to one embodiment may be mixed simultaneously, then melt extruded in an extruder and prepared in pellet form.

According to another embodiment, a molded article manufactured by molding the above-described thermoplastic resin composition is provided. Specifically, the molded article may include a molded article having a large size, a complicated structure, or a thin thickness, in which mechanical properties, thermal properties, and moldability are required, and more specifically, an automobile exterior material, and the like.

Hereinafter, preferred embodiments of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited by the following examples.

실시예EXAMPLE

Each component used for manufacture of the thermoplastic resin composition of the following Example is as follows.

(A-1) Graft Acrylic Copolymer:

Monomer mixture consisting of 33% by weight of acrylonitrile and 67% by weight of styrene relative to 50 parts by weight of a butylacrylate rubber having a double core structure composed of an inner core copolymerized with butyl acrylate and styrene and an outer core made of butyl acrylate rubber. Graft ASA resin in double core-shell form prepared by emulsion part polymerization by weight

(A-2) Core-shell structured graft MABS resin containing (meth) acrylic acid alkyl ester component:

Methyl methacrylate-acrylonitrile-butadiene-styrene copolymer, core-shell structure, the shell is composed of a cabinet shell and an outer shell, the composition is 55 parts by weight of butadiene rubber, 33 parts by weight of methyl methacrylate, acryl Graft MABS resin consisting of 3 parts by weight of ronitrile and 9 parts by weight of styrene

(B-1) Styrene-Acrylonitrile Copolymer:

SAN resin with an acrylonitrile content of 20% by weight, a styrene content of 80% by weight, and a weight average molecular weight of 100,000

(B-2) Methyl methacrylate-styrene-acrylonitrile copolymer:

MSAN resin with 20% by weight acrylonitrile, 65% by weight styrene, 15% by weight methacrylate and 100,000 weight average molecular weight

(B-3) Styrene-Acrylonitrile Copolymer:

SAN resin with 15 weight percent acrylonitrile content and 85 weight percent styrene content and 120,000 weight average molecular weight

(B-4) Styrene-Acrylonitrile Copolymer:

SAN resin with an acrylonitrile content of 32% by weight and a styrene content of 68% by weight and a weight average molecular weight of 120,000

(B-5) Alphamethylstyrene-acrylonitrile copolymer:

SAN resin with 30% acrylonitrile content and 70% alphamethylstyrene content and 120,000 weight average molecular weight

(C) polymethyl methacrylate:

PMMA resin with a weight average molecular weight of 110,000 consisting of methyl methacrylate

실시예 1 내지 6 및 비교예 1 내지 5Examples 1-6 and Comparative Examples 1-5

The thermoplastic resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 7 were prepared in the compositions shown in Table 1 using the above-mentioned components.

To the thermoplastic resin composition of the composition shown in Table 1 below was added to other additives by extrusion / processing to prepare a thermoplastic resin in the form of pellets. Extrusion used a twin screw extruder of L / D = 29 and a diameter of 45 mm, and the barrel temperature was set to 230 ° C. After drying the prepared pellets for 2 hours at ℃ 80 ℃, using a 6 oz injection molding machine to set the cylinder temperature 240 ℃, mold temperature 60 ℃ by using a specimen and 9cm × 5cm × 0.2cm scratch resistance, optical characteristics and A specimen for measuring weatherability was prepared.

시험예 1: 기계적 물성 측정Test Example 1: Measurement of Mechanical Properties

The prepared physical specimens were measured in the following physical properties and the results are shown in Table 2 below.

(1) Permeability and Haze: Measured according to the standards of ASTM D1003.

(2) BSP (Ball type Scratch Profile) width: According to the Cheil method, using a tungsten carbide stylus, the tip of which is 0.7mm in diameter, gives a load of 300g, 500g and 1000g, respectively, and the 75mm / min After scratching the specimen at speed, the surface roughness was measured using a surface profiler and the scratch width was measured.

(3) Pencil hardness: Hardness value when scratch does not occur by pushing the pencil 5 times at the speed of 10mm / s by lifting the weight of 500g with a pencil according to the hardness. (Measuring pencil and pencil hardness determined in JIS K5401)

(4) Weather resistance: measured according to SAE J 1960 (3,000 hours, ΔE)

Table 1

division	To conduct						Comparative example
division	One	2	3	4	5	6	One	2	3	4	5	6	7
Graft Acrylic Copolymer (A-1)	25	30	30	30	30	30	30	30	-	30	25	25	25
MABS Resin (A-2)	-	-	-	-	-	-	-	-	30	-	-	-	-
SAN Resin (B-1)	-	-	28	-	-	-	-	-	28	-	-	-	-
SAN Resin (B-2)	30	28	-	-	35	42	-	-	-	-	-	-	-
SAN Resin (B-3)	-	-	-	28	-	-	-	-	-	-	-	-	-
SAN Resin (B-4)	-	-	-	-	-	-	-	-	-	28	20	20	20
SAN Resin (B-5)	-	-	-	-	-	-	-	70	-	-	40	40	40
PMMA Resin (C)	45	42	42	42	35	28	70	-	42	42	2	3	4

TABLE 2

division	To conduct						Comparative example
division	One	2	3	4	5	6	One	2	3	4	5	6	7
Transmittance [%]	83.8	81.2	80.8	82.6	80.1	79.0	46.3	21.0	95.1	30.2	2.3	3.4	5.1
HAZE [%]	15.0	17.9	20.3	18.2	19.1	21.0	50.3	89.6	4.2	88.0	99.9	99.9	99.9
BSP width [-]	252	260	261	258	262	268	240	262	262	262	320	310	315
Pencil hardness	H	H	H	H	H	H	H	F	H	H	2B	B	B
Weather Resistance (3000hrs, dE)	2.7	2.6	2.6	2.9	2.9	3.0	2.8	2.8	over 10	2.9	2.2	2.0	1.7

In Examples 1 to 6, all exhibit excellent haze and scratch resistance. On the other hand, Comparative Examples except Comparative Example 3 can be seen that the transparency and haze characteristics are very poor, Comparative Example 3 satisfies the transparency and the haze characteristics, but the weather resistance is greatly degraded to maintain the balance of physical properties.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims

Graft acrylic copolymer (A);

Aromatic vinyl-vinyl cyanide copolymer (B); And

Polyalkyl (meth) acrylate resin (C)

Including,

The aromatic vinyl-vinyl cyanide copolymer (B) is a thermoplastic resin composition comprising a unit derived from 5 to 25% by weight of a vinyl cyanide compound.
The method of claim 1,

The thermoplastic resin composition comprises 50 to 200 parts by weight of the aromatic vinyl-vinyl cyanide copolymer (B) based on 100 parts by weight of the graft acrylic copolymer (A). 　
The method of claim 1,

The thermoplastic resin composition comprises 50 to 300 parts by weight of the polyalkyl (meth) acrylate (C) based on 100 parts by weight of the graft acrylic copolymer (A).
The method of claim 1,

A thermoplastic resin composition having a content ratio of the aromatic vinyl-vinyl cyanide copolymer (B) and the polyalkyl (meth) acrylate (C) in a range of 6: 4 Pa to 3: 7.
The method of claim 1,

The graft acrylic copolymer (A) is a copolymer in which an acrylic rubber-like polymer is copolymerized with the aromatic vinyl monomer, the monomer copolymerizable with the aromatic vinyl monomer, or a combination thereof, graft or two or more thereof. A thermoplastic resin composition that is a combination.
The method of claim 5,

The monomer copolymerizable with the aromatic vinyl monomer may include a vinyl cyanide compound, and the vinyl cyanide compound may be contained in an amount of 20 to 30 wt% of the total amount of the monomer graft-polymerized to the acrylic rubber polymer. .
The method of claim 1,

The aromatic vinyl cyanide copolymer (B) is a thermoplastic resin that is a copolymer of styrene and acrylonitrile, a copolymer of α-methylstyrene and acrylonitrile, or a copolymer of styrene, α-methylstyrene and acrylonitrile. Composition.
The method of claim 1,

The polyalkyl (meth) acrylate resin (C) is an alkyl (meth) acrylate having a C1 to C10 alkyl group, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, The thermoplastic resin composition which is a polymer of glycidyl (meth) acrylate, hydroxyethyl (meth) acrylate, or a combination thereof.
The method of claim 1,

The thermoplastic resin composition further comprises an additive including a dye, a pigment, a flame retardant, a filler, a stabilizer, a lubricant, an antibacterial agent, a release agent, or a combination thereof.
Molded article manufactured using the thermoplastic resin composition of any one of claims 1 to 9.
The method of claim 10,

Molded product with a haze value of 5 to 20 according to ASTM D1003.