WO2013062170A1

WO2013062170A1 - Thermoplastic resin composition and molding using same

Info

Publication number: WO2013062170A1
Application number: PCT/KR2011/009111
Authority: WO
Inventors: 김인철; 홍창민; 하진욱
Original assignee: 제일모직 주식회사
Priority date: 2011-10-27
Filing date: 2011-11-28
Publication date: 2013-05-02
Also published as: KR20130046162A

Abstract

Provided is a thermoplastic resin composition comprising a graft diene copolymer (A) and a highly refractive acrylic copolymer (B), wherein the highly refractive acrylic copolymer comprises units having a structure of formula 1 defined in the description. The graft diene copolymer (A) may be a polymer comprising structural units induced from a (meth)acrylic acid alkyl ester compound in a rubber polymer induced from a diene compound, or may be a graft-polymerized copolymer.

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.

ABS / PMMA resin, which has excellent colorability and scratch resistance, has been widely used for high quality design of home appliances. However, due to the difference in refractive index between ABS and PMMA, scratch characteristics are excellent, but transparency over a certain level is not realized, and high coloration is impossible.It is limited in application to applications requiring heat resistance, such as household appliances, due to the limitation of heat resistance. There is.

One embodiment of the present invention is to provide a thermoplastic resin composition excellent in high coloration, high transparency, scratch resistance and heat resistance.

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

According to one embodiment of the invention, graft diene copolymer (A); And a high refractive index acrylic copolymer (B), wherein the graft diene copolymer (A) is a polymer comprising a structural unit derived from a (meth) acrylic acid alkyl ester compound in a rubbery polymer derived from a diene compound or The copolymer is graft polymerized, and the high refractive index acrylic copolymer provides a thermoplastic resin composition comprising a structural unit of the following formula (1).

[Formula 1]

Where

X is a single bond, oxygen (O) or sulfur (S),

Y is selected from the group consisting of cyclohexyl group, phenyl group, methylphenyl group, methylethylphenyl group, propylphenyl group, methoxyphenyl group, cyclohexylphenyl group, chlorophenyl group, bromophenyl group, phenylphenyl group and benzylphenyl group,

m is an integer of 0-10.

The high refractive index acrylic copolymer (B) may include the structural unit of Chemical Formula 1 in an amount greater than 0 to 40 wt% or less of the total content of the high refractive index acrylic copolymer.

The refractive index of the high refractive index acrylic copolymer (B) is greater than 1.49 and less than or equal to 1.55 　 Can be.

The absolute value of the difference between the refractive index of the graft diene copolymer (A) and the refractive index of the high refractive index acrylic copolymer (B) may be 0.00 to 0.05 kV.

The absolute value of the difference between the refractive index of the graft diene copolymer (A) and the refractive index of the high refractive index acrylic copolymer (B) may be 0.00 to 0.01 kPa.

In the graft diene copolymer (A), a polymer of at least two compounds of an aromatic vinyl compound, a vinyl cyanide compound, and an acrylic compound is first grafted to a rubbery polymer derived from the diene compound, and a (meth) acrylic acid alkyl ester The compound may be a secondary grafted copolymer.

The rubbery polymer forms a core, a polymer of at least two compounds of an aromatic vinyl compound, a vinyl cyanide compound, and an acrylic compound is first grafted to form a cabinet shell, and the (meth) acrylic acid alkyl ester compound is secondary. The graft diene copolymer (A) may be grafted to form an outer shell such that the copolymer is a core and a double shell structure.

The graft diene copolymer (A) is one comprising 30 to 70 parts by weight of diene rubber, 15 to 55 parts by weight of (meth) acrylic acid alkyl ester, 1 to 5 parts by weight of vinyl cyanide and 5 to 35 parts by weight of aromatic vinyl. Can be.

Monomer compound of the structural unit of Formula 1 is cyclohexyl methacrylate, 2-ethylphenoxy methacrylate, 2-ethylthiophenyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-phenylethyl methacrylate Rate, 3-phenylpropyl methacrylate, 4-phenylbutyl methacrylate, 2-2-methylphenylethyl methacrylate, 2-3-methylphenylethyl methacrylate, 2-4-methylphenylethyl methacrylate, 2- (4-propylphenyl) ethyl methacrylate, 2- (4- (1-methylethyl) phenyl) ethyl methacrylate, 2- (4-methoxyphenyl) ethyl methacrylate, 2- (4-cyclohexyl Phenyl) ethyl methacrylate, 2- (2-chlorophenyl) ethyl methacrylate, 2- (3-chlorophenyl) ethyl methacrylate, 2- (4-chlorophenyl) ethyl methacrylate, 2- (4 -Bromophenyl) ethyl methacrylate, 2- (3-phenylphenyl) ethyl methacrylate, 2- (4-benzylphenyl) ethyl From other methacrylate and combinations thereof may include one selected.

The high refractive index acrylic copolymer (B) may be a structural unit derived from one selected from the group consisting of a vinyl monomer copolymerizable with the structural unit of Formula 1, an acrylic monomer copolymerizable with the structural unit of Formula 1, and a combination thereof. It may further include.

The vinyl monomer copolymerizable with the structural unit of Formula 1 and the acrylic monomer copolymerizable with the structural unit of Formula 1 include methacrylic acid esters, acrylic acid esters, acid anhydrides, esters containing hydroxyl groups, acrylamide, and methacryl Amide, acrylonitrile, methacrylonitrile, allyl glycidyl ether, glycidyl methacrylate, styrenic monomers, and combinations thereof.

The thermoplastic resin composition may include greater than 0 to 150 parts by weight or less of the high refractive index acrylic copolymer (B) relative to 100 parts by weight of the graft diene copolymer (A).

The thermoplastic resin composition may further include a vinyl copolymer (C).

The vinyl copolymer (C) may be a copolymer formed by polymerizing 10 to 30 wt% of an aromatic vinyl compound, 0 to 20 wt% of a vinyl cyanide compound, and 50 to 90 wt% of a (meth) acrylic acid alkyl ester compound.

The thermoplastic resin composition may include 50 to 400 parts by weight of the vinyl copolymer (C) relative to 100 parts by weight of the graft acrylic copolymer (A).

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.

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

The thermoplastic resin composition is excellent in colorability, transparency, scratch resistance and heat resistance characteristics.

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.

In addition, in this specification, "*" means the part connected with the same or different atom or formula.

The thermoplastic resin composition according to the embodiment of the present invention includes (A) a graft diene copolymer and (B) a high refractive index acrylic copolymer. The thermoplastic resin composition may optionally further include a vinyl copolymer (C), and may further include additional resins and / or additives depending on the properties to be implemented.

The thermoplastic resin composition includes a graft diene-based copolymer (A) having excellent transparency and (B) a high refractive index acrylic copolymer together with high transparency to enable high coloration, and at the same time, scratch resistance and Excellent heat resistance. Therefore, the thermoplastic resin composition can be variously applied to various uses, and is suitable for use in applications such as housings such as home appliances. Hereinafter, each component included in the thermoplastic resin composition will be described in detail.

(A) Graft Diene Copolymer

The graft diene copolymer is a resin having transparency by graft polymerization of a polymer or copolymer comprising a structural unit derived from a (meth) acrylic acid alkyl ester compound to a rubbery polymer or copolymer derived from a diene compound. to be. For example, the graft diene copolymer (A) may be prepared to have a refractive index of 1.50 to 1.52.

Specifically, the graft diene copolymer is a rubbery polymer or copolymer derived from a diene compound, the polymer of at least two compounds of an aromatic vinyl compound, a vinyl cyanide compound, and an acrylic compound is first grafted, and again ( The meta) acrylic acid alkyl ester compound may be a secondary grafted copolymer. Preferably, the rubbery polymer forms a core, and the polymer of at least two of the aromatic vinyl compound, the vinyl cyanide compound, and the acrylic compound forms the inner shell while primary graft polymerizing the core, and the (meth) As the acrylic acid alkyl ester compound is secondary grafted to form an outer shell, the graft diene-based copolymer may form a core-shell structure.

The rubbery polymer may be derived from a diene-based compound, and specifically, polybutadiene, polyisoprene, polychloroprene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, or the like, or a combination thereof may be used. It is not limited, Among these, polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, or a combination thereof can be used.

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.

As said acryl-type compound, a (meth) acrylic-acid alkylester, (meth) acrylic acid ester, or a combination thereof can be used. In this case, the alkyl means C1 to C10 alkyl.

As a specific example of the said (meth) acrylic-acid alkylester, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, etc. are mentioned, Preferably methyl ( Meta) acrylates may be used. By including the (meth) acrylic acid alkyl ester, the graft diene copolymer may implement transparency, and may also compensate for scratch and strength.

The graft diene copolymer may include a structure formed by primary grafting on the rubbery polymer and may include a structure formed by secondary grafting on the structure. As described above, the rubbery polymer forms a core structure, and the structure formed of the primary graft is an inner shell, and the structure formed of the secondary graft is an outer shell, and may form a core and a double shell structure.

For example, the inner shell of the graft diene copolymer may be a styrene-acrylonitrile resin, and the outer shell may be a polymethyl methacrylate (PMMA) resin. In another example, the inner shell and the outer shell are both methylmethacrylate-acrylonitrile-styrene copolymers.

The graft diene copolymer may be prepared by a known method and is not limited to any particular manufacturing method. For example, the graft diene copolymer may be prepared by the following method.

For example, the shell grafted on the rubber surface is a first method of forming the inner shell and the outer shell to have a different double monomer composition. The first method comprises the first step of graft polymerization of an aromatic vinyl monomer and a vinyl cyanide monomer under a fat-soluble redox-based initiator system to form a cabinet shell on the surface of the rubber, followed by alkyl (meth) acrylates under a water-soluble initiator. It is prepared by a second stage polymerization which adds an ester monomer to form an outer shell to surround the inner shell. The graft diene copolymer (A) having the core and the double shell structure formed by the second step polymerization may be prepared in a powder state through a post-treatment process such as coagulation, washing, and dehydration in a post-treatment process.

As another example, the second method is a method in which a shell layer grafted on a rubber surface is doubled but the monomer composition ratio is the same, and a mixture of (meth) acrylic acid alkyl ester monomers, aromatic vinyl monomers and vinyl cyanide monomers, which are graft monomers, is used. By adding a portion, the core is subjected to the first graft reaction under a fat-soluble redox-based initiator system, and the second step of adding a residual graft monomer mixture under a water-soluble initiator to proceed the second graft reaction. And a graft diene copolymer having a double shell structure formed thereon. The graft diene copolymer (A) having the core and the double shell structure formed by the second step polymerization may be prepared in a powder state through a post-treatment process such as coagulation, washing, and dehydration in a post-treatment process.

The graft diene copolymer which forms the core and the double shell structure prepared by the above two methods is a copolymer of a diene rubber which is a core layer and a (meth) acrylic acid alkyl ester-aromatic vinyl-vinyl cyanide monomer which is a shell layer (Example For example, the refractive index of methyl methacrylate-styrene-acrylonitrile (MSAN) can be the same to improve colorability, and the copolymer of the (meth) acrylic acid alkyl ester-aromatic vinyl-vinyl cyanide monomer which is the shell layer. By inducing polymerization conditions such that the meta) acrylic acid alkyl ester monomer in the composition of the (meth) acrylic acid alkyl ester-aromatic vinyl-vinyl cyanide monomer is located at the chain end, it is possible to suppress scratch reduction, By covering the rubber surface with the (meth) acrylic acid alkyl ester at the outermost side, it is possible to suppress a decrease in weather resistance.

For example, the graft diene copolymer (A) in which the core-double shell structure is formed is methyl methacrylate-acrylonitrile-butadiene-styrene copolymer resin (g-MABS).

The graft diene-based copolymer (A) forming the core-double shell structure is, for example, 30 to 70 parts by weight of rubber, 15 to 55 parts by weight of (meth) acrylic acid alkyl ester, 1 to 5 parts by weight of vinyl cyanide and aromatic It consists of 5 to 35 parts by weight of vinyl.

When the g-MABS resin is manufactured by the first method, the content of polybutadiene or butadiene-styrene rubber latex is 30 to 70% by weight (based on solids), and then the primary cabinet is prepared using acrylonitrile and styrene monomer. The secondary graft polymerization is carried out to form a shell and then to form an outer shell that surrounds the inner shell formed primarily of methyl methacrylate monomer, wherein the graft monomers are combined with the same composition as each rubber refractive index to emulsify the polymerization. After coagulation-dehydration-drying, g-MABS resin in the form of fine powder is obtained.

When the g-MABS resin is prepared by the second method, the polybutadiene or butadiene-styrene rubber latex is 30 to 70% by weight (based on solids), and then methyl methacrylate-acrylonitrile-styrene monomer is used for each rubber. After graft emulsion polymerization in combination with the same composition as the refractive index, coagulation-dehydration-drying gives a g-MABS resin in a fine powder state.

In the preparation of the methyl methacrylate-acrylonitrile-butadiene-styrene copolymer resin (g-MABS), the average particle size of the rubber is preferably in the range of 0.1 to 0.3 ㎛. When the rubber particle size in the above range is provided, the rubber particle size may be excellent in terms of impact resistance, colorability and glossiness.

The butadiene rubber used in the preparation of the methyl methacrylate-acrylonitrile-butadiene-styrene copolymer resin (g-MABS) uses polybutadiene rubber alone or butadiene-styrene copolymer rubber, and has a styrene content of 0 to 30 wt%. The range of% is preferable.

When using polybutadiene rubber in one embodiment of the present invention g-MABS resin is 22.2 to 50.3 parts by weight of methyl methacrylate, 1.5 to 4.2 parts by weight of acrylonitrile, 30 to 70 parts by weight of polybutadiene rubber, and styrene 6.3 To 15.5 parts by weight.

In another embodiment of the present invention when using butadiene-styrene copolymer rubber g-MABS resin is 15.8 to 36.4 parts by weight of methyl methacrylate, 1.5 to 3.5 parts by weight of acrylonitrile, 30 to 70 parts by weight of butadiene-styrene rubber And styrene 12.7 to 30.1 parts by weight.

The graft diene copolymer (A) having the core-double shell structure preferably has a graft ratio in the range of 30 to 70%.

(B) high refractive index acrylic copolymer

The high refractive index acrylic copolymer is a copolymer including a structural unit represented by the following Chemical Formula 1.

[Formula 1]

Where

X is a single bond, oxygen (O) or sulfur (S),

m is an integer of 0-10.

The refractive index of the high refractive index acrylic copolymer may be adjusted to reduce the difference in refractive index of the graft diene copolymer (A), thereby further improving transparency of the thermoplastic resin composition. For example, the refractive index of the high refractive index acrylic copolymer is greater than 1.49 and less than or equal to 1.55, preferably greater than 1.49 to 1.53. Since the structural unit of Chemical Formula 1 has a higher refractive index than that of the heterogeneous structural units copolymerized together, it is possible to obtain a high refractive index acrylic copolymer by adjusting the content thereof. For example, the monomer of the structural unit of Formula 1 may be copolymerized with methyl methacrylate, and the refractive index of methyl methacrylate is known as 1.49. Since the structural unit of Formula 1 has a refractive index of more than 1.49 but less than 1.55, when the content thereof is increased, the acrylic copolymer (B) having a higher refractive index may be lowered, and when the content thereof is lowered, the refractive index may be relatively lowered.

As such, the high refractive index acrylic copolymer may control the refractive index by adjusting the content of the structural unit of Chemical Formula 1. For example, the high refractive index acrylic copolymer may include the structural unit of Formula 1 in an amount greater than 0 to 40 wt% or less in the total content of the high refractive index acrylic copolymer. Preferably, the high refractive index acrylic copolymer may include 20 to 40% by weight of the structural unit of Formula 1 of the total content of the high refractive index acrylic copolymer.

Preferably, the refractive index of the high refractive index acrylic copolymer (B) may be such that the difference in refractive index of the graft diene copolymer (A) is 0.00 to 0.05, more preferably the difference is 0.00 to 0.01 days Can be. The thermoplastic resin composition including the graft diene copolymer (A) and the high refractive index acrylic copolymer (B) having a difference in refractive index within the above range may have excellent transparency and high color performance.

Examples of the monomer compound of the structural unit of Formula 1 include cyclohexyl methacrylate, 2-ethylphenoxy methacrylate, 2-ethylthiophenyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2- Phenylethyl methacrylate, 3-phenylpropyl methacrylate, 4-phenylbutyl methacrylate, 2-2-methylphenylethyl methacrylate, 2-3-methylphenylethyl methacrylate, 2-4-methylphenylethyl methacrylate Late, 2- (4-propylphenyl) ethyl methacrylate, 2- (4- (1-methylethyl) phenyl) ethyl methacrylate, 2- (4-methoxyphenyl) ethyl methacrylate, 2- ( 4-cyclohexylphenyl) ethyl methacrylate, 2- (2-chlorophenyl) ethyl methacrylate, 2- (3-chlorophenyl) ethyl methacrylate, 2- (4-chlorophenyl) ethyl methacrylate, 2- (4-bromophenyl) ethyl methacrylate, 2- (3-phenylphenyl) ethyl methacrylate, 2- (4-benzyl Phenyl) ethyl methacrylate, and the like, but is not necessarily limited thereto. These can be used individually or in mixture of 2 or more types.

The high refractive index acrylic copolymer may further include a conventional copolymerizable vinyl and / or acrylic monomer in addition to the structural unit of Chemical Formula 1. Specific examples of vinyl and / or acrylic monomers copolymerizable with the monomer of the structural unit of Formula 1 include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and benzyl methacrylate. Methacrylic acid esters; Acrylic esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and 2-ethylhexyl acrylate; Acid anhydrides such as unsaturated carboxylic acids such as acrylic acid and methacrylic acid, maleic anhydride and the like; Esters containing hydroxy groups such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, monoglycerol acrylate; Acrylamide, methacrylamide, and the like. Nitriles such as acrylonitrile and methacrylonitrile are also possible, including allyl glycidyl ether; Glycidyl methacrylate; Styrene-based monomers such as styrene and α-methylstyrene may be used, but is not necessarily limited thereto. These can be used individually or in mixture of 2 or more types.

The high refractive index acrylic copolymer is obtained by polymerizing a monomer of the structural unit represented by Chemical Formula 1 and a conventional copolymerizable vinyl-based and / or acrylic monomer mixture, and the polymerization of the high refractive index acrylic copolymer is performed in a usual bulk, solution, suspension and Emulsification polymerization may be applied, but is not necessarily limited thereto.

When the graft diene copolymer (A) is included in the content ratio of the above range, it may be excellent in terms of the balance of physical properties of impact resistance, scratch resistance, gloss and coloring.

The high refractive index acrylic copolymer (B) may be included in an amount of greater than 0 to 150 parts by weight or less relative to 100 parts by weight of the graft diene copolymer (A), preferably the graft diene copolymer (A) 100 It may be included in the range of 25 to 100 parts by weight relative to the weight part. The high refractive index acrylic copolymer (B) is a graft diene copolymer (A) in an amount ratio of greater than 0 to 150 parts by weight or less relative to 100 parts by weight of the graft diene copolymer (A). ) And the scratch resistance of the graft diene copolymer (A) can be compensated for, and the physical properties of the color and transparency properties and the scratch resistance can be maintained.

The weight average molecular weight of the high refractive index acrylic copolymer (B) may be 10,000 to 50,000.

(C) vinyl copolymer

The vinyl copolymer may be a copolymer of an aromatic vinyl compound and a vinyl cyanide compound.

Specific examples of the aromatic vinyl cyanide copolymer include copolymers 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-vinyl cyanide copolymer may be polymerized by further including a (meth) acrylic acid alkyl ester compound together with the aromatic vinyl compound and the vinyl cyanide compound.

It is preferable that the said (meth) acrylic-acid alkylester compound 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.

The vinyl copolymer may be prepared by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization, and a weight average molecular weight of 15,000 kPa to 400,000 g / mol may be used.

For example, the vinyl copolymer may be a copolymer formed by polymerizing 10 to 30 wt% of an aromatic vinyl compound, 0 to 20 wt% of a vinyl cyanide compound, and 50 to 90 wt% of a (meth) acrylic acid alkyl ester compound. Specifically, the copolymer may be formed by polymerizing 15% to 25% by weight of aromatic vinyl compound, 5% to 15% by weight of vinyl cyanide compound, and 70% to 80% by weight of (meth) acrylic acid alkyl ester compound.

The thermoplastic resin composition may include a vinyl copolymer having a content of 50 to 400 parts by weight based on 100 parts by weight of the graft acrylic copolymer (A).

(D) other additives

The thermoplastic resin composition may further include additional additives 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 may be appropriately included within a range 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 May be included in an amount of 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.

The following presents specific embodiments of the present invention. However, the examples described below are merely to specifically illustrate or explain the present invention, and the present invention is not limited thereto.

(실시예)(Example)

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

(A-1) Graft Diene Copolymer

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 It consists of 3 parts by weight of ronitrile and 9 parts by weight of styrene.

(A-2) Graft Diene Copolymer

Butadiene is a resin consisting of a core of 58 parts by weight and a shell of 42 parts by weight, the shell is composed of 31 parts by weight and 11 parts by weight of styrene and acrylonitrile, respectively.

(B-1) Benzyl methacrylate-methyl methacrylate copolymer

A copolymer having 30% by weight of phenylmethacrylate and .70% by weight of methyl methacrylate having an average refractive index of 1.52 and having a weight average molecular weight of 20,000.

(B-2) polymethyl methacrylate

A resin having methyl methacrylate as a monomer and having a weight average molecular weight of 100,000.

(C-1) vinyl copolymer

SAN resin containing 25% by weight of acrylonitrile and 75% by weight of styrene and having a weight average molecular weight of 100,000

(C-2) vinyl copolymer

MSAN resin containing 5% by weight of acrylonitrile, 22% by weight of styrene and 73% by weight of methacrylate and having a weight average molecular weight of 120,000

(C-3) vinyl copolymer

MSAN resin containing 5% by weight of acrylonitrile, 22% by weight of styrene and 73% by weight of methacrylate and having a weight average molecular weight of 80,000

실시예 1 내지 3 및 비교예 1 내지 6Examples 1 to 3 and Comparative Examples 1 to 6

The thermoplastic resin compositions according to Examples 1 to 3 and Comparative Examples 1 to 6 were prepared in the compositions shown in Table 1 using the above-mentioned components. Graft diene copolymer (A-1) or graft diene copolymer (A-2) and benzyl methacrylate-methyl methacrylate copolymer used in each of Examples 1 to 3 and Comparative Examples 1 to 6 The refractive index difference of (B-1) or polymethyl methacrylate (B-2) is shown in Table 1 below.

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.

Table 1

division	To conduct			Comparative example
division	One	2	3	One	2	3	4	5	6
(A-1) Graft Diene Copolymer	25	25	25	25	25	25	-	-	-
(A-2) Graft Diene Copolymer	-	-	-	-	-	-	25	25	25
(B-1) Benzyl methacrylate-methyl methacrylate copolymer	10	20	30	-	-	-	-	-	-
(B-2) polymethyl methacrylate	-	-	-	10	20	30	-	-	75
(C-1) vinyl copolymer	-	-	-	-	-	-	75	-	-
(C-2) vinyl copolymer	25	20	15	30	30	30	-	75	-
(C-2) vinyl copolymer	40	35	30	45	45	45	-	-	-
Difference in refractive index between graft diene copolymer and benzyl methacrylate-methyl methacrylate copolymer (B-1) or polymethyl methacrylate (B-2)	0.001	0.003	0.005	0.05	0.01	0.015	-	-	-

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 pencil 5 times at the speed of 10mm / s by lifting the weight of 500g with a pencil according to hardness. (Measuring pencil and pencil hardness determined in JIS K5401)

(4) VST: measured based on ISO R306 standard (unit, ℃)

TABLE 2

division	To conduct			Comparative example
division	One	2	3	One	2	3	4	5	6
Transmittance (%)	90	89	89	88	85	80	3.5	2.5	3.5
HAZE (%)	3.8	4.0	4.0	10.5	20.2	25.0	99	98	99
BSP width	275	262	255	273	258	250	340	320	276
Pencil hardness	F	H	H	F	H	H	2B	B	F
VST (℃)	98	100	102	95	96	95	92	92	93

Examples 1 to 3 are thermoplastic resin compositions prepared by using the high refractive index acrylic copolymer (B) at 10 parts by weight, 20 parts by weight, and 30 parts by weight of the (B-1) benzyl methacrylate-methyl methacrylate copolymer, respectively. Is an evaluation result of, and Comparative Examples 1 to 3 are evaluation results of the thermoplastic resin composition prepared to be compared to Examples 1 to 3 in the same amount of (B-2) polymethyl methacrylate instead of the high refractive index acrylic copolymer . In comparison with Comparative Examples 1 to 3, Examples 1 to 3 can be confirmed that the haze evaluation is very excellent, and all other evaluation results such as scratch resistance, heat resistance and the like.

On the other hand, Comparative Examples 4 and 5 did not use a graft diene copolymer (A) that is not grafted alkyl methacrylate ester, and does not use a high refractive index acrylic copolymer, very poor transmittance and haze evaluation . Comparative Example 7 (B-2) in the case of using an excessive amount of polymethyl methacrylate improved the BSP results than Comparative Examples 4 and 5, but it was confirmed that it does not help to improve the transmittance, haze, hardness, heat resistance, etc. .

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention and the accompanying drawings. Naturally, it belongs to the scope of the invention.

Claims

(A) graft diene copolymer; And

(B) high refractive index acrylic copolymer;

Including,

The graft diene copolymer (A) is a graft polymer or copolymer comprising a structural unit derived from a (meth) acrylic acid alkyl ester compound to a rubbery polymer derived from a diene compound,

The high refractive index acrylic copolymer (B) is a thermoplastic resin composition comprising a structural unit of the following formula (1):

[Formula 1]

Where

X is a single bond, oxygen (O) or sulfur (S),

Y is selected from the group consisting of cyclohexyl group, phenyl group, methylphenyl group, methylethylphenyl group, propylphenyl group, methoxyphenyl group, cyclohexylphenyl group, chlorophenyl group, bromophenyl group, phenylphenyl group and benzylphenyl group,

m is an integer of 0-10.
The method of claim 1,

The high refractive index acrylic copolymer (B) is a thermoplastic resin composition comprising a structural unit of the formula (1) greater than 0 to 40% by weight or less of the total content of the high refractive index acrylic copolymer.
The method of claim 1,

The thermoplastic resin composition whose refractive index of the said high refractive index acrylic copolymer (B) is more than 1.49 and 1.55 or less.
The method of claim 1,

The thermoplastic resin composition whose absolute value of the difference between the refractive index of the said graft diene type copolymer (A) and the refractive index of the said high refractive index acrylic copolymer (B) is 0.00 kPa-0.05 kPa.
The method of claim 1,

In the graft diene copolymer (A), a polymer of at least two compounds of an aromatic vinyl compound, a vinyl cyanide compound, and an acrylic compound is first grafted to a rubbery polymer derived from the diene compound, and a (meth) acrylic acid alkyl ester The thermoplastic resin composition wherein the compound is a secondary grafted copolymer.
The method of claim 5,

The rubbery polymer forms a core, a polymer of at least two compounds of an aromatic vinyl compound, a vinyl cyanide compound, and an acrylic compound is first grafted to form a cabinet shell, and the (meth) acrylic acid alkyl ester compound is secondary. The graft diene copolymer (A) is grafted to form an outer shell such that the thermoplastic resin composition is a copolymer of a core and a double shell structure.
The method of claim 1,

The graft diene copolymer (A) comprises 30 to 70 parts by weight of diene rubber, 15 to 55 parts by weight of (meth) acrylic acid alkyl ester, 1 to 5 parts by weight of vinyl cyanide and 5 to 35 parts by weight of aromatic vinyl Thermoplastic resin composition.
The method of claim 1,

Monomer compound of the structural unit of Formula 1 is cyclohexyl methacrylate, 2-ethylphenoxy methacrylate, 2-ethylthiophenyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-phenylethyl methacrylate Rate, 3-phenylpropyl methacrylate, 4-phenylbutyl methacrylate, 2-2-methylphenylethyl methacrylate, 2-3-methylphenylethyl methacrylate, 2-4-methylphenylethyl methacrylate, 2- (4-propylphenyl) ethyl methacrylate, 2- (4- (1-methylethyl) phenyl) ethyl methacrylate, 2- (4-methoxyphenyl) ethyl methacrylate, 2- (4-cyclohexyl Phenyl) ethyl methacrylate, 2- (2-chlorophenyl) ethyl methacrylate, 2- (3-chlorophenyl) ethyl methacrylate, 2- (4-chlorophenyl) ethyl methacrylate, 2- (4 -Bromophenyl) ethyl methacrylate, 2- (3-phenylphenyl) ethyl methacrylate, 2- (4-benzylphenyl) ethyl The thermoplastic resin composition other methacrylate and comprises one selected from the group consisting of.
The method of claim 1,

The high refractive index acrylic copolymer (B) may be a structural unit derived from one selected from the group consisting of a vinyl monomer copolymerizable with the structural unit of Formula 1, an acrylic monomer copolymerizable with the structural unit of Formula 1, and a combination thereof. It further comprises a thermoplastic resin composition.
The method of claim 9,

The vinyl monomer copolymerizable with the structural unit of Formula 1 and the acrylic monomer copolymerizable with the structural unit of Formula 1 include methacrylic acid esters, acrylic acid esters, acid anhydrides, esters containing hydroxy groups, acrylamide, and methacryl The amide, acrylonitrile, methacrylonitrile, allyl glycidyl ether, glycidyl methacrylate, styrene-based monomers, and combinations thereof.
The method of claim 1,

The thermoplastic resin composition comprises more than 0 to 150 parts by weight of the high refractive index acrylic copolymer (B) relative to 100 parts by weight of the graft-diene copolymer (A).
The method of claim 1,

The thermoplastic resin composition further comprises (C) a vinyl-based copolymer.
The method of claim 1,

The vinyl-based copolymer (C) is a thermoplastic resin composition in which a copolymer of 10 to 30% by weight of an aromatic vinyl compound, 0 to 20% by weight of a vinyl cyanide compound and 50 to 90% by weight of a (meth) acrylic acid alkyl ester compound is polymerized.
The method of claim 1,

The thermoplastic resin composition includes 50 to 400 parts by weight of the vinyl-based copolymer (C) relative to 100 parts by weight of the graft acrylic copolymer (A).
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 15.