KR101438260B1 - Thermoplastic resin composition - Google Patents

Abstract

More particularly, the present invention relates to a polycarbonate thermoplastic resin composition comprising (A) 10 to 90% by weight of a polycarbonate resin; And (B) 5 to 30% by weight of a polymethyl methacrylate resin; And (C) 5 to 30% by weight of a rubber-modified graft copolymer comprising a hydroxy clock (meth) acrylate; And (D) 5 to 30% by weight of an acrylic copolymer. According to the present invention, there is provided a polycarbonate thermoplastic resin having excellent scratch resistance and impact resistance as well as excellent appearance and coloring property can do.

Description

[0001] Thermoplastic resin composition [0002]

The present invention relates to a polycarbonate-based thermoplastic resin composition, and more particularly, to a rubber-modified graft copolymer containing (A) 10 to 85% by weight of a polycarbonate resin; And (B) 5 to 30% by weight of a polymethyl methacrylate resin; And (C) 5 to 30% by weight of a rubber-modified graft copolymer; And (D) 5 to 30% by weight of an acrylic copolymer to thereby provide a polycarbonate-based thermoplastic resin composition having excellent scratch resistance and impact resistance as well as excellent appearance and coloring properties.

The polycarbonate resin is excellent in impact resistance, heat resistance and dimensional stability, and is excellent in flame retardancy and electrical characteristics, and is used in a wide range of applications from electrical and electronic equipment to office automobiles and automobile products. However, Lt; / RTI >

On the other hand, acrylic resins such as polymethyl methacrylate are excellent in scratch resistance and gloss, but they are very difficult to achieve desired flame retardancy with current flame retardant, and have a low impact strength, so that they are limited to various exterior materials.

A polycarbonate / polymethyl methacrylate blend resin is provided as a method for simultaneously completing the problems of the above two resins and simultaneously exhibiting scratch resistance, flame retardancy and impact resistance. However, there is a problem that the coloring property is deteriorated due to a large difference in refractive index and compatibility between the two resins, and a sufficient impact strength can not be obtained.

JP-A-1991-124764 proposes a polycarbonate / polymethylmethacrylate blend resin using an acrylic rubber impact modifier. However, in order to solve the problem of compatibility of a blend resin due to insufficient increase in impact strength, 2010-0075078 discloses that a rubber-modified vinyl-based graft copolymer containing an acrylic monomer is incorporated in a polycarbonate resin to improve flow mark resistance, but the scratch resistance and impact resistance are not sufficiently improved.

On the other hand, in US Pat. Nos. 5,302,646 and 5,310,791, a polycarbonate-based blend resin is proposed using a graft copolymer containing hydroxy (meth) acrylate, but there is no mention of scratch resistance, Respectively.

Disclosure of the Invention An object of the present invention is to provide a rubber-modified graft copolymer which is excellent in scratch resistance and impact resistance, A polycarbonate-based thermoplastic resin composition having colorability and a molded product thereof.

The above object of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention provides a thermoplastic resin composition comprising (A) 10 to 85% by weight of a polycarbonate resin; And (B) 5 to 30% by weight of a polymethyl methacrylate resin; And (C) 5 to 30% by weight of a rubber-modified graft copolymer comprising a hydroxy clock (meth) acrylate; And (D) 5 to 30% by weight of an acrylic copolymer. The present invention also provides a polycarbonate thermoplastic resin composition.

According to the present invention, by using a rubber-modified graft copolymer containing a hydroxy clock (meth) acrylate, a polycarbonate thermoplastic resin composition having excellent appearance and coloring as well as excellent scratch resistance and impact resistance Can be provided.

The polycarbonate thermoplastic resin composition according to one embodiment of the present invention comprises (A) 10 to 85% by weight of a polycarbonate resin; (B) 5 to 30% by weight of a polymethylmethacrylate resin; (C) 5 to 30% by weight of a rubber-modified graft copolymer comprising a hydroxy clock (meth) acrylate; And (D) 5 to 30% by weight of an acrylic copolymer.

Hereinafter, each component constituting the polycarbonate thermoplastic resin composition according to one embodiment of the present invention will be described in detail.

(A) Polycarbonate resin

The polycarbonate resin preferably has a weight average molecular weight of 10,000 to 200,000 g / mol, but is not limited thereto. It is possible to obtain physical properties such as excellent impact strength in the above-mentioned molecular weight range, and it is possible to obtain appropriate flowability and excellent workability.

When the weight average molecular weight of the polycarbonate resin is less than 10,000 g / mol, the impact resistance tends to be lowered. When the weight average molecular weight is more than 200,000 g / mol, the flowability is lowered and processing becomes difficult.

The polycarbonate resin may be a mixture of copolymers prepared from two or more diphenols. The polycarbonate resin may be a linear polycarbonate resin, a branched polycarbonate resin, or a polyester carbonate copolymer resin.

Examples of the linear polycarbonate resin include a bisphenol-A polycarbonate resin and the like. Examples of the branched polycarbonate resin include those prepared by reacting with a polyfunctional aromatic compound, such as trimellitic anhydride, trimellitic acid, etc., and a carbonate. Examples of the polyester carbonate copolymer resin include those prepared by reacting a bifunctional carboxylic acid with a diphenol and a carbonate. At this time, examples of the carbonate include diaryl carbonate such as diphenyl carbonate, ethylene carbonate, and the like.

The polycarbonate resin is contained in an amount of 10 to 85% by weight, more preferably 20 to 70% by weight, based on the total amount of the thermoplastic resin composition. When the content of the polycarbonate resin is less than 10% by weight, it is difficult to impart flame retardancy to the resin and the impact resistance is low. When the content exceeds 85% by weight, workability and scratch resistance are deteriorated.

(B) Polymethyl methacrylate  Suzy

The polymethyl methacrylate resin preferably has a weight average molecular weight of 90,000 to 120,000 g / mol, but is not limited thereto. It is possible to obtain an effect of having excellent flowability, moldability and appropriate impact strength in the above molecular weight range.

The polymethyl methacrylate resin is contained in an amount of 5 to 30% by weight, more preferably 10 to 25% by weight, based on the total amount of the thermoplastic resin composition. When the polymethylmethacrylate resin is used in an amount of less than 5% by weight, the scratch resistance is lowered. When the polymethylmethacrylate resin is used in an amount exceeding 30% by weight, flame retardancy and impact strength are lowered.

(C) Hydro clock  ( Meta ) Acrylate  Including rubber degeneration Graft  Copolymer

The rubber-modified graft copolymer used in the present invention is a rubber-modified graft copolymer including a hydroxyl clock (meth) acrylate.

The rubber-modified graft copolymer may be prepared by graft-polymerizing a rubbery polymer, a vinyl monomer, and a hydroxyl clock (meth) acrylate monomer.

The hydroxy clock (meth) acrylate may be at least one selected from the group consisting of hydroxyethyl (meth) acrylate, hydroxymethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl At least one kind selected from the group consisting of

The vinyl-based monomer includes an acrylic monomer, and may further include an aromatic vinyl monomer and an unsaturated nitrile monomer.

The acrylic monomer may be selected from the group consisting of (meth) acrylic acid alkyl ester, (meth) acrylic acid ester, maleic anhydride, alkyl and phenyl N-substituted maleimide. Here, the alkyl group means an alkyl group having 1 to 10 carbon atoms. Specific examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, Acrylate can be preferably used.

The aromatic vinyl monomer is selected from the group consisting of styrene, alkylstyrenes having 1 to 10 carbon atoms, and halogen-substituted styrenes. Specific examples of the alkyl-substituted styrene include o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, and alpha methylstyrene.

The unsaturated nitrile monomer is selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile.

The rubbery polymer may be at least one selected from the group consisting of a butadiene rubber, an acrylic rubber, an ethylene propylene rubber, a styrene / butadiene rubber, an acrylonitrile / butadiene rubber, an isoprene rubber, a terpolymer of ethylene / propylene / diene (EPDM) or a polyorganosiloxane / ) Acrylate rubber composite may be used.

When the vinyl monomer according to the present invention is in the form of a mixture of an acrylic monomer, an aromatic vinyl monomer and an unsaturated nitrile monomer, it is preferable that 30 to 70 wt% of the acrylic monomer, 5 to 25 wt% of the aromatic vinyl monomer, and 1 to 15 wt% of the unsaturated nitrile monomer % Can be used by graft copolymerizing the above monomers with polybutadiene rubber.

The rubber-modified graft copolymer containing the hydroxy clock (meth) acrylate is contained in an amount of 5 to 30% by weight, more preferably 10 to 25% by weight based on the total amount of the thermoplastic resin composition. When a rubber-modified graft copolymer containing a hydroxyl-containing (meth) acrylate is included in the above-mentioned range, excellent impact strength and compatibility with other resins can be increased to obtain a good appearance.

The content of hydroxy clock (meth) acrylate is 0.1 to 2% by weight in the preparation of a rubber-modified graft copolymer containing a hydroxy clock (meth) acrylate, and the other acrylic monomer is prepared by using a methyl methacrylate monomer do.

(D) an acrylic copolymer

The acrylic copolymer preferably has a weight average molecular weight of 80,000 to 300,000 g / mol, but is not limited thereto. If the weight average molecular weight is less than 80,000 g / mol, the impact strength of the final product is lowered. If the weight average molecular weight is more than 300,000,000 g / mol, the fluidity is lowered and the processing difficulty is present.

The acrylic copolymer is prepared by copolymerizing 40 to 75% by weight of an alkyl acrylate, 15 to 40% by weight of an aromatic vinyl compound and 3 to 20% by weight of a vinyl cyan compound.

Particularly, it is preferable to be produced by suspension polymerization or bulk polymerization, and continuous bulk polymerization is most preferable in consideration of manufacturing cost.

When polymerization is carried out in aqueous phase, such as emulsion polymerization or suspension polymerization, when the content of vinyl cyanide is high, acrylonitrile, which is a hydrophilic monomer, generates homopolymer in a large amount in the aqueous phase and yellowing of the resin occurs. In the bulk polymerization, Even if the content is increased to a large extent, the homopolymer formation is small and the degree of yellowing is reduced, and the chemical resistance and impact resistance are improved.

Even if the amount of the vinyl cyan derivative exceeds 20% by weight, the yellowing phenomenon also occurs. When the amount of the vinyl cyan derivative is less than 3% by weight, the chemical resistance, scratch resistance and impact strength are lowered.

The alkyl acrylate may be selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and butyl (meth) acrylate, but is not limited thereto .

The aromatic vinyl compound may be selected from the group consisting of styrene, alkylstyrene having 1 to 10 carbon atoms, and halogen-substituted styrene, but is not limited thereto.

The vinyl cyan compound may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile, but is not limited thereto.

The acrylic copolymer is contained in an amount of 5 to 30% by weight, and more preferably 10 to 25% by weight based on the total amount of the thermoplastic resin composition. When the acrylic copolymer is used in an amount less than 5% by weight, the flowability is deteriorated and the workability is deteriorated. When the acrylic copolymer is used in an amount exceeding 30% by weight, the scratch resistance is lowered.

The polycarbonate thermoplastic resin composition of the present invention may further contain additives such as known ultraviolet absorbers, antioxidants, light stabilizers, dyes, and pigments, if necessary.

The finished polycarbonate thermoplastic resin composition is excellent in appearance, scratch resistance and impact resistance by extrusion, injection molding, extrusion-blow molding and the like, which are conventionally used. A molded body can be provided.

The present invention provides a molded article produced from the polycarbonate-based thermoplastic resin composition.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Changes and modifications may fall within the scope of the appended claims.

[Example]

The constituent components used in the thermoplastic resin composition according to the embodiment for realizing the object of the present invention are as follows.

(A) Polycarbonate resin

The polycarbonate resin used was LG-Dow Polycarbonate Caliber PC300-15 having a weight average molecular weight of 25,000 g / mol.

(B) Polymethyl methacrylate resin

The polymethylmethacrylate resin used was IH830 from LG MMA, and the weight average molecular weight was 101,000 g / mol.

(C) Preparation of rubber-modified graft copolymer

To 100 parts by weight of ion-exchanged water, 1.5 parts by weight of sodium oleate emulsifier, 34.5 parts by weight of methyl methacrylate, 11.6 parts by weight of styrene, 2.5 parts by weight of acrylonitrile, 0.5 part by weight of ethyl methacrylate, 0.5 part by weight of tertiary dodecylmercaptan, 0.048 part by weight of sodium pyrophosphate, 0.012 part by weight of dextrose, 0.001 part by weight of ferrous sulfate and 0.04 part by weight of cumene hydroperoxide were added at 75 DEG C For 5 hours. After the reaction, the temperature was raised to 80 DEG C, aged for 1 hour, and the reaction was terminated. At this time, the polymerization conversion was 99.7% and the solid solid content was 0.1%. The latex was coagulated with a 1% aqueous solution of sulfuric acid, washed and then used as a powder.

And 1 part by weight of (C-2) hydroxyethyl methacrylate, a powder was prepared in the same manner as in Production Example C-1. At this time, the polymerization conversion was 99.5% and the solid content was 0.11%.

And 1.5 parts by weight of (C-3) hydroxyethyl methacrylate, a powder was prepared in the same manner as in Production Example C-1. At this time, the polymerization conversion was 99.7% and the solid content was 0.12%.

(C-4) 2.0 parts by weight of hydroxyethyl methacrylate was used to prepare a powder in the same manner as in Production Example C-1. At this time, the polymerization conversion was 99.5% and the solid content was 0.13%.

(C-5) To 50 parts by weight of polybutadiene rubber latex, 100 parts by weight of ion-exchanged water, 1.5 parts by weight of sodium oleate emulsifier, 35.8 parts by weight of methyl methacrylate, 11.7 parts by weight of styrene and 2.5 parts by weight of acrylonitrile Powder was prepared in the same manner as C-1. At this time, the polymerization conversion was 99.6% and the solid content was 0.15%.

Using 60 parts by weight of the polybutadiene rubber latex (C-6), 100 parts by weight of ion-exchanged water, 1.0 part by weight of sodium oleate emulsifier, 30 parts by weight of styrene, and 10 parts by weight of acrylonitrile, . At this time, the polymerization conversion was 99.4% and the solid content was 0.05%.

(D) Production of acrylic copolymer

A raw material obtained by mixing 74 parts by weight of methyl methacrylate, 19 parts by weight of styrene, 7 parts by weight of acrylonitrile, 30 parts by weight of toluene as a solvent, and 0.15 part by weight of di-tertiary dodecyl mercaptan as a molecular weight adjusting agent, And the reaction temperature was maintained at 150 ° C. The polymer solution discharged from the reaction tank was heated in a preheating tank, the unreacted monomers were volatilized in a volatilizing tank, and the temperature of the polymer was kept at 210 ° C., and the copolymer resin was processed into a pellet form using a polymer transfer pump extrusion machine . The molecular weight of the prepared acrylic copolymer is 120,000 g / mol.

(E) a styrenic copolymer

The styrenic copolymer used was a copolymer consisting of 25% by weight of acrylonitrile and 75% by weight of styrene and had a weight average molecular weight of 130,000 g / mol.

[Test Example]

The above-mentioned components were mixed in the contents as shown in the following Table 1, and then melt-kneaded with a 40Φ twin-screw extruder to prepare pellets, which were then injected to prepare specimens, and physical properties thereof were measured.

1. Pencil Hardness: Measured according to ASTM D-3365.

2. Flow Mark: The extruded pellet was prepared as a specimen through an injection machine and the surface of the specimen was visually measured.

◯: many flow mark was observed, △: flow mark was not observed, x: no flow mark

3. Notched Izod Impact Strength: The impact strength was measured using a 1/8 "specimen using ASTM D256.

4. Color (b value): The b value (yellowness) was measured using Color Quest II (Hunter Lab).

Physical properties of Examples and Comparative Examples Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 Example 2 Example 3 Implementation 4 (A)
(Parts by weight) 65 65 65 65 65 65 65 (B)
(Parts by weight) 13 13 13 13 13 13 13 (C1)
(Parts by weight) 10 (C2)
(Parts by weight) 10 (C3)
(Parts by weight) 10 (C4)
(Parts by weight) 10 (C5)
(Parts by weight) 10 10 (C6)
(Parts by weight) 10 (D)
(Parts by weight) 12 12 12 12 12 (E)
(Parts by weight) 12 12 Pencil Hardness HB HB HB H H F F Flow mark ○ ○ ○ △ × × × 1/8 " 42.4 41.4 43.8 47.2 45.5 44.8 44.3 b 5.8 4.5 4.3 2.3 2.4 2.7 2.9

As can be seen from Examples 1 to 4, when 5 to 30% by weight of a rubber-modified graft copolymer containing a hydroxyl-containing (meth) acrylate is used, it has excellent scratch resistance and impact resistance as compared with Comparative Examples It has an excellent appearance and coloring property.

Claims (7)

(A) 10 to 85% by weight of a polycarbonate resin;
(B) 5 to 30% by weight of a polymethylmethacrylate resin;
(C) 5 to 30% by weight of a rubber-modified graft copolymer comprising a hydroxyl clock (meth) acrylate; And
(D) 5 to 30% by weight of an acrylic copolymer. The method according to claim 1,
The hydroxy clock (meth) acrylate may be at least one selected from the group consisting of hydroxyethyl (meth) acrylate, hydroxymethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl Based on the total weight of the polycarbonate-based thermoplastic resin composition. The method according to claim 1,
Wherein the acrylic copolymer is prepared by copolymerizing 40 to 75 wt% of an alkyl acrylate, 15 to 40 wt% of an aromatic vinyl compound, and 3 to 20 wt% of a vinyl cyan compound. The method of claim 3,
Wherein the alkyl acrylate is at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and butyl (meth) acrylate. Composition. The method of claim 3,
Wherein the aromatic vinyl compound is at least one selected from the group consisting of styrene, alkylstyrenes having 1 to 10 carbon atoms, and halogen-substituted styrenes. The method of claim 3,
Wherein the vinyl cyan compound is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile. A molded article produced from the polycarbonate thermoplastic resin composition according to any one of claims 1 to 6.