KR20190083850A - Thermoplastic resin composition - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition comprising: a first copolymer including a conjugated diene polymer having the average diameter of 0.1 to 0.5 μm, an aromatic vinyl monomer derived unit and a vinyl cyanide monomer derived unit; a second copolymer including a conjugated diene polymer having the average diameter of 1 to 1.5 μm, an aromatic vinyl monomer derived unit and a vinyl cyanide monomer derived unit; a third copolymer including an aromatic vinyl monomer derived unit and a vinyl cyanide monomer derived unit; a first additive including zeolite; and a second additive including an aliphatic polyol compound. The thermoplastic resin composition has excellent thermal stability and falling sphere impact strength.

Description

[0001] THERMOPLASTIC RESIN COMPOSITION [0002]

The present invention relates to a thermoplastic resin composition, and more particularly, to a thermoplastic resin composition comprising an aliphatic polyol compound and a zeolite.

Acrylonitrile-butadiene-styrene graft copolymer (hereinafter referred to as 'ABS graft copolymer') is excellent in processability and mechanical strength and has an excellent appearance, and can be used as an internal or external material for electric and electronic products, automobile parts and OA products .

Methods for producing ABS graft copolymers include bulk polymerization, suspension polymerization and emulsion polymerization. When ABS graft copolymer is prepared by emulsion polymerization, the adjustment of the average particle size of the butadiene polymer is a very important process. However, when a butadiene copolymer having an average particle diameter of 0.3 탆 or more is prepared by emulsion polymerization, a very long reaction time of 40 hours or more is required. Therefore, in order to overcome such disadvantages, a butadiene copolymer latex having a small diameter is prepared and agglomerized in a short time to prepare large diameter particles to reduce the reaction time and increase the impact strength.

Unlike the emulsion polymerization, ABS copolymers are prepared by bulk polymerization by dissolving butadiene polymers in styrene and acrylonitrile monomers, and occlusion phenomenon appears in the butadiene polymer of about 1 ㎛ or more.

Large-scale butadiene polymer can be produced in a relatively short time in bulk polymerization, but it is rather difficult to control the distribution of butadiene polymer. Emulsion polymerization is easy to control the distribution of butadiene polymer, but is not advantageous for production of large-diameter butadiene polymer.

As a result, a resin composition using an ABS graft copolymer prepared by emulsion polymerization and an ABS graft copolymer prepared by bulk polymerization has been proposed.

However, despite such mixed use, the resin composition containing the ABS graft copolymer is not excellent in heat stability and impact strength. By using the aliphatic polyol compound as a heat stabilizer, the thermal stability was improved, but the impact strength was still poor.

As a result, studies have been continuing to improve the impact strength of the droppings while realizing excellent thermal stability.

KR2017-0047553A

It is an object of the present invention to provide a thermoplastic resin composition which realizes excellent thermal stability and impact strength.

In order to solve the above-mentioned problems, there is provided a copolymer comprising a first copolymer comprising a conjugated diene polymer having an average particle diameter of 0.1 to 0.5 탆, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer; A second copolymer comprising a conjugated diene polymer having an average particle size of 1 to 1.5 탆, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer; A third copolymer comprising an aromatic vinyl monomer-derived unit and a vinylcyanide monomer-derived unit; A first additive comprising an aliphatic polyol compound; And a second additive comprising zeolite.

Further, the present invention provides a thermoplastic resin molded article produced from the above-mentioned thermoplastic resin composition, wherein the impact resistance of fall resistance based on ASTM D 3763 is 3,000 N or more and the discoloration degree (DELTA E) is 3.3 or less.

The thermoplastic resin composition according to the present invention can achieve excellent thermal stability and impact strength.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

The thermoplastic resin composition according to one embodiment of the present invention comprises: 1. a first copolymer comprising a conjugated diene polymer having an average particle diameter of 0.1 to 0.5 탆, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer; 2. A second copolymer comprising a conjugated diene polymer having an average particle diameter of 1 to 1.5 탆, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer; 3. A third copolymer comprising an aromatic vinyl-based monomer-derived unit and a vinylcyanide monomer-derived unit; 4. a first additive comprising an aliphatic polyol compound; And 5. a second additive comprising zeolite.

The thermoplastic resin composition according to an embodiment of the present invention may further include a 6. organohalogen compound.

Hereinafter, the constituent elements of the thermoplastic resin composition according to one embodiment of the present invention will be described in detail.

1. First copolymer

The first copolymer is a graft copolymer and includes a conjugated diene polymer having an average particle diameter of 0.1 to 0.5 탆, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer.

The first copolymer can impart excellent gloss and impact resistance to the thermoplastic resin composition.

The conjugated diene polymer may include a conjugated diene polymer modified by graft polymerizing an aromatic vinyl monomer and a vinyl cyan monomer to a conjugated diene polymer produced by polymerization of a conjugated diene monomer.

Here, the conjugated diene-based monomer may be at least one member selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, and piperylene, and 1,3-butadiene may be preferable.

The average particle diameter of the conjugated diene-based polymer is 0.1 to 0.5 占 퐉, preferably 0.2 to 0.4 占 퐉, and more preferably 0.25 to 0.35 占 퐉.

When the above-mentioned range is satisfied, the impact resistance of the first copolymer can be further improved. When the amount is less than the above-mentioned range, the impact resistance of the first copolymer is remarkably deteriorated, and if it exceeds the above-mentioned range, the surface gloss characteristics are lowered.

The conjugated diene polymer may be contained in an amount of 45 to 75% by weight, 50 to 65% by weight or 55 to 60% by weight based on the total weight of the first copolymer, preferably 55 to 60% by weight Do. When the above-mentioned range is satisfied, the impact resistance and processability of the first copolymer can be further improved.

The aromatic vinyl-based monomer-derived unit may be at least one derived unit selected from the group consisting of styrene,? -Methylstyrene,? -Ethylstyrene, and p-methylstyrene, and styrene-derived units are preferred.

The aromatic vinyl monomer-derived unit may be contained in an amount of 15 to 45% by weight, 20 to 40% by weight or 25 to 35% by weight based on the total weight of the first copolymer, and 25 to 35% . When the above-mentioned range is satisfied, the chemical resistance, stiffness, impact resistance, workability and surface gloss of the heat-resistant resin composition can be further improved.

The unit derived from the vinyl cyan monomer may be at least one derived unit selected from the group consisting of acrylonitrile, methacrylonitrile, phenyl acrylonitrile and? -Chloroacrylonitrile, and the unit derived from acrylonitrile Unit is preferable.

The unit derived from the vinyl cyan monomer may be contained in an amount of 1 to 20 wt%, 3 to 17 wt%, or 5 to 12 wt% based on the total weight of the first copolymer, and 5 to 12 wt% . When the above-mentioned range is satisfied, the chemical resistance, stiffness, impact resistance, workability and surface gloss of the heat-resistant resin composition can be further improved.

The first copolymer may have a graft rate of 10 to 60%, 20 to 50%, or 30 to 40%, and preferably 30 to 40%. When the above-mentioned range is satisfied, a balance can be made between the thermal stability and the impact resistance of the first copolymer.

The first copolymer may be prepared by polymerizing an aromatic vinyl monomer and a vinyl cyan monomer in the presence of a conjugated diene polymer by at least one method selected from the group consisting of emulsion polymerization, suspension polymerization and bulk polymerization, It is preferable to be produced by emulsion polymerization.

The first copolymer may be contained in an amount of 15 to 40 wt%, 20 to 35 wt%, or 25 to 30 wt% based on the total weight of the first to third copolymers, and 25 to 30 wt% . When the above-mentioned range is satisfied, the impact resistance of the thermoplastic resin composition can be improved, and the thermal stability can be further improved, so that generation of surface gas and discoloration can be minimized.

2. Second copolymer

The second copolymer is a graft copolymer and includes a second copolymer comprising a conjugated diene polymer having an average particle diameter of 1 to 1.5 탆, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer.

The second copolymer can impart excellent impact resistance and impact strength to the thermoplastic resin composition.

The conjugated diene polymer may include a conjugated diene polymer modified by graft polymerizing an aromatic vinyl monomer and a vinyl cyan monomer to a conjugated diene polymer produced by polymerization of a conjugated diene monomer.

Here, the conjugated diene-based monomer may be at least one member selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, and piperylene, and 1,3-butadiene may be preferable.

The average particle diameter of the conjugated diene polymer is 1 to 1.5 占 퐉, preferably 1.1 to 1.3 占 퐉, and more preferably 1.15 to 1.25 占 퐉.

When the above-mentioned range is satisfied, the impact resistance and the drop impact strength of the second copolymer can be further improved. If the amount is less than the above-mentioned range, the drop impact strength of the second copolymer is remarkably lowered, and if it exceeds the above-mentioned range, the gloss characteristics and the low temperature drop impact strength of the second copolymer are remarkably lowered.

The conjugated diene polymer may be contained in an amount of 1 to 25% by weight, 5 to 20% by weight, or 10 to 15% by weight based on the total weight of the second copolymer, preferably 10 to 15% by weight Do. When the above-mentioned range is satisfied, the impact resistance and the drop impact strength of the second copolymer can be further improved.

The aromatic vinyl-based monomer-derived unit may be at least one derived unit selected from the group consisting of styrene,? -Methylstyrene,? -Ethylstyrene, and p-methylstyrene, and styrene-derived units are preferred.

The aromatic vinyl-based monomer-derived unit may be contained in an amount of 50 to 75% by weight, 55 to 70% by weight or 60 to 65% by weight based on the total weight of the second copolymer, and 60 to 65% . When the above-mentioned range is satisfied, the processability of the second copolymer can be further improved.

The unit derived from the vinyl cyan monomer may be at least one derived unit selected from the group consisting of acrylonitrile, methacrylonitrile, phenyl acrylonitrile and? -Chloroacrylonitrile, and the unit derived from acrylonitrile Unit is preferable.

The unit derived from the vinyl cyan monomer may be contained in an amount of 15 to 40% by weight, 20 to 35% by weight or 25 to 30% by weight based on the total weight of the second copolymer, and 25 to 30% . When the above range is satisfied, the yellowing of the second copolymer does not occur, and the chemical resistance can be further improved.

The second copolymer may be produced by polymerizing an aromatic vinyl monomer and a vinyl cyan monomer in the presence of a conjugated diene polymer by at least one method selected from the group consisting of emulsion polymerization, suspension polymerization and bulk polymerization, Lt; / RTI > by mass bulk polymerization.

The second copolymer may be contained in an amount of 5 to 15% by weight, 5 to 12% by weight, or 5 to 10% by weight based on the total weight of the first to third copolymers, and 5 to 10% . When the above-mentioned range is satisfied, the impact resistance and the drop impact strength of the thermoplastic resin composition can be further improved.

3. Third copolymer

The third copolymer is a matrix copolymer and includes an aromatic vinyl monomer-derived unit and a vinylcyanide monomer-derived unit.

The third copolymer can balance the physical properties of the thermoplastic resin composition, that is, balance of impact resistance, heat resistance and fluidity.

The aromatic vinyl-based monomer-derived unit may be at least one derived unit selected from the group consisting of styrene,? -Methylstyrene,? -Ethylstyrene, and p-methylstyrene, and styrene-derived units are preferred.

The unit derived from the vinyl cyan monomer may be at least one derived unit selected from the group consisting of acrylonitrile, methacrylonitrile, phenyl acrylonitrile and? -Chloroacrylonitrile, and the unit derived from acrylonitrile Unit is preferable.

The third copolymer may contain the aromatic vinyl-based monomer-derived unit and the vinyl cyan-based monomer-derived unit in a weight ratio of 85:15 to 70:30 or 80:20 to 75:25, 75:25 by weight.

When the above-mentioned range is satisfied, the third copolymer can give a high fluidity while giving a balance of physical properties of the thermoplastic resin composition, that is, a balance of impact resistance, heat resistance and fluidity.

The weight average molecular weight of the third copolymer may be 100,000 to 150,000 g / mol or 110,000 to 140,000 g / mol, preferably 110,000 to 140,000 g / mol. The third copolymer gives a good balance of physical properties of the thermoplastic resin composition, that is, a balance of impact resistance, heat resistance and fluidity, and can impart excellent impact resistance.

The third copolymer may be prepared by polymerizing an aromatic vinyl monomer and a vinyl cyan monomer with at least one method selected from the group consisting of emulsion polymerization, suspension polymerization and bulk polymerization, desirable.

The third copolymer may be contained in an amount of 55 to 80% by weight, 60 to 75% by weight or 65 to 70% by weight based on the total weight of the first to third copolymers, and 65 to 70% by weight thereof . When the above-mentioned range is satisfied, the third copolymer can balance the physical properties of the thermoplastic resin composition, that is, balance of impact resistance, chemical resistance, heat resistance and fluidity.

4. First additive

The first additive includes an aliphatic polyol compound.

The aliphatic polyol compound is excellent in compatibility with the first to third copolymers, can be uniformly dispersed in the thermoplastic resin composition, and can impart excellent thermal stability to the thermoplastic resin composition.

The aliphatic polyol compound may mean an aliphatic compound containing two or more, preferably 2 to 8, hydroxyl groups.

The aliphatic polyol compound may be at least one member selected from the group consisting of trimethylol propane, pentaerythritol, tripentaerythritol, xylitol, mannitol, sorbitol, glycerin and hydroxystearyl alcohol, Pentaerythritol, which can be uniformly dispersed, is preferred.

The first additive may be contained in an amount of 0.01 to 1 part by weight, 0.05 to 0.7 part by weight or 0.1 to 0.5 part by weight based on 100 parts by weight of the sum of the first to third copolymers, and 0.1 to 0.5 parts by weight thereof Do.

When the above-mentioned range is satisfied, deterioration in mechanical properties, specifically, impact resistance, tensile properties and bending properties can be prevented while improving the thermal stability of the thermoplastic resin composition.

5. Second additive

The second additive comprises zeolite.

The second additive can impart excellent thermal stability and impact strength to the thermoplastic resin composition. As a result, the gas mark on the surface of the molded article made of the thermoplastic resin composition can be remarkably reduced.

In addition, the zeolite contains pores, and the cations have relatively mobility within the pores, so that they can act as catalysts or halogen scavengers in the thermal stability mechanism. Accordingly, the zeolite can impart excellent thermal stability to the thermoplastic resin composition.

The zeolite may be zeolite X or zeolite Y having a molar ratio (Si / Al) of Si to Al of 1.0 to 3.0.

The zeolite may have an inlet average diameter of pores of 0.7 to 0.8 nm or 0.72 to 0.76 nm, of which 0.72 to 0.76 nm is preferred. In addition, the average diameter of the inside of the pores may be 1.0 to 1.5 nm or 1.2 to 1.4 nm, and preferably 1.2 to 1.4 nm.

When the above-mentioned conditions of the molar ratio and pore are satisfied, the thermal stability of the thermoplastic resin composition can be further improved.

The zeolite may have an average particle diameter of 1 to 10 탆, 2 to 7 탆 or 3 to 5 탆, preferably 3 to 5 탆. When the above-mentioned range is satisfied, the thermal stability and the drop impact strength of the thermoplastic resin composition can be further improved.

The second additive may be included in an amount of 0.01 to 1 part by weight, 0.05 to 0.7 part by weight or 0.1 to 0.5 part by weight based on 100 parts by weight of the sum of the first to third copolymers, and 0.15 to 0.6 parts by weight thereof Do. When the above-mentioned range is satisfied, the thermal stability and the drop impact strength of the thermoplastic resin composition can be further improved.

The weight ratio of the first additive to the second additive may be 70:30 to 50:50 or 60:40 to 50:50, and the weight ratio of the first additive to the second additive may be 60:40 to 50:50, while the first additive and the second additive satisfy the above- 50:50. When the above-mentioned range is satisfied, the heat resistance and the gas trail can be remarkably reduced after the stay, as the impact strength of the impact resistance is remarkably increased.

6. Organohalogen compounds

The organohalogen compound may be included to impart flame retardancy to the thermoplastic resin composition.

The organic halogen-based compound may be an organic bromine-based compound, and the organic bromine-based compound can provide excellent flame retardancy and impart excellent fluidity even when the thermoplastic resin composition is processed into a thin film.

The organohalogen compound may be at least one selected from the group consisting of tetrabromo Bisphenol A, decabromodiphenyl oxide, decabromo diphenyl ethane, 1,2-bis (2,4,6- Bis (2,4,6-tribromophenyl) ethane), octabromo-1,3,3-trimethyl-1-phenylindane -1-phenylindane, tetrabromo bisphenol A-bis (2,3-dibromopropyl ether), and 2,4,6-tris (2, (2,4,6-tribromophenoxy) -1,3,5-triazine) is selected from the group consisting of 4,6-tribromophenoxy) -1,3,5-triazine And 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine (2,4,6-tris (2,4 , 6-tribromophenoxy) -1,3,5-triazine.

The organohalogen compound may be contained in an amount of 10 to 40 parts by weight, 15 to 35 parts by weight or 8 to 22 parts by weight based on 100 parts by weight of the sum of the first to third copolymers, . When the above-mentioned range is satisfied, excellent flame retardancy and fluidity can be imparted to the thermoplastic resin composition without deteriorating other physical properties.

The thermoplastic resin composition according to an embodiment of the present invention preferably does not contain an organotin compound.

If an organotin compound is included in the thermoplastic resin composition according to an embodiment of the present invention, both the impact resistance, the impact strength and the thermal stability may be significantly lowered.

The organotin compounds include dibutyltin dilaurate, dibutyltin maleate, dibutyltin laurate-maleate, dibutyltin bis (mono-C4 to C8 alkyl maleate), dibutyltin bis Mercaptide), dibutyltin S-S '(isooctyl mercaptoacetate), and the like.

The thermoplastic resin molded article, that is, the thermoplastic resin injection molded article produced from the thermoplastic resin composition according to one embodiment of the present invention has a fall impact strength of 3,000 N or more and a discoloration degree (DELTA E) of 3.3 or less based on ASTM D3763. It is possible to provide a molded article which realizes excellent drop impact strength and thermal stability since the above-mentioned conditions are satisfied.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

≪ Production of Thermoplastic Resin Composition >

Example  1 to Example  4

(Trade name: DP270, manufactured by LG Chem) as a first copolymer, ABS graft copolymer (trade name: ER400, manufactured by LG Chemical Co., Ltd.) as a second copolymer, SAN copolymer Pentaerythritol as a first additive, zeolite (Cas No. 68989-22-0) as a second additive, 2,4,6-tris (2, (Product name: SR 245, manufacturer: Woohin copolymer), chlorinated polyethylene (trade name: CPE-135C, manufacturer: Keli chemical) as an impact modifier, The ingredients were mixed in a Henschel mixer in the amounts shown in Table 1 below. The mixture was homogeneously mixed and then charged into a twin-screw extruder set at 220 캜 to prepare a thermoplastic resin composition in the form of a pellet.

division Example 1
(Parts by weight) Example 2
(Parts by weight) Example 3
(Parts by weight) Example 4
(Parts by weight) The first copolymer 27 27 27 27 The second copolymer 5 5 5 5 The third copolymer 68 68 68 68 The first additive 0.3 0.3 0.3 0.3 Second additive 0.3 0.15 0.4 0.6 Organohalogen compounds 20 20 20 20 Impact modifier 5 5 5 5

Comparative Example  One

A thermoplastic resin composition was prepared in the same manner as in Example 1, except that the second additive was not added.

Comparative Example  2

A thermoplastic resin composition was prepared in the same manner as in Example 1, except that the first additive was not added.

Comparative Example  3

A thermoplastic resin composition was prepared in the same manner as in Example 1, except that 0.3 part by weight of dibutyl tin dimaleate was added without adding the first additive.

Comparative Example  4

Except that 30 parts by weight of the first copolymer was added and 70 parts by weight of the third copolymer was not added but the second copolymer was not added and the second additive was not added. To prepare a resin composition.

Reference example  One

A thermoplastic resin composition was prepared in the same manner as in Example 3, except that 0.15 part by weight of dibutyltin dimalate was further added.

Reference example  2

A thermoplastic resin composition was prepared in the same manner as in Example 3, except that 0.15 parts by weight of the first additive, 0.3 parts by weight of the second additive, and 0.15 parts by weight of dibutyltin dimaleate were added.

Components and contents of Comparative Examples and Reference Examples are summarized in Table 2 below.

division Comparative Example 1
(Parts by weight) Comparative Example 2
(Parts by weight) Comparative Example 3
(Parts by weight) Comparative Example 4
(Parts by weight) Reference Example 1
(Parts by weight) Reference Example 2
(Parts by weight) The first copolymer 27 27 27 30 27 27 The second copolymer 5 5 5 - 5 5 The third copolymer 68 68 68 70 68 68 The first additive 0.3 - - 0.3 0.3 0.15 Second additive - 0.3 0.3 - 0.15 0.3 Organohalogen compounds 20 20 20 20 20 20 Impact modifier 5 5 5 5 5 5 Organotin-based compound - - 0.3 - 0.15 0.15

Experimental Example

The thermoplastic resin compositions in the form of pellets of Examples, Comparative Examples and Reference Examples were injected, and the properties were evaluated by the following methods.

1) Notched Izod Impact Strength (kgf · cm / cm): Measured according to ASTM D256 using a 1/8 "specimen.

2) Impact strength of fall: It was measured according to ASTM D3763.

3) Discoloration degree (? E): The thermoplastic resin composition in the form of pellets was placed in an injection molding machine and allowed to stand for 15 minutes, and then a specimen for thermal discoloration measurement was obtained. The specimen was extruded without staying at each retention temperature, A, b, and L ', a', and b 'of the specimens before and after the retention were obtained using a Suga color computer. The degree of discoloration was calculated by the following equation (1).

&Quot; (1) "

4) Silver amount: Silver is a phenomenon that occurs during continuous injection molding, and refers to a phenomenon in which fine lines of silver are formed along the direction of flow of a raw material on the surface of a resin composition, Water vapor, volatiles in raw materials, etc.). Therefore, the more the amount of silver on the surface of the molded article injected under the same conditions, the better the appearance of the molded article.

The silver amount was evaluated by visually observing the surface of the specimen on which the degree of discoloration was measured.

○: When silver is rarely observed

X: When silver was over-exposed throughout the specimen

△: Silver appears slightly throughout the specimen

△△: Silver appears halfway across the specimen

division Impact strength The discoloration degree (? E) Silver sheep after stay Impact strength Example 1 3,340 2.78 ○ 28.5 Example 2 3,078 3.28 ○ 27.8 Example 3 3,220 2.15 ○ 28.3 Example 4 3,150 2.42 △ 26.8 Comparative Example 1 2,820 3.50 ○ 27.5 Comparative Example 2 1,950 9.94 × 26.0 Comparative Example 3 1,840 6.42 △△ 20.1 Comparative Example 4 2,450 3.67 △ 26.8 Reference Example 1 2,640 4.31 △ 24.8 Reference Example 2 2,020 4.57 △ 27.0

Referring to Table 3, it can be confirmed that Examples 1 to 4 have excellent fall strength, low discoloration degree, and low silver amount after retention, as well as excellent thermal stability in comparison with Comparative Examples and Reference Example.

Particularly, in the case of Examples 1, 3 and 4 in which the zeolite is equal to or excessively charged to the aliphatic polyol compound, the impact strength is not less than 3,150 N and the discoloration degree (d) is not more than 3.0, It was confirmed that the thermal stability was also excellent.

Comparing Example 1, Comparative Example 1, and Comparative Example 2, it was confirmed that when the zeolite was not included in Comparative Example 1, the drop impact strength and the discoloration degree were lowered. It was confirmed that when the aliphatic polyol compound was not included as in Comparative Example 2, the dropout impact strength, discoloration degree, silver amount after impact and impact strength were all lowered.

Comparing Example 2 and Reference Example 1, it was found that inclusion of an organotin compound in the same manner as in Reference Example 1 significantly lowered the drop impact strength, the degree of discoloration was high, the amount of silver after stay was large, .

In addition, it was confirmed that Reference Example 2 also significantly decreased the drop impact strength, discoloration degree, surface characteristics and impact strength as compared with the Examples.

From these results, it was confirmed that, in the case of the thermoplastic resin composition containing zeolite, the mechanical properties are deteriorated if the organotin compound is further contained.

When the aliphatic polyol compound and the zeolite are used together, it is confirmed that the synergistic action of the aliphatic polyol compound and the zeolite enables the improvement of the impact strength and discoloration of the golf ball, which were not exhibited when used.

Claims (14)

A first copolymer comprising a conjugated diene polymer having an average particle diameter of 0.1 to 0.5 탆, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer;
A second copolymer comprising a conjugated diene polymer having an average particle size of 1 to 1.5 탆, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer;
A third copolymer comprising an aromatic vinyl monomer-derived unit and a vinylcyanide monomer-derived unit;
A first additive comprising an aliphatic polyol compound; And
And a second additive comprising zeolite.
The method according to claim 1,
The zeolite
The average diameter of the inlet of the pores is 0.7 to 0.8 nm,
Wherein an average diameter of the inside of the pores is 1.0 to 1.5 nm.
The method according to claim 1,
Wherein the zeolite has a molar ratio (Si / Al) of Si to Al of 1.0 to 3.0.
The method according to claim 1,
Wherein the zeolite has an average particle diameter of 1 to 10 占 퐉.
The method according to claim 1,
Wherein the aliphatic polyol compound comprises at least one member selected from the group consisting of trimethylol propane, pentaerythritol, tripentaerythritol, xylitol, mannitol, sorbitol, glycerin and hydroxystearyl alcohol. .
The method according to claim 1,
The first copolymer
Wherein, based on the total weight of the first copolymer,
45 to 75% by weight of the conjugated diene polymer;
15 to 45% by weight of the aromatic vinyl-based monomer-derived unit; And
And 1 to 20% by weight of the vinyl-based monomer-derived unit.
The method according to claim 1,
The second copolymer
Based on the total weight of the second copolymer,
1 to 25% by weight of the conjugated diene-based polymer;
50 to 75% by weight of the aromatic vinyl-based monomer-derived unit; And
And 15 to 40% by weight of the vinyl-based monomer-derived unit.
The method according to claim 1,
Wherein the third copolymer comprises an aromatic vinyl-based monomer unit and a vinylcyanide monomer-derived unit in a weight ratio of 85:15 to 70:30.
The method according to claim 1,
Wherein the thermoplastic resin composition further comprises an organohalogen compound.
The method of claim 9,
The organohalogen compound may be selected from the group consisting of tetrabromobisphenol A, decabromodiphenyl oxide, decabromo diphenyl ethane, 1,2-bis (2,4,6- Bis (2,4,6-tribromophenyl) ethane, octabromo-1,3,3-trimethyl-1,3,5-trimethyl- -1-phenylindane, tetrabromo bisphenol A-bis (2,3-dibromopropyl ether) and 2,4,6-tris (2, (2,4,6-tribromophenoxy) -1,3,5-triazine) is selected from the group consisting of 4,6-tribromophenoxy) -1,3,5-triazine Wherein the thermoplastic resin composition is a thermoplastic resin composition.
The method according to claim 1,
Wherein the thermoplastic resin composition does not contain an organotin compound.
The method according to claim 1,
With respect to 100 parts by weight of the sum of the first to third copolymers,
0.01 to 1 part by weight of the first additive; And
0.01 to 1 part by weight of the second additive.
The method of claim 12,
Wherein the weight ratio of the first additive to the second additive is 70:30 to 50:50.
A thermoplastic resin composition which is produced from the thermoplastic resin composition according to any one of claims 1 to 13,
The impact strength according to ASTM D3763 is not less than 3,000 N,
And a discoloration degree (DELTA E) of 3.3 or less.