KR20190083537A - A thermoplastic resin composition having improved self-lubricative property and surface appearance - Google Patents

Abstract

The present invention is to provide a thermoplastic resin composition comprising: a graft copolymer resin in which a monomer mixture including an aromatic vinyl monomer and an unsaturated nitrile monomer are grafted and polymerized to diene rubber; a first copolymer consisting of an aromatic vinyl monomer and an unsaturated nitrile monomer; a second copolymer consisting of one or more monomers of an N-substituted maleimide monomer and a thermal resistant aromatic vinyl monomer, an aromatic vinyl monomer and an unsaturated nitrile monomer; silicon oil having the kinematic viscosity of 50-500,000 cst at 25°C; and a fluorine processing aid.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a thermoplastic resin composition having excellent self-

The present invention relates to a thermoplastic resin composition excellent in self-lubricating property and appearance.

Generally, ABS resin obtained by graft copolymerizing styrene and acrylonitrile monomer to a butadiene rubber-like polymer has excellent impact resistance and processability, excellent mechanical strength and heat distortion temperature, and excellent coloring property, Devices and the like.

In addition, the ABS resin has excellent mechanical properties such as impact resistance and is excellent in processing characteristics such as injection molding and painting, and is widely used as an automobile interior and exterior material. ABS (acrylonitrile-butadiene-styrene), which is used as an interior material, is widely used in automobile door trims and center fascia.

However, ABS resin is amorphous resin and has a higher coefficient of friction than crystalline resin. If it is used just in case of using in switches and so on, it will cause a creaking noise due to friction and stick slip phenomenon during use or running.

In order to solve this problem, when the ABS resin is used as a door trim and a switch in a center fascia, a lubricant such as grease is applied on the part to prevent the noise caused by the stick slip phenomenon.

However, when a lubricant such as a grease is used for the interior of automobiles, there may be a problem of odor and VOCs due to grease, and cracks due to a difference in chemical resistance between some grease and ABS may occur.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide a thermoplastic resin composition having excellent self-lubricating properties and surface appearance while maintaining excellent mechanical properties and heat resistance.

One aspect of the present invention relates to a graft copolymer resin formed by graft-polymerizing a monomer mixture comprising an aromatic vinyl monomer and an unsaturated nitrile monomer in a diene rubber; A first copolymer comprising an aromatic vinyl monomer and an unsaturated nitrile monomer; A second copolymer comprising at least one of an N-substituted maleimide monomer and a heat-resistant aromatic vinyl monomer, an aromatic vinyl monomer, and an unsaturated nitrile monomer; A silicone-based oil having a kinematic viscosity of 50 to 500,000 cst at 25 占 폚; And a fluorine-based processing aid.

In one embodiment, the diene rubber is a butadiene-aromatic vinyl compound copolymer such as polybutadiene, butadiene-styrene copolymer, butadiene-vinyl toluene copolymer; Butadiene-acrylonitrile copolymer, butadiene-acrylonitrile copolymer, and butadiene-methacrylonitrile copolymer; Or polyisoprene, and may be a mixture of two or more of them.

In one embodiment, the average particle size of the diene rubber may range from 2,000 to 5,000 ANGSTROM.

In one embodiment, the first copolymer may comprise from 60 to 85 parts by weight of an aromatic vinyl monomer and from 15 to 40 parts by weight of an unsaturated nitrile monomer.

In one embodiment, the second copolymer comprises 15 to 25 parts by weight of an N-substituted maleimide monomer, 35 to 45 parts by weight of a heat resistant aromatic vinyl monomer, 10 to 15 parts by weight of an aromatic vinyl monomer, and 15 to 25 parts by weight of an unsaturated nitrile monomer Parts by weight.

In one embodiment, the aromatic vinyl monomer is selected from the group consisting of styrene,? -Methylstyrene vinyltoluene, t-butylstyrene, halogen substituted styrene, 1,3-dimethylstyrene, 2,4-dimethylstyrene, And combinations thereof.

In one embodiment, the unsaturated nitrile monomer is selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, and combinations of two or more thereof. .

In one embodiment, the N-substituted maleimide monomer is selected from the group consisting of N-phenylmaleimide, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N- Butyl maleimide, N-isobutyl maleimide, N-cyclohexyl maleimide, N-chlorophenyl maleimide, N-methylphenyl maleimide, N- N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-benzylmaleimide, and at least two of them And combinations thereof.

In one embodiment, the heat-resistant aromatic vinyl monomer may be selected from the group consisting of? -Methylstyrene,? -Ethylstyrene, methyl? -Methylstyrene, and a combination of two or more thereof.

In one embodiment, the content of the silicone oil may be 0.1 to 7% by weight based on the total weight of the thermoplastic resin composition.

In one embodiment, the content of the fluorine-based processing aid may be 0.1 to 5% by weight based on the total weight of the thermoplastic resin composition.

According to one aspect of the present invention, excellent self-lubricating properties and surface appearance can be effectively realized while maintaining excellent mechanical properties and heat resistance including a silicone oil.

It should be understood that the effects of the present invention are not limited to the effects described above, but include all effects that can be deduced from the description of the invention or the composition of the invention set forth in the claims.

Hereinafter, the present invention will be described in detail. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Throughout the specification, when a part is referred to as being "connected" to another part, it includes not only "directly connected" but also "indirectly connected" . Also, when an element is referred to as "comprising ", it means that it can include other elements, not excluding other elements unless specifically stated otherwise

One aspect of the present invention relates to a graft copolymer resin formed by graft-polymerizing a monomer mixture comprising an aromatic vinyl monomer and an unsaturated nitrile monomer in a diene rubber; A first copolymer comprising an aromatic vinyl monomer and an unsaturated nitrile monomer; A second copolymer comprising at least one of an N-substituted maleimide monomer and a heat-resistant aromatic vinyl monomer, an aromatic vinyl monomer, and an unsaturated nitrile monomer; A silicone-based oil having a kinematic viscosity of 50 to 500,000 cst at 25 占 폚; And a fluorine-based processing aid.

In the graft polymerization, the monomer mixture may be collectively administered to the diene rubber together with known emulsifiers, polymerization initiators, catalysts and the like, and may be continuously administered for a predetermined period of time, if necessary.

The graft copolymer resin originally obtained by the graft polymerization may be in the form of a latex, which may be obtained by treating with an acid or a salt, followed by coagulation and drying to give a powdery solid.

The graft copolymer resin may be obtained by polymerizing 55 to 65 parts by weight of a diene rubber and 35 to 45 parts by weight of a monomer mixture comprising the aromatic vinyl monomer and the unsaturated nitrile monomer.

If the amount of the diene rubber is less than 55 parts by weight, mechanical properties such as impact resistance of the final molded plastic molded article may deteriorate. If the amount exceeds 65 parts by weight, aggregation of particles in the thermoplastic resin composition may occur excessively, Plating adhesion and the like may be lowered.

Butadiene-aromatic vinyl compound copolymer such as polybutadiene, butadiene-styrene copolymer, and butadiene-vinyl toluene copolymer; Butadiene-acrylonitrile copolymer, butadiene-acrylonitrile copolymer, and butadiene-methacrylonitrile copolymer; Or polyisoprene, and may be a mixture of two or more of them, preferably styrene, but is not limited thereto.

The diene rubber may be one prepared by an emulsion polymerization method in which the diameter of particles is easily controlled, but is not limited thereto.

The average particle size of the diene rubber may be from 2,000 to 5,000 Å, preferably from 3,500 to 4,000 Å. If the average particle size of the diene rubber is less than 2,000 angstroms, the impact resistance may be lowered. If the average particle size is more than 5,000 angstroms, the glossiness may be lowered.

The graft copolymer resin may have a graft rate of 30 to 40%. The graft rate can be calculated from the following equation (1).

<Formula 1>

In the formula (1), G is the graft rate (%), Mg is the weight (g) of the graft-polymerized monomer to the rubbery polymer, and Wc is the weight (g) of the rubbery polymer.

If the graft ratio of the graft copolymer resin is less than 30% or exceeds 40%, the degree of dispersion of the thermoplastic resin composition may be lowered and the moldability, plating adhesion, etc. may be deteriorated.

The first copolymer may be composed of 60 to 85 parts by weight of an aromatic vinyl monomer and 15 to 40 parts by weight of an unsaturated nitrile monomer.

The first copolymer may be 10 to 60 parts by weight, preferably 20 to 40 parts by weight. If the first copolymer is less than 10 parts by weight, impact resistance and moldability may be deteriorated. If 60 parts by weight The heat resistance may be lowered.

The method of producing the first copolymer is not particularly limited as long as it can satisfy the molecular weight and the molecular weight distribution, and one or more of ordinary emulsion polymerization, bulk polymerization and suspension polymerization can be selected, But are not limited thereto.

The second copolymer may be a ternary copolymer or a quaternary copolymer comprising at least one of an N-substituted maleimide monomer and a heat-resistant aromatic vinyl monomer, an aromatic vinyl monomer, and an unsaturated nitrile monomer .

For example, the second copolymer may contain 15 to 25 parts by weight of an N-substituted maleimide monomer, 35 to 45 parts by weight of a heat resistant aromatic vinyl monomer, 10 to 15 parts by weight of an aromatic vinyl monomer, and 15 to 25 parts by weight of an unsaturated nitrile monomer Lt; / RTI &gt; The weight average molecular weight (Mw) of the second copolymer may be 80,000 to 120,000 g / mol.

Substituted maleimide monomer which is excellent in heat resistance and thermal stability but raises the viscosity of the resin, and a heat-resistant aromatic resin having a relatively low heat resistance and thermal stability as compared with the N-substituted maleimide monomer, The use of less expensive N-substituted maleimide monomers, including all of the vinyl monomers, can lower the melt viscosity and reduce the manufacturing cost.

Further, the problem of lowering the heat resistance due to the weight loss of the N-substituted maleimide monomer is supplemented by an appropriate amount of the heat resistant aromatic vinyl monomer, and the unsaturated nitrile monomer is used as a solvent for the N-substituted maleimide monomer which is solid, And can be applied to bulk polymerization. By applying an aromatic vinyl monomer having excellent processability and coloring property, it is possible to lower the melt viscosity of the copolymer and improve the compatibility with other resins or other monomers and the kneadability.

The second copolymer may be prepared by bulk polymerization. This is because physical properties at least satisfying the content of the additive in bulk polymerization can be obtained and gel generation is also small. When the amount of the additive added in the polymerization of the second copolymer is large, defects such as bubbles appear in the molded product during injection molding. When the second copolymer contains gel, the surface of the molded article protrudes, .

Wherein the aromatic vinyl monomer is selected from the group consisting of styrene,? -Methylstyrene vinyltoluene, t-butylstyrene, halogen substituted styrene, 1,3-dimethylstyrene, 2,4-dimethylstyrene and ethylstyrene, And may be selected. Preferably, it may be styrene, but is not limited thereto.

The unsaturated nitrile monomer may be selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, and combinations of two or more thereof, , Acrylonitrile, but is not limited thereto.

Wherein the N-substituted maleimide monomer is at least one selected from the group consisting of N-phenylmaleimide, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N- But are not limited to, isobutyl maleimide, Nt-butyl maleimide, N-cyclohexyl maleimide, N-chlorophenyl maleimide, N-methylphenyl maleimide, N-bromophenyl maleimide, Maleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-benzylmaleimide, and combinations of two or more thereof , And preferably N-phenylmaleimide, but is not limited thereto.

The heat-resistant aromatic vinyl monomer may be selected from the group consisting of? -Methylstyrene,? -Ethylstyrene, methyl? -Methylstyrene, and a combination of two or more thereof.

The kinematic viscosity of the silicone oil may be 50 to 500,000 cst, preferably 500 to 350,000 cst, more preferably 1,000 to 100,000 at 25 ° C. When the viscosity of the silicone oil is less than 50 cst, the viscosity of the oil may be drastically lowered due to the extrusion of the oil having a low viscosity. If the viscosity of the silicone oil is more than 500,000 cst, mechanical properties, particularly impact strength and tensile strength, Can be degraded.

The silicone-based oil may be any of those having a polyorganosiloxane structure. Specific examples thereof include unmodified silicone oils such as dimethylsilicone oil, methylphenylsilicone oil and methylhydrogen silicone oil, and polyorganosiloxane structures such as polyorganosiloxane structure Modified silicone oil, and partially denatured modified silicone oil. However, the present invention is not limited thereto.

The content of the silicone oil may be 0.1 to 7% by weight, preferably 0.5 to 5% by weight, more preferably 1.5 to 3% by weight based on the total weight of the thermoplastic resin composition. When the content of the silicone oil is less than 0.1% by weight, the resin can not impart a self-lubricating property. If the content of the silicone oil is more than 7% by weight, the mechanical properties, particularly, the tensile strength may be lowered. Can be degraded.

The fluorine processing aid may be at least one selected from the group consisting of hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), tetrafluoroethylene (TFE), trifluoroethylene, hexafluoroisobutylene, (PPVE), perfluoroethyl vinyl ether (PEVE), perfluoromethyl vinyl ether (PMVE), perfluoro-2,2-dimethyl-1,3-dioxole (PDD), purple Methylene-4-methyl-1,3-dioxolane (PMD), and combinations of two or more of them. However, the present invention is not limited thereto.

The content of the fluorine-based processing aid may be 0.1 to 5 wt%, preferably 0.3 to 2 wt%, based on the total weight of the thermoplastic resin composition. When the content of the fluorine-containing processing aid is less than 0.1% by weight, the resin can not impart a self-lubricating property. If it exceeds 5% by weight, the compatibility with the thermoplastic resin is deteriorated and the mechanical properties, particularly, the tensile strength and the impact strength, .

Hereinafter, embodiments of the present invention will be described in detail.

Examples and Comparative Examples

A thermoplastic resin composition comprising a graft copolymer resin, a first copolymer, a second copolymer, a silicone oil (high viscosity, low viscosity), a processing aid, a lubricant and an antioxidant in the contents as shown in Table 1 was kneaded in a twin- .

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Graft copolymer resin 28.0 28.0 28.0 28.0 28.0 28.0 28.0 28.0 The first copolymer 30.7 29.2 28.2 51.2 33.2 28.2 30.2 32.2 The second copolymer 38.0 38.0 38.0 15.0 38.0 38.0 38.0 38.0 High viscosity silicone oil 1.5 3.0 3.0 3.0 0 0 3 0 Low viscosity silicone oil 0 0 0 0 0 3.0 0 0 Processing aid 1.0 1.0 2.0 2.0 0 2.0 0 1.0 Lubricant 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Antioxidant 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

(Unit: wt%)

The product names or specifications of the graft copolymer resin, the first copolymer, the second copolymer, the silicone oil (high viscosity, low viscosity), the processing aid, the lubricant and the antioxidant are as follows.

-Grafted copolymer resin: an ABS resin having an average particle diameter of 3,500 to 4,000 Å, a rubbery content of 59% by weight and a graft rate of 35%

First copolymer: styrene and acrylonitrile were contained in a weight ratio of 72:28, respectively, and a SAN resin having a number average molecular weight of 180,000

- Second copolymer: a quaternary copolymer of alpha methyl styrene, phenyl maleimide, styrene and acrylonitrile copolymerized in a weight ratio of 40:20:15:25, respectively, and having a number average molecular weight of 100,000

- High viscosity silicone oil: viscosity 10,000 cst, Shin-Etsu KF-96H-10,000CS

- Low viscosity silicone oil: Viscosity 30 cst, Shin-Etsu KF-96-30CS

- Processing aid: 3M FX 5911

- Lubricant: ethylene bis-stearamide

- Antioxidant: Adeka A-541

Experimental Example

Impact strength, tensile strength, heat resistance (HDT) and self-lubricating activity of the thermoplastic resin compositions prepared in Examples and Comparative Examples were measured and evaluated by the following methods, and the results are shown in Table 2 below.

Impact strength (kgf · cm / cm): Measured according to ASTM D256.

Tensile strength (kgf / cm ² ): Measured according to ASTM D638.

Heat resistance (HDT, 1.8 MPa, 占 폚): Measured according to ASTM D648.

- Self-lubrication: The specimens were extruded at an injection temperature of 240 캜 and a mold temperature of 50 캜 in a mirror-finished mold of L 90 mm, w 55 mm and T 3 mm. The two specimens were rolled up and hand- And judged that there was lubricity. (X: not at all,?: About 1/3 of the length of the test piece,?: More than half of the test piece?: Over 2/3 of the test piece length).

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Impact strength 14 16 16 18 14 8 16 16 The tensile strength 430 410 410 420 460 380 420 430 HDT 102 101 101 94 104 101 101 104 Self-lubricating ○ ○ ◎ ◎ X ◎ △ X

Referring to Table 2, when the graft copolymer resin, the first copolymer, the second copolymer, and the high viscosity silicone oil fluorine processing aid were simultaneously used (Examples 1 to 4), the impact strength, tensile strength, And excellent lubricity was obtained in evaluation of the lubricity, and in particular, the self-lubricating properties were superior to those in the case where the content of the high viscosity silicone oil and the fluorine processing aid was limited (Examples 3 and 4).

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

Claims (11)

A graft copolymer resin formed by graft polymerizing a monomer mixture comprising an aromatic vinyl monomer and an unsaturated nitrile monomer in a diene rubber;
A first copolymer comprising an aromatic vinyl monomer and an unsaturated nitrile monomer;
A second copolymer comprising at least one of an N-substituted maleimide monomer and a heat-resistant aromatic vinyl monomer, an aromatic vinyl monomer, and an unsaturated nitrile monomer;
A silicone-based oil having a kinematic viscosity of 50 to 500,000 cst at 25 占 폚; And
Wherein the thermoplastic resin composition comprises a fluorine-based processing aid. The method according to claim 1,
Butadiene-aromatic vinyl compound copolymer such as polybutadiene, butadiene-styrene copolymer, and butadiene-vinyl toluene copolymer; Butadiene-acrylonitrile copolymer, butadiene-acrylonitrile copolymer, and butadiene-methacrylonitrile copolymer; Or polyisoprene, and two or more of them are mixed. The method according to claim 1,
Wherein the diene rubber has an average particle size of from 2,000 to 5,000 ANGSTROM. The method according to claim 1,
Wherein the first copolymer comprises 60 to 85 parts by weight of an aromatic vinyl monomer and 15 to 40 parts by weight of an unsaturated nitrile monomer. The method according to claim 1,
Wherein the second copolymer comprises 15 to 25 parts by weight of an N-substituted maleimide monomer, 35 to 45 parts by weight of a heat resistant aromatic vinyl monomer, 10 to 15 parts by weight of an aromatic vinyl monomer, and 15 to 25 parts by weight of an unsaturated nitrile monomer. Composition. The method according to claim 1,
Wherein the aromatic vinyl monomer is selected from the group consisting of styrene,? -Methylstyrene vinyltoluene, t-butylstyrene, halogen substituted styrene, 1,3-dimethylstyrene, 2,4-dimethylstyrene and ethylstyrene, Selected from the thermoplastic resin composition. The method according to claim 1,
Wherein the unsaturated nitrile monomer is one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, and a combination of two or more thereof. 6. The method of claim 5,
Wherein the N-substituted maleimide monomer is at least one selected from the group consisting of N-phenylmaleimide, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N- But are not limited to, isobutyl maleimide, Nt-butyl maleimide, N-cyclohexyl maleimide, N-chlorophenyl maleimide, N-methylphenyl maleimide, N-bromophenyl maleimide, Maleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-benzylmaleimide, and combinations of two or more thereof Wherein the thermoplastic resin composition is a thermoplastic resin composition. 6. The method of claim 5,
Wherein the heat resistant aromatic vinyl monomer is one selected from the group consisting of? -Methylstyrene,? -Ethylstyrene, methyl? -Methylstyrene, and a combination of two or more thereof. The method according to claim 1,
Wherein the content of the silicone oil is 0.1 to 7% by weight based on the total weight of the thermoplastic resin composition. The method according to claim 1,
Wherein the content of the fluorine-based processing aid is 0.1 to 5% by weight based on the total weight of the thermoplastic resin composition.