KR101228347B1 - Thermoplastic resin composition with high gloss and anti-scrach propertis - Google Patents

Abstract

High-gloss scratch-resistant thermoplastic resin composition having a permanent antistatic property according to the present invention is (A) polymethyl methacrylate resin (PMMA resin), (B) acrylonitrile-styrene copolymer resin (SAN resin), (C A thermoplastic resin comprising (D) carbon nanotubes (CNT) in a base resin mixed with a modified methyl methacrylate-acrylonitrile-butadiene copolymer resin (modified MABS resin). More specifically, (A) 10 to 70 parts by weight of the PMMA resin, (B) 10 to 70 parts by weight of the SAN resin, (C) 100 parts by weight of the base resin consisting of 5 to 40 parts by weight of the modified MABS resin, (D) CNT 0.1 It relates to a high gloss scratch resistant thermoplastic resin composition having a permanent antistatic property of ˜7 parts by weight.

The thermoplastic resin composition may optionally add heat stabilizers, antioxidants, light stabilizers, compatibilizers, pigments, dyes or inorganic additives to improve performance.

Description

Thermoplastic resin composition with high gloss and anti-scrach propertis

The present invention relates to a high gloss scratch resistant thermoplastic resin composition having permanent antistatic properties. More specifically, the present invention relates to a high-gloss, scratch-resistant thermoplastic resin composition having permanent antistatic properties by applying carbon nanotubes to a base resin in which PMMA resins, SAN resins, and modified MABS resins are blended in an appropriate ratio.

Recently, home appliances have been required to have various characteristics of resins according to trends of large size, high functionality, and high quality. In particular, as high-performance specifications of electric and electronic products are becoming more common, the appearance of exterior materials is becoming more important, such as high glossiness, high-quality color expression, and scratch resistance. In addition, there is also a demand for antistatic properties that can fundamentally improve problems such as dust, moisture deposition in the air due to static electricity in electrical and electronic products.

ABS / PMMA alloy resin is easy to process and has excellent appearance quality characteristics such as high gloss, high quality color texture, scratch resistance, and various mechanical properties and characteristics such as impact strength and resin flow characteristics depending on the combination of basic resin. It is easy to change, and is a resin widely used for high-end electric and electronic products, especially for exterior materials such as LCD / PDP TV, which are in the spotlight these days.

In addition, ABS / PMMA resins are produced as unpainted products because most of them do not require painting or coating, which has advantages such as reducing processing costs and secondary environmental pollution prevention, but they do not have their own antistatic properties. If you frequently stick to the surface and wipe it with a cloth, surface scratches will appear. Research has continued to impart antistatic properties to overcome these disadvantages of resins. The following methods have been used to impart antistatic properties to resins.

There is a method of imparting antistatic properties by mixing a low molecular weight antistatic agent and a surfactant type antistatic agent having good surface migration properties in the resin manufacturing process. However, in this method, the antistatic agent is present on the surface of the antistatic agent is easily removed when washed with water or cloth, the antistatic ability is lost.

In order to solve this problem, when the polymer type antistatic agent is used, the antistatic property due to washing or friction is less, and the effect can be expressed for a long time, but it is relatively expensive than the low molecular weight antistatic agent and incompatible with the resin. There are disadvantages.

And there is a method for imparting antistatic properties by coating the antistatic agent on the surface. In this method, the surface resistance value can be expressed as about 10 ⁹ 후, but it requires a post-processing, which has a disadvantage of cost increase.

In order to prevent loss due to washing or friction by using an antistatic agent, conductive carbon black may be mixed during resin production to provide antistatic properties. In this method, the conductive carbon black should be added in an amount of about 20 parts by weight to about 40 parts by weight, so that the antistatic performance can be expressed and mechanical properties are greatly reduced.

For example, in Korean Patent Laid-Open Publication No. 10-2009-0026534, in order to impart an antistatic performance to a resin, an antistatic performance is imparted by coating a multilayer film in which a thermoplastic resin composite layer in which carbon nanotubes are dispersed is laminated on a thermoplastic resin layer. There is a disadvantage in that the processing cost increases due to the need for secondary and tertiary processing after the resin production and molding.

In Korean Patent Laid-Open Publication No. 10-2004-0076576, a conductive carbon black master batch is prepared and resin is mixed to impart electrical conductivity. However, the amount of the master batch is used close to 40 parts by weight, so that mechanical properties are degraded.

In Korean Patent Registration No. 10-0804547, low molecular weight antistatic agents such as glycerin, glyceryl monostearate, and polyethylene glycol are used to impart antistatic properties to polymethylmethacrylate. The antistatic agent is lost and its function does not last long.

Accordingly, there is a continuing demand for a new product that can exhibit antistatic properties while using a small amount of carbon nanotubes, and that there is no loss of antistatic properties or deterioration of physical properties.

An object of the present invention is to provide a thermoplastic resin having antistatic properties but not deteriorating in physical properties.

Still another object of the present invention is to provide a high-gloss scratch resistant thermoplastic resin composition having permanent antistatic properties and excellent physical properties.

Still another object of the present invention is to provide a new high-gloss scratch resistant thermoplastic resin composition having excellent antistatic properties and excellent high black color.

High gloss scratch resistant thermoplastic resin composition having a permanent antistatic property according to the present invention for solving the above problems is (A) polymethyl methacrylate resin (PMMA resin), (B) acrylonitrile-styrene copolymer It consists of a thermoplastic resin containing (D) carbon nanotubes (CNT) in the base resin mixed with resin (SAN resin) and (C) modified methyl methacrylate-acrylonitrile-butadiene copolymer resin (modified MABS resin). It is possible to obtain a thermoplastic resin composition having permanent antistatic properties without deterioration in physical properties.

The permanent antistatic resin according to the present invention comprises 100 parts by weight of a polymethyl methacrylate resin, an acrylonitrile-styrene copolymer resin, and a modified methyl methacrylate-acrylonitrile-butadiene copolymer resin (modified MABS) resin. It is made by mixing 5 parts by weight to 0.1 parts by weight of carbon nanotubes to the thermoplastic resin.

The permanent antistatic resin excellent in blackness according to the present invention is a polymethyl methacrylate resin, an acrylonitrile-styrene copolymer resin, and a modified methyl methacrylate-acrylonitrile-butadiene copolymer resin (modified MABS) resin. It can be prepared by mixing 5 parts by weight of 0.5 parts by weight of carbon nanotubes to 100 parts by weight of the thermoplastic resin, and 0.01 to 6 parts by weight of pigments and dyes.

In the present invention, the antistatic thermoplastic resin composition is (A) 10 to 70 parts by weight of PMMA resin, (B) 10 to 70 parts by weight of SAN resin, (C) the base resin 100 consisting of 5 to 40 parts by weight of modified MABS resin It relates to a scratch resistant thermoplastic resin composition having a permanent antistatic property consisting of 0.5 to 5 parts by weight of (D) CNT in parts by weight.

The thermoplastic resin composition may optionally add heat stabilizers, antioxidants, light stabilizers, compatibilizers, pigments, dyes or inorganic additives to improve performance.

(A) Polymethyl methacrylate resin (PMMA resin)

In the present invention, the polymethyl methacrylate may be prepared by suspension polymerization. In the practice of the present invention, a high molecular weight polymethyl methacrylate is obtained by addition reaction of a methyl methacrylate monomer with a polymerization initiator, and product properties are classified according to molecular weight (viscosity). A flow index (230 ° C./3.8 kg) of between 1 and 25 products is possible but preferably between 8 and 18 products are suitable. More than 18 products have good flow, but impact characteristics are inadequate, and below 8, it is impossible to obtain a good product depending on the surface of molded products and the size of molded products due to the deterioration of flow (viscosity).

In the practice of the present invention, the polymethyl methacrylate resin is preferably a polymethyl methacrylate having high fluidity in consideration of moldability and impact strength, more preferably Mw is 60,000-120,000, Even more preferably Mw is on the order of 80,000 to 95,000.

In the present invention, the polymethyl methacrylate resin is more preferably used 10 to 70% by weight in the resin composition. If the content is less than 10% by weight, it is difficult to obtain desired impact strength, scratch resistance, colorability, and the like, and if the amount is more than 70% by weight, the moldability is poor, resulting in a defect.

(B) Acrylonitrile-styrene copolymer resin (SAN resin)

In the present invention, the styrenic monomer may be styrene, alpha-methylstyrene, p-methylstyrene, vinyltoluene, or a mixture of two or more thereof as the aromatic vinyl monomer, preferably styrene.

In the present invention, the vinyl cyan monomer may be acrylonitrile, methacrylonitrile, or a mixture thereof, and preferably acrylonitrile.

In the present invention, the styrene-vinyl cyan monomer copolymer is preferably a wide molecular weight distribution so as to increase the kneading with the polycarbonate, more preferably the ratio of the weight average molecular weight and the number average molecular weight is 2.5 to 5.5. When the molecular weight distribution is wide and the ratio of weight average molecular weight and number average molecular weight is 2.5 to 5.5, it is possible to manufacture a product having excellent surface gloss and scratch resistance. Although not limited in theory, if the molecular weight distribution is wide, the low molecular weight resin can be melted at a low temperature on the surface to increase the smoothness of the molded product, and the high molecular weight resin can increase the rigidity of the molded product to maintain durability required for the final product. It will be possible.

However, if the molecular weight distribution is too wide to reach 5.5 or more, macromolecules, that is, polymers having a molecular weight of 1 million or more, are formed and are not melted during extrusion, such as gel or fish-eye on the surface of the molded product. Excessive surface defects are also generated and low molecular weights are volatilized during extrusion, resulting in deterioration of surface gloss.

In the present invention, the styrene-vinyl cyan-based copolymer preferably has a weight average molecular weight of 130,000 or more, more preferably 150,000 to 500,000, so that the final product can maintain physical properties, particularly rigidity. Do.

In the present invention, it is preferable to use 10-70 parts by weight of the styrene-vinyl cyan-based copolymer, and when less than 10 parts by weight, it is difficult to obtain the appearance performance and the appearance of the resin is poor due to the compatibility decrease during extrusion. When used in excess of 70 parts by weight, mechanical properties such as impact strength are lowered, which causes defects in injection molding.

In the practice of the present invention, the styrene-vinyl cyan-based copolymer is more preferably a composition ratio of styrene-based and vinyl cyanide is 70-90 parts by weight and 10-30 parts by weight, respectively.

When the content of the vinyl cyanide is high, the thermal stability of the polymer is low, and when the content of the styrene is high, the rigidity of the polymer may be weakened.

In the present invention, the method for preparing the styrene-vinyl cyan-based copolymer is not particularly limited as long as it can satisfy the above molecular weight and molecular weight distribution, and may be prepared using conventional emulsion polymerization, block polymerization or suspension polymerization. . In the practice of the present invention, it is preferable that the acrylonitrile-styrene copolymer uses bulk polymerization.

(C) Modified methyl methacrylate-acrylonitrile-butadiene copolymer resin (modified MABS resin)

In the present invention, the methyl methacrylate-acrylonitrile-butadiene copolymer resin is methacrylic in a rubber latex mixture (R) made of a diene rubber polymer (R ₁ , R ₂ ) having different particle diameters having a high rubber content. A monomer mixture comprising an acid alkylaster, an aromatic vinyl compound and an unsaturated nitrile monomer and an emulsifier and a dispersant of an alkyl aryl sulfonate salt are added and stirred to graft polymerization. Copolymer resin prepared by the above method is 5 to 25 parts by weight of a diene rubber polymer (R ₁ ) having an average particle diameter of 700 ~ 1500A and 20 to 50 parts by weight of a diene rubber polymer (R ₂ ) having an average particle diameter of 2000 ~ 4000A. 20 to 40 parts by weight of an alkyl methacrylate compound 10 to 20 parts by weight of an unsaturated nitrile-based compound is prepared by graft copolymerization into a rubber latex mixture (R) having a high solid content.

In the present invention, the methyl methacrylate-acrylonitrile-butadiene copolymer is preferably used 5-40 parts by weight, when less than 5 parts by weight, the compatibility between the resins is lowered to cause phase separation between the resins, mechanical Deterioration in physical properties causes appearance defects. If it is used in excess of 40 parts by weight, problems with extrusion occur and appearance performance deteriorates.

(D) Carbon Nanotubes (CNT)

In the present invention, carbon nanotubes are tubular materials consisting of carbons connected in a hexagonal ring shape and have diameters of several tens of nanometers. Carbon nanotubes are not damaged or worn out even after repeated use, and they are not only chemically stable but also excellent in thermal and electrical properties. It is applied to many applications.

There are various methods of synthesizing carbon nanotubes, including electric discharge, laser deposition, chemical vapor deposition, thermal decomposition, and plasma chemical vapor deposition.

The carbon nanotubes may preferably use multi-walled carbon nanotubes (MWCNTs), and more preferably minimize the deterioration of physical properties while exhibiting antistatic properties when kneading with the thermoplastic resin. It is recommended to use carbon nanotubes with an average diameter of 5 to 20 nm and aspect ratio of 100 to 10,000.

In the present invention, carbon nanotubes are preferably used in an amount of 0.5 to 5 parts by weight, more preferably 1 to 5 parts by weight, and when less than 0.5 parts by weight, it is difficult to express antistatic performance. Falls, surface defects increase, and mechanical properties are difficult to express.

(E) Other additives

Other additives to be used in the present invention comprises 0.01 to 6.0 parts by weight of pigments and dyes, 0.01 to 5.0 parts by weight of UV absorbers, 0.3 to 5.0 parts by weight of lubricant and optionally 0.01 to 10 parts by weight of compatibilizers.

In the present invention, the ultraviolet absorber used as an additive is preferably 0.01 to 5.0 parts by weight of benzotriazole or HALS, respectively or mixed.

The lubricant used as an additive in the present invention may be ethylene bis stearamide or polyethylene wax stearic acid, PE-wax, acrylic polymer WAX, etc., and 0.1 to 5.0 parts by weight is added. Preferably it is 0.2-3.0 weight part.

In the present invention, other pigments can be colored and added according to the required color, and the pigment and dye amount are preferably 0.01 to 6.0 parts by weight.

The compatibilizer used in the present invention can usually be selectively used to increase the compatibility between the CNT and the matrix resin, preferably 0.01 to 10 parts by weight.

As described above, the present invention provides a polymethyl methacrylate resin, an acrylonitrile-styrene copolymer resin and a modified methyl methacrylate-acrylonitrile- in preparing a high-gloss scratch resistant thermoplastic resin composition having permanent antistatic properties. By using carbon nanotubes as an antistatic agent as the base resin content of butadiene copolymer resin, it was possible to prepare a high-gloss, scratch-resistant thermoplastic resin composition having a permanent antistatic property with superior high functionality.

The resin composition according to the present invention can produce a resin composition using a general mixed melt processing apparatus such as a Banbury mixer and an extruder. The resin components are prepared by uniformly dispersing each other in an extruder and pelletizing the melt by cooling in a conventional synthetic resin manufacturing method.

Hereinafter, the present invention will be described in detail with reference to the following Examples, but the present invention is not limited to the Examples.

Examples 1-3

After mixing sufficiently with a small tumbler mixer for uniform mixing at the composition ratio as shown in Table 1, the extrusion temperature in the twin screw extruder with Φ = 32mm was extruded in the range of 220 ℃ ~ 260 ℃ cooled and solidified to form a pellet. After drying for 4 hours in a circulating hot air dryer maintained at 100 ° C, change the injection temperature from 160 ton injection machine to 220-250 ° C and prepare the specimen for measuring the mechanical strength at the mold temperature of 65 ° C. Was carried out.

After 4 hours drying in a circulating hot air dryer maintained at 100 ° C, the injection temperature can be changed from 220 to 250 ° C in a 220-ton injection machine and the mold temperature can be changed to 70 ~ 150 ° C. After the specimens for quality measurement were prepared, the evaluation was carried out according to the following method.

Comparative Example 1-3

Specimens were prepared in the same manner as in the compositions and compositions described in Table 1 above.

Test Example 1

After leaving the specimens prepared according to Examples 1 to 3 and Comparative Examples 1 to 3 for 24 hours, physical properties were measured according to the following method, and pellets were shown in Table 1 by measuring fluidity after drying.

<Test method>

(1) pencil hardness

It measured at 500g load like ASTM D336, and when the value is 1H or more, it was judged that it is suitable for scratch-resistant resin.

The test was conducted in the order of a soft pencil (6B) to a hard pencil (9H).

The test is conducted five times, and the pencil is used for hardness when the coating film of the specimen is damaged.

(2) Meltflow Index (g / 10min)

ASTM D1238 was used and was 220 ° C. and 10 kg.

(3) glossiness measurement

Glossiness was measured using a Micro Haze Plus.

(4) Izod impact strength measurement

Izod impact strength was measured at 1/8 inch thickness according to the method specified in ASTM D256.

(5) Heat resistance (HDT) measurement

The HDT measurement was measured under the conditions of 18.6Kg load according to the method specified in ASTM D648.

(7) Antistatic measurement-surface electrical resistance

Surface electrical resistance measurement was performed using TRUSTAT of SIMCO JAPAN.

(8) appearance characteristics

Appearance is made in the heating mold (heating mold) that can change the mold temperature up to 70 ~ 150 ℃, and visually distinguish the abnormalities such as Weld-line dichroic, Sink, Flow Mark, Surface Pinhole or Fish-eye Nothing was judged good.

[Table 1]

Item Example Comparative Example One 2 3 One 2 3 Furtherance
(A + B + C
= 100% by weight)
A 50 50 10 50 50 50 B 30 30 60 30 30 30 C 20 20 30 20 20 20 D One 2 2 0 0.5 15 E 0.3 0.3 0.3 0.3 0.3 0.3 F 0.5 0.5 0.5 0.5 0.5 0.5 Properties Pencil hardness 1H 1H F 1H 1H 1H liquidity 11 8 25 15 12 5 Glossiness 93 93 100 93 93 63 Impact strength 9 8 12 11 10 3 Heat resistance degree (HDT) (℃) 86 88 89 86 86 86 Surface electrical resistance
(Ω) 10 ⁹ 10 ⁵ 10 ^5.5 10 ¹⁵ 10 ¹³ 10 ⁴ Heating mold temperature (℃) 100 100 100 100 100 100 Appearance Characteristics Good Good Good Good Good Bad

(week)

A) Polymethylmethacrylate Resin (Akema V-150)

B) Acrylonitrile-Styrene Copolymer

(Kumho Petrochemical SAN 326 weight average molecular weight 120,000, AN 26%)

C) Modified methyl methacrylate-acrylonitrile-butadiene copolymer resin (Kumho Petrochemical M560)

D) Carbon Nanotubes (Kumho Petrochemical)

E) Antioxidant (CIBA B-900)

F) PE-wax (Lion Chemical LC-104N)

In Examples 1 to 3, the pencil hardness, fluidity, gloss, impact strength, heat resistance, surface electrical resistance, and appearance characteristics of the Examples 1 to 3 were generally better than those of the comparative examples. Properties and mechanical properties indicate that they have suitable properties for high-gloss, scratch-resistant resin with permanent antistatic properties.

In order to improve the impact strength and fluidity, increasing the content of the modified methyl methacrylate-acrylonitrile-butadiene copolymer resin together with the loss of the PMMA resin as shown in Example 3 can easily improve the impact strength and fluidity.

Referring to Comparative Example 1 in the table, when the content of carbon nanotubes is lowered to 0, it is difficult to express surface electrical resistance and thus may not have antistatic performance. In Comparative Example 2, when the content of the carbon nanotubes is lowered to 0.5 level, the surface electrical resistance appears but is not suitable for the antistatic resin. In order to show the performance of the antistatic resin, the surface electrical resistance should have a value of 10 ¹⁰ Ω or less. In Comparative Example 3, when carbon nanotubes are used in excess of 10, problems of mechanical properties such as difficulty in expressing fluidity and impact strength occur, and appearance quality is also deteriorated.

Although the present invention has been described in detail with reference to the described embodiments, various modifications and variations within the technical scope of the present invention can be readily used by those skilled in the art, and all such modifications and modifications are described in the present invention. It can be seen to be included in the area of.

Claims (9)

10 to 70 parts by weight of polymethyl methacrylate resin; 10 to 70 parts by weight of acrylonitrile-styrene copolymer resin; Methyl methacrylate-acrylonitrile-butadiene copolymer resin containing 0.5 to 5 parts by weight of carbon nanotubes in 100 parts by weight consisting of 5 to 40 parts by weight, and a high-gloss scratch-resistant thermoplastic resin characterized by exhibiting permanent antistatic properties Composition. delete The high gloss scratch resistant thermoplastic resin composition of claim 1, wherein the polymethyl methacrylate resin has a permanent antistatic property having a weight average molecular weight of 60,000 to 120,000. According to claim 1, wherein the acrylonitrile-styrene copolymer resin has a weight average molecular weight and a number average molecular weight of 2.5 to 5.5, a weight average molecular weight of 130,000 to 500,000, acrylonitrile of 10 to 30% by weight, styrene A high gloss scratch resistant thermoplastic resin composition having a permanent antistatic property of 70 to 90% by weight. According to claim 1, wherein the methyl methacrylate-acrylonitrile-butadiene copolymer resin is 5 to 25 parts by weight of butadiene rubber having an average particle diameter of 700 ~ 1500 kPa; 20-50 parts by weight of butadiene rubber having an average particle diameter of 2000 to 4000 mm 3; 20-40 parts by weight of methyl methacrylate; 10 to 20 parts by weight of styrene; High-gloss scratch-resistant thermoplastic resin composition having a permanent antistatic property consisting of 1 to 10 parts by weight of acrylonitrile. According to claim 1, 0.01 to 6 parts by weight of pigment and dye, 0.01 to 5.0 parts by weight of antioxidant, 0.01 to 5.0 parts by weight of UV absorber, 0.1 to 5.0 parts by weight of lubricant, 0-10 parts by weight of compatibilizer High-gloss scratch-resistant thermoplastic resin composition having a permanent antistatic property further comprising a part. The method of claim 6, wherein the carbon nanotubes are carbon nanotubes produced by one or more of the electrical discharge method, laser deposition method, chemical vapor deposition method, thermal decomposition method, plasma chemical vapor deposition method, high-precision scratch-resistant thermoplastic having a permanent antistatic properties Resin composition. According to claim 7, The carbon nanotubes are high-strength scratch-resistant thermoplastic resin having a permanent antistatic properties, characterized in that the multi-walled carbon nanotubes having an average diameter of 5 ~ 20 nm and an aspect ratio of 100 ~ 10,000 Composition. A pellet obtained by extruding the high-gloss scratch-resistant thermoplastic resin composition having permanent antistatic properties according to claim 1.