KR20090095764A - Termoplastic Resin Composition Having A Good Weather Resistance And Low Gloss - Google Patents

Abstract

A thermoplastic resin composition, and an automobile interior material using the composition are provided to improve weather resistance, heat resistance and anti-glare property. A thermoplastic resin composition comprises 10-40 parts by weight of an ABS graft copolymer prepared by bulk polymerization; 10-40 parts by weight of an ASA copolymer; 20-50 parts by weight of a heat-resistant copolymer manufactured from N-phenylmaleimide, acrylonitrile and styrene; and 0.5-5 parts by weight of a matting agent comprising at least one selected from a syndiotactic polystyrene and its derivatives, to 100 parts by weight of a base resin. The base resin comprises the ABS, ASA and heat-resistant copolymers.

Description

Thermoplastic Resin Composition Having A Good Weather Resistance And Low Gloss}

The present invention relates to a thermoplastic resin composition having excellent light and matte properties. More particularly, the present invention relates to an ABS polymer manufactured by bulk polymerization, an ASA polymer having excellent weather resistance, and a certain amount of syndiotactic polystyrene as a matting agent. The present invention relates to a thermoplastic resin having excellent heat resistance and matte properties and suitable for automobile interior materials.

Acrylonitrile-butadiene-styrene (hereinafter referred to as 'ABS') thermoplastic resin has excellent physical properties such as impact resistance, chemical resistance, molding processability, etc. and is widely used in various office equipment, electrical / electronic parts, automobile interior and exterior materials, etc. to be. Recently, as the design of a product becomes an important criterion for product selection, development of not only a high gloss resin but also a low gloss resin is required to satisfy various needs of consumers.

Particularly, in the case of automotive interior materials, the light resistance and matte properties are further required. In order to realize the matte properties of the resin used as the material thereof, a conventional method such as matte coating has been used.

However, due to the recent environmental pollution, safety in the workplace, new car syndrome, etc., instead of eliminating the matte coating process, the resin itself has light and matte properties, thereby reducing workers' damage due to environmental damage, solvent toxicity and scattering. As a result, research is being actively conducted to meet the needs of consumers.

Korean Patent No. 0422123 discloses a method for manufacturing a thermoplastic resin composition having excellent light resistance based on an acrylate-styrene-acrylonitrile (ASA) resin as a patent related to light resistance, and US Pat. No. 5,965,655 as a patent related to matt properties. Korean Patent No. 0459323 discloses a thermoplastic resin composition containing a crosslinking type organic microparticle.

However, the patents have a problem in that the matting property is poor if the light resistance (weather resistance) is good, and the light resistance (weather resistance) is poor if the matting property is excellent.

In order to solve the problems of the prior art as described above, the present invention includes a ABS graft copolymer prepared by bulk polymerization, an ASA graft copolymer having excellent weather resistance and syndiotactic polystyrene, which is a matte, It is an object of the present invention to provide a thermoplastic resin excellent in heat resistance and matte properties and suitable for automobile interior materials.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention is a) based on a total of 100 parts by weight of the base resin consisting of ABS, ASA and heat-resistant copolymer a) 10 to 40 parts by weight of ABS graft copolymer prepared by bulk polymerization; b) 10 to 40 parts by weight of the ASA graft copolymer; c) 20 to 50 parts by weight of a heat resistant copolymer prepared from N-phenylmaleimide, acrylonitrile and styrene; And d) 0.5 to 5 parts by weight of a matte agent selected from the group consisting of syndiotactic polystyrene and derivatives thereof; and excellent light resistance and matt properties. To provide.

As described above, according to the present invention, the present invention includes ABS graft copolymer prepared by bulk polymerization, ASA graft copolymer having excellent weather resistance, and syndiotactic polystyrene which is a matte agent. It is excellent in matt characteristics and has an effect of providing a thermoplastic resin suitable for automobile interior materials and the like.

The thermoplastic resin composition having excellent light and matte properties of the present invention is based on a total of 100 parts by weight of a base resin composed of ABS, ASA, and a heat resistant copolymer.

a) 10 to 40 parts by weight of the ABS graft copolymer prepared by bulk polymerization;

b) 10 to 40 parts by weight of the ASA graft copolymer;

c) 20 to 50 parts by weight of a heat resistant copolymer prepared from N-phenylmaleimide, acrylonitrile and styrene; And

d) 0.5 to 5 parts by weight of a matte agent selected from the group consisting of syndiotactic polystyrene and derivatives thereof; and characterized in that it comprises a.

The base resin may further include 20 to 50 parts by weight of the SAN copolymer.

The thermoplastic resin composition may further include a lubricant, an antioxidant, a light stabilizer, or a mixture thereof.

Hereinafter, the present invention will be described in detail by dividing the a) to d), the SAN resin (e), the lubricant (f), and the like sequentially.

a) By block polymerization  Manufactured ABS Graft  Copolymer

The ABS graft copolymer may be an ABS graft copolymer prepared by bulk polymerization, but preferably 10 to 45 parts by weight of reaction medium, 40 to 60 parts by weight of styrene monomer, and 10 to 25 acrylonitrile monomer. It is an ABS graft copolymer prepared by bulk polymerization of 5 to 12 parts by weight, butadiene or styrene-butadiene rubber, 0.01 to 15 parts by weight of polybutene, 0.01 to 1 part by weight of initiator, and 0.01 to 1 part by weight of molecular weight modifier.

The reaction medium is generally not particularly limited in the case of the reaction medium that can be used in the production of the ABS copolymer by bulk polymerization, but is preferably ethylbenzene, toluene or the like.

The ABS graft copolymer is preferably 10 to 40 parts by weight based on a total of 100 parts by weight of a base resin (hereinafter, referred to as a 'base resin') consisting of ABS, ASA, and a heat resistant copolymer. There exists a problem that the flowability and workability of a thermoplastic resin composition fall, and when it is less than 10 weight part, there exists a problem that a matte characteristic falls.

The ABS graft copolymer prepared by the bulk polymerization has a larger particle diameter than the ABS graft copolymer prepared by emulsion polymerization, and less residues resulting in a decrease in physical properties by not using an emulsifier or a flocculant. And it does not need to go through the dehydration drying process has the advantage of being economic.

b) ASA Graft  Copolymer

The ASA graft copolymer may be prepared by emulsion polymerization of a reaction mixture including an acrylate rubber polymer, a styrene monomer, an acrylonitrile monomer, an emulsifier, a polymerization initiator, and a molecular weight regulator.

The acrylate-based rubbery polymer is a large diameter acrylate-based rubbery polymer having an average particle diameter of 2,500 to 5,000 mm 3 and preferably of 3,000 to 4,500 mm 3 or a small-diameter acrylate rubbery having an average particle diameter of 500 to 2,000 mm 3 and preferably 700 to 1,500 mm 3 Polymer.

The large-diameter and small-diameter acrylate-based rubbery polymers include contents related to the large-diameter and small-diameter acrylate-based rubbery polymers disclosed in Korean Patent Application No. 0694456 (published on April 26, 2006).

The acrylate-based rubbery polymer is preferably included in 10 to 60% by weight based on the total content of the ASA graft copolymer. When the content is less than 10% by weight, the thermoplastic resin composition to be produced has an impact strength lowered, and when the content exceeds 60% by weight, the graft ratio is lowered, leading to a decrease in hardness and scratch resistance.

The styrene-based monomer and acrylonitrile-based monomer are preferably 10 to 50% by weight and 5 to 20% by weight based on the total content of the ASA graft copolymer.

The method for preparing the ASA graft copolymer is not particularly limited in the case of the emulsion polymerization method generally used in the ASA graft copolymer, but is preferably Korean Patent No. 0694456 filed by the present applicant (2006.04.26) Emulsion polymerization method used in the preparation of the ASA graft copolymer disclosed in).

After the emulsion polymerization is terminated, the polymerization solution is preferably pH 8 to 11, more preferably pH 9 to 10.5.

The ASA graft copolymer may be an ASA graft copolymer including a large diameter acrylate rubbery polymer, an ASA graft copolymer including a small diameter acrylate rubbery polymer, or a mixture thereof.

The mixture is improved in flowability and processability when the content of the small diameter acrylate rubbery polymer is high, but the glossiness of the base resin is increased, and the gloss is decreased when the content of the large diameter acrylate rubbery polymer is high, but impact strength and processability are increased. This feature is deteriorated.

The ASA graft copolymer may be 10 to 40 parts by weight, preferably 15 to 37 parts by weight, based on 100 parts by weight of the total base resin.

c) heat resistant copolymer

The heat resistant copolymer is prepared from 30 to 50 parts by weight of N-phenylmaleimide monomer, 0 to 20 parts by weight of acrylonitrile monomer and 20 to 50 parts by weight of styrene monomer, and the production apparatus is inputted into a raw material. It consists of a pump, a continuous stirring bath, a preheating bath, a volatilization tank, a polymer transfer pump, and an extrusion process, and the manufacturing process is a continuous process.

The heat-resistant copolymer is 20 to 40 parts by weight, preferably 25 to 35 parts by weight based on 100 parts by weight of the total base resin, the effect of excellent heat resistance and impact strength of the thermoplastic resin composition prepared within this range have.

d) Matte

The matting agent may be at least one selected from the group consisting of syndiotactic polystyrene (hereinafter referred to as sPS) and derivatives thereof as a crystalline polymer.

The syndiotactic polystyrene is a phenyl group or a substituted phenyl group which is a side chain with respect to the main chain formed of a carbon-carbon bond and is located in opposite directions, and has a crystalline structure unlike the conventional amorphous general purpose atactic polystyrene. Tacticity can be measured quantitatively based on ¹³ C-NMR.

The stereoregularity diagram of the sPS is 85% or more in the case of the diad fraction (the ratio of isotactic chains to the diad unit in the molecular chain), and the pentad (racemicpentad) fraction (pentad in the molecular chain). Ratio of isotactic chain in units) is preferably at least 35%.

The matting agent has a melting temperature of 260 to 280 ° C., and is superior in heat resistance and mechanical properties to the atactic polystyrene-based polymer.

The matting agent is preferably 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total base resin, and the impact strength and matte properties of the thermoplastic resin composition prepared within the above range Is improved.

e) SAN  Copolymer

The SAN copolymer is composed of 20 to 40% by weight of acrylonitrile and 60 to 80% by weight of styrene monomer, and the production apparatus is a raw material input pump, continuous stirring tank, preheating tank, volatilization tank, polymer transfer pump and extrusion processing machine The manufacturing process is a continuous process.

The SAN copolymer is 0 to 50 parts by weight, preferably 5 to 30 parts by weight based on 100 parts by weight of the total base resin, and the impact strength and heat resistance of the thermoplastic resin composition prepared when the content exceeds 50 parts by weight. If the degree is lowered, and less than 20 parts by weight, the fluidity is lowered.

f) Lubricant , Antioxidants, light stabilizers or mixtures thereof

The thermoplastic resin composition may further include one or more selected from the group consisting of additives such as lubricants, antioxidants, light stabilizers, and the like.

The lubricant may be 0.1 to 5 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the total base resin, and the thermoplastic resin composition prepared without giving excessive force to the extruder during melt kneading within the above range. The heat resistance of the is excellent effect.

The antioxidant may be 0.1 to 3 parts by weight based on 100 parts by weight of the total base resin, preferably 0.2 to 1 parts by weight, the thermal stability of the thermoplastic resin composition produced within the above range is not lowered, The impact strength is excellent.

The light stabilizer may be 0.1 to 5 parts by weight based on a total of 100 parts by weight of the base resin, preferably 0.2 to 1 part by weight, the light stability of the thermoplastic resin composition produced within the above range is not lowered, The impact strength is excellent.

Automobile interior materials of the present invention is characterized in that the thermoplastic resin composition.

The automotive interior material is preferably a power window switch housing or the like.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.

EXAMPLE

Example  One

<Production of Copolymer>

a) By block polymerization  Manufactured ABS Graft  Copolymer

After dissolving 7.5 parts by weight of butadiene rubber in a mixed solution of 41 parts by weight of styrene monomer and 13.5 parts by weight of acrylonitrile in 35 parts by weight of ethyl benzene as the reaction medium, 5 parts by weight of polybutene having a number average molecular weight of 900 and initiator 1,1- A polymerization solution is prepared by adding 0.02 part by weight of bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and 0.03 part by weight of t-dodecyl mercaptan, which is a molecular weight regulator. The solution was introduced into the reactor at a rate of 10 L / hr, polymerized at 110 ° C. in one step, polymerized at 130 ° C. in two steps, and then 99.2 parts by weight of 0.8 parts by weight of t-dodecyl mercaptan was added to the polymerization solution in three steps. A mixed solution dissolved in parts of ethyl benzene at 10 L / hr was polymerized at 145 ° C., followed by volatilization to remove unreacted monomer and reaction medium, thereby preparing a pellet-type ABS graft copolymer.

b) ASA Graft  Copolymer

5 parts by weight of butyl acrylate, 0.015 parts by weight of di 2-ethylhexyl sulfo succinate sodium salt, 0.02 parts by weight of ethylene glycol dimethacrylate, 0.1 parts by weight of sodium hydrogencarbonate (NaHCO ₃ ), potassium persulfate 0.04 parts by weight and a predetermined amount of ion-exchanged water were collectively administered, the reaction temperature was raised to 70 ° C, and then reacted for 1 hour to prepare a polymer seed.

Here, 45 parts by weight of butyl acrylate, 0.285 parts by weight of di 2-ethylhexyl sulfo succinate sodium salt, 0.1 part by weight of sodium bicarbonate, and 0.06 part by weight of potassium persulfate as an initiator were mixed at 70 ° C., respectively. Polymerization was carried out with continuous administration for 3 hours to prepare a large diameter acrylate rubbery polymer having an average particle diameter of 3,000 to 4,000 mm 3.

50 wt% of the large-diameter acrylate-based rubbery polymer having an average particle diameter of 3,000 to 4,000 mm 3 was mixed with 35 wt% of styrene and 15 wt% of acrylonitrile. After the polymerization reaction, a mixture of 1 part by weight, 1.4 parts by weight of potassium rosinate, 0.042 part by weight of potassium hydroxide and 0.05 part by weight of t-dodecyl mercaptan and 0.1 part by weight of potassium persulfate were continuously administered at 70 ° C. for 5 hours, In order to increase the polymerization conversion rate, the reaction was further performed at 80 ° C. for 1 hour, and then cooled to 60 ° C. to prepare an ASA graft copolymer including a large diameter acrylate rubbery polymer.

The average particle diameter of the prepared ASA graft copolymer including the large diameter acrylate rubbery polymer was 4,500 mm 3, the polymerization conversion rate was 99%, the pH was 9.5, and the graft rate was 45%.

The ASA graft copolymer comprising the large-diameter acrylate-based rubbery polymer prepared above was agglomerated at 85 ° C. and atmospheric pressure using an aqueous calcium chloride solution, aged at 95 ° C., dehydrated and washed, and then heated at 30 ° C. in a hot air at 90 ° C. Drying for minutes gave an ASA-based graft copolymer powder finally containing a large diameter acrylate rubbery polymer.

c) N- Phenylmaleimide , Acrylonitrile  And heat resistant copolymers prepared from styrene

As the heat-resistant copolymer, MSNB product (manufactured by DENKA) having a weight average molecular weight of 100,000, a glass transition temperature of 165 ° C, and an N-phenylmaleimide content of 50% by weight was used.

d) Matte

As the matting agent, sPS (130ZC, manufactured by Idemitsu Co., Ltd.) having a melting temperature of 270 ° C was used.

e) SAN  Copolymer

As the SAN copolymer, LG Chem SAN 92HR product having an acrylonitrile content of 27% by weight and a weight average molecular weight of 130,000 was used.

<Production of the thermoplastic resin composition>

35 parts by weight of the ABS graft copolymer of a), 35 parts by weight of the ASA graft copolymer of b), 30 parts by weight of the heat resistant copolymer of c), 3 parts by weight of the matte agent of d), lubricant EBA (Ethylene bis stearamide) 1 part by weight and 0.2 part by weight of antioxidant were mixed and prepared into pellets using a twin screw extruder at 270 ° C.

Example  2

In Example 1, 28 parts by weight of the ABS graft copolymer of a), 26 parts by weight of the heat resistant copolymer of b), 32 parts by weight of the ASA graft copolymer of c) and 14 parts by weight of the SAN copolymer of d) were used. Except that was carried out in the same manner as in Example 1.

Example  3

In Example 1, 28 parts by weight of the ABS graft copolymer of a), 26 parts by weight of the heat resistant copolymer of b), 16 parts by weight of the large-diameter ASA graft copolymer of c), and 16 parts by weight of the small-diameter ASA graft copolymer And d) was carried out in the same manner as in Example 1, except that 14 parts by weight of the SAN copolymer.

Comparative example  One

The same process as in Example 1 was conducted except that the matting agent was not used in Example 1.

Comparative example  2

Example 1 was the same as in Example 1 except that the ASA graft copolymer of c) and 32 parts by weight of the SAN copolymer of d) were not used.

Comparative example  3

In Example 1, a) 35 parts by weight of ABS graft copolymer (emulsion polymerization ABS, LG Chemical) having a particle size of 300 nm prepared by emulsion polymerization instead of the ABS graft copolymer prepared by bulk polymerization was used. Except that the ASA graft copolymer of b) is not used and d) 32 parts by weight of the SAN copolymer of B-MAT (crosslinked organic microparticles, manufactured by GE) and e) is used as a matte agent. It carried out by the same method as Example 1.

[Test Example]

Physical properties of the thermoplastic resin compositions prepared in Examples 1 to 2 and Comparative Examples 1 to 3 were measured by the following methods, and the results are shown in Table 1 below.

A) Weather resistance (light resistance)-evaluated on Gray Scale according to SAE J1885.

B) Fluidity-measured according to ASTM D1238.

C) Heat resistance (heat deformation temperature, HDT)-was measured according to ASTM D648.

D) glossiness-measured according to ASTM D1003.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Weather resistance Grade 4 Grade 4 Grade 4 Level 3 Level 3 Level 3 Fluidity (g / 10min) One 1.8 2.3 3.8 0.1 5.1 Heat resistance (1/4 ", ℃) 106.0 103.5 104 105.9 96 96.3 Glossiness (45 °) 5.5 7.5 12 25 15 14

As shown in Table 1, the thermoplastic resin compositions (Examples 1 to 3) of the present invention have excellent weather resistance (light resistance) and matte properties (low gloss), but are ABS graft copolymers prepared by emulsion polymerization or It was confirmed that the thermoplastic resin composition (Comparative Examples 1 to 3) containing no matting agent sSP or the like has very low weather resistance and matte properties (high gloss).

Claims (9)

Based on a total of 100 parts by weight of the base resin consisting of ABS, ASA and a heat resistant copolymer a) 10 to 40 parts by weight of the ABS graft copolymer prepared by bulk polymerization; b) 10 to 40 parts by weight of the ASA copolymer; c) 20 to 50 parts by weight of a heat resistant copolymer prepared from N-phenylmaleimide, acrylonitrile and styrene; And d) 0.5 to 5 parts by weight of a matte agent selected from the group consisting of syndiotactic polystyrene and derivatives thereof; Thermoplastic resin composition excellent in light resistance and matte properties. The method of claim 1, The base resin further comprises 20 to 50 parts by weight of the SAN copolymer, characterized in that Thermoplastic resin composition excellent in light resistance and matte properties. The method of claim 1, The thermoplastic resin composition further comprises 0.1 to 5 parts by weight of lubricant, 0.1 to 3 parts by weight of antioxidant, 0.1 to 5 parts by weight of light stabilizer or both based on 100 parts by weight of the base resin. Thermoplastic resin composition excellent in light resistance and matte properties. The method of claim 1, The a) ABS graft copolymer has an average particle diameter of 10000 mm 3 or more, including 5 to 15 parts by weight of butadiene or styrene-butadiene rubber, 40 to 60 parts by weight of aromatic vinyl compound and 10 to 25 parts by weight of vinyl cyan compound Characterized in that Thermoplastic resin composition excellent in light resistance and matte properties. The method of claim 1, The b) ASA graft copolymer is characterized in that it is prepared comprising 10 to 60 parts by weight of acrylate-based rubbery polymer, 30 to 50 parts by weight of styrene monomer and 5 to 20 parts by weight of acrylonitrile monomer. Thermoplastic resin composition excellent in light resistance and matte properties. The method of claim 1, The d) syndiotactic polystyrene is characterized in that the dyad fraction is 85% or more or the pentad fraction is 35% or more Thermoplastic resin composition excellent in light resistance and matte properties. The method of claim 1, The derivative of d) syndiotactic polystyrene is polyhalogenated styrene, polyalkoxy styrene, polyalkylstyrene, polybenzoic acid ester styrene, syndiotactic polystyrene maleic anhydride (sPS-MAH), carboxyl terminal syndiotactic polystyrene (sPS) -COOH), maleic anhydride-syndiotactic polystyrene (sPS-MAH), maleic acid-syndiotactic polystyrene (sPS-MA), fumaric acid-syndiotactic polystyrene (sPS-FA), glycidyl methacrylate- At least one member selected from the group consisting of syndiotactic polystyrene (sPS-GMA) and copolymers containing these as main components Thermoplastic resin composition excellent in light resistance and matte properties. An automobile interior material, which is prepared from the thermoplastic resin composition according to any one of claims 1 to 4. The method of claim 8, The vehicle interior, power window switch housing, Automotive interior material, characterized in that the room mirror housing or console box.