KR100779519B1 - Thermoplastic resin composition having improved gloss at metal deposition, scratching-resistance and heat-resistance - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition, (A) 100 parts by weight of graft ABS polymer; (B) 200 to 250 parts by weight of α-methylstyrene copolymer; And (C) 5 to 50 parts by weight of a low-viscosity styrene acrylonitrile acrylate terpolymer having a fluidity of 45 to 65 g / 10 minutes at a load of 220 ° C. and 10 kg, and having excellent deposition gloss, scratch resistance, and heat resistance. It provides a thermoplastic resin composition.

Deposition gloss, scratch resistance, heat resistance, styrene acrylonitrile acrylate terpolymer

Description

Thermoplastic resin composition having improved gloss at metal deposition, scratching-resistance and heat-resistance}

The present invention relates to a thermoplastic resin composition, and more particularly, to an ABS thermoplastic resin composition excellent in deposition gloss, scratch resistance, and heat resistance.

In general, acrylonitrile-butadiene-styrene (hereinafter referred to as ABS) resin having excellent impact resistance, processability, and chemical resistance is widely used for interior and exterior materials such as automobiles, billboards, and electronic and electronic device components. ABS, which is used for automotive exterior materials, is increasingly required for high performance and high heat resistance. In particular, ABS, which is used as a rear lamp housing for automobiles, is subjected to a painting and aluminum deposition process, which causes problems of environmental pollution and cost increase. Therefore, in order to increase the efficiency of post-processing and to reduce environmental pollution, the conventional coating process is omitted, and the coating process is carried out to aluminium deposition directly on the injection molding. The important thing is that the light reflectance of the deposition surface after deposition should be excellent and there should be no heat deformation generated in the bulb. In addition, scratch resistance is important to maintain the appearance properties of ABS after uncoated deposition.

The ABS polymer is a copolymer of acrylonitrile monomer, butadiene monomer and styrene monomer. They are in harmony with various physical properties such as stiffness, weather resistance, chemical resistance, impact resistance, glossiness, moldability in the ABS polymer.

In order to improve the heat resistance of the ABS polymer, a general method of introducing a monomer having excellent heat resistance is, first, a method of adding a maleimide-based or α-methylstyrene monomer having excellent heat resistance in a polymerization process. There is a method of mixing a heat resistant copolymer containing a monomer having excellent heat resistance with an ABS resin.

As a specific example, a graft ABS resin prepared by replacing part or all of styrene with α-methylstyrene having excellent heat resistance may be prepared by mixing α-methylstyrene copolymer, that is, heat resistant copolymer (US Patent No. 3,111,501) or In some cases, a heat-resistant copolymer such as α-methylstyrene copolymer and an imide substituted copolymer such as N-phenylmaleimide may be used as a heat-resistant reinforcing agent for kneading (US Pat. No. 4,567,233). The heat resistant ABS resin thus prepared has excellent heat resistance but has a low reflectance of light when uncoated aluminum is deposited.

KR application 10-2002-0087176 discloses a polyester resin composition having improved aluminum deposition properties. The composition satisfies heat resistance to high heat emitted from the engine, but has a high manufacturing cost and complicated processing. Therefore, it is not economical to use for the tail lamp.

US Pat. No. 6,605,656 describes that scratching can be improved by alloying olefin resins and nylon resins with a compatibilizer, but there is no mention of gloss.

In order to solve the problems in the prior art as described above, the technical problem of the present invention is to provide a thermoplastic resin composition excellent in gloss, scratch resistance and heat resistance after uncoated deposition.

The present invention to achieve the above technical problem,

(A) 100 parts by weight of graft ABS polymer;

(B) 200 to 250 parts by weight of α-methylstyrene copolymer; And

(C) It provides a thermoplastic resin composition comprising 5 to 50 parts by weight of styrene acrylonitrile acrylate terpolymer.

According to one embodiment of the invention, the graft ABS polymer,

 (a) a mixture of polybutadiene rubber latex having an average particle diameter of 800 to 1500 mm 3 and a gel content of 70 to 95%, and a polybutadiene rubber latex having an average particle diameter of 2500 to 3500 mm 3 and a gel content of 70 to 95%;

(b) aromatic vinyl compounds; And

(c) can be prepared by graft reaction of a vinylcyan compound.

According to another embodiment of the present invention, the thermoplastic resin composition may further include 50 to 75 parts by weight of N-phenylmaleimide copolymer based on 100 parts by weight of the graft ABS polymer.

According to another embodiment of the present invention, the N-phenylmaleimide-based copolymer copolymerizes 45 to 55% by weight of N-phenylmaleimide, 40 to 50% by weight of styrene, and 1 to 4% by weight of maleic anhydride. Can be prepared.

According to another embodiment of the invention, the styrene acrylonitrile acrylate terpolymer, 10 to 20% by weight of styrene monomer, 50 to 60% by weight of acrylate monomer and 3 to 15% by weight of acrylonitrile monomer And 20% by weight of the reaction medium.

Hereinafter, the present invention will be described in more detail.

The thermoplastic resin composition according to the present invention includes 100 parts by weight of the graft ABS polymer, 200 to 250 parts by weight of α-methylstyrene copolymer and 5 to 50 parts by weight of styrene acrylonitrile acrylate terpolymer, further increasing heat resistance. While maintaining gloss after vapor deposition of aluminum, it is excellent in scratch resistance.

In addition, it may further include an N-phenylmaleimide-based copolymer in an amount of 50 to 75 parts by weight.

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

(A) graft ABS polymer

The graft ABS polymer is prepared by graft polymerization of an aromatic vinyl compound and a vinyl cyan compound on a conjugated diene rubber latex. The conjugated diene rubber latex uses a large-diameter rubber latex prepared by preparing a small-caliber rubber latex and then fusing it with an acid.

The particle diameter and the gel content of the conjugated diene rubber latex used to prepare the graft ABS polymer have a great influence on the impact strength and processability of the resin. In general, the smaller the particle diameter of the rubber latex, the lower the impact resistance and workability, and the larger the particle diameter, the better the impact resistance. The lower the gel content, the more the monomer swells in the rubber latex and the polymerization takes place, thereby increasing the apparent particle size, thereby improving the impact strength. However, the higher the content of the rubber latex and the larger the particle size, there is a problem that the graft rate is lowered. The graft rate greatly affects the physical properties of the graft ABS polymer. When the graft rate is lowered, there are many rubber grafts that are not grafted.

Therefore, a method for producing conjugated diene rubber latex having an appropriate particle diameter and gel content is important, and a method for increasing the graft ratio when grafting aromatic vinyl compound and vinyl cyan compound to large diameter rubber latex is important.

The following is a method for producing a graft ABS copolymer, which will be described in detail in each step by dividing into a manufacturing process of a small diameter rubber latex, a manufacturing process of a large diameter rubber latex, and a graft polymerization process.

Manufacturing Process of Small Diameter Rubber Latex

The small-diameter rubber latex used in the present invention is a conjugated diene polymer, the particle diameter is preferably 600 Pa to 1500 Pa, the gel content is preferably 70% to 95%, and the swelling index is 12 to 30. At this time, if the gel content is less than 80%, the thermal stability is lowered, if the gel content is more than 90% there is a problem that the impact strength is lowered.

The small diameter rubber latex is 100 parts by weight of conjugated diene, 1 to 4 parts by weight of emulsifier, 0.1 to 0.6 parts by weight of polymerization initiator, 0.1 to 1.0 parts by weight of electrolyte, 0.1 to 0.5 parts by weight of molecular weight regulator, 90 to 130 parts by weight of ion-exchanged water. After the batch administration, the reaction is carried out at 50 ° C. to 65 ° C. for 7 to 12 hours, and then 0.05 to 1.2 parts by weight of the molecular weight modifier is further added to the batch to react at 55 to 70 ° C. for 5 to 15 hours.

The emulsifiers include alkyl aryl sulfonates, alkali metal alkyl sulfates, sulfonated alkyl esters, fatty acid soaps, alkali salts of rosin acid, and the like, and can be used alone or in mixture of two or more thereof.

A water-soluble persulfate or a peroxy compound can be used as the polymerization initiator, and an oxidation-reduction system can also be used. The most suitable water-soluble persulfates are sodium and potassium persulfates, and fat-soluble polymerization initiators include cumenehydro peroxide, diisopropyl benzenehydroperoxide, azobis isobutylnitrile, tertiary butyl hydroperoxide and paramethane hydroperoxide. , Benzoyl peroxide and the like can be used alone or as a mixture of two or more thereof.

As the electrolyte, KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , K ₄ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ PO ₄ , K ₂ HPO ₄ , Na ₂ HPO ₄ and the like can be used alone or as a mixture of two or more thereof.

Although it does not specifically limit as said molecular weight modifier, Preferably mercaptans are mainly used.

The polymerization temperature is very important for adjusting the gel content and swelling index of the rubber latex, and the choice of initiator should also be considered.

<Large Diameter Rubber Latex Manufacturing Process (Small Diameter Rubber Latex Fusion Process)>

Since the large-diameter rubber latex particle diameter imparts a high impact to the thermoplastic resin, its preparation is very important, and the particle size required for satisfying the physical properties in the present invention is preferably about 2500 mm to 5000 mm.

The large-diameter rubber latex may be manufactured by welding a small-diameter rubber latex with an acid, and the manufacturing process thereof is as follows.

The particle size was 600 ~ 1500Å, gel content 70% to 95%, swelling index 12 to 30 parts of small diameter rubber latex to 2.5 parts by weight of the aqueous solution of acetic acid was slowly administered for 1 hour to enlarge the particles and then stirred To stop the particle diameter is 2500Å to 5000Å, the gel content is 70% to 95% and the swelling index is fused to 12 to 30 to prepare a large diameter conjugated diene rubber latex.

<Graft polymerization process>

The present invention provides a graft ABS polymer by graft copolymerization of an aromatic vinyl compound and a vinyl cyan compound on a large diameter conjugated diene rubber latex, a small diameter conjugated diene rubber latex or a mixture thereof.

The aromatic vinyl compound includes styrene, α-methylstyrene, ο-ethylstyrene, p-ethyl styrene, vinyltoluene, derivatives thereof, and the like. The vinyl cyanide compound is acrylonitrile, methacrylonitrile, ethacrylonitrile. And derivatives thereof.

The temperature of the polymerization reaction is suitable 45 ℃ to 80 ℃ and the polymerization time is preferably 3 to 5 hours.

The method of adding each component in the graft polymerization may include a method of collectively administering each component, a method of divided administration in multiple stages, and a method of continuously administering multiple components. In order to improve graft ratio and minimize coagulation formation, Continuous dosing methods are preferred.

The emulsifiers used in the polymerization reaction are alkylaryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, fatty acid soaps, alkali salts of rosin acids, and the like, and these may be used alone or as a mixture of two or more thereof.

As the molecular weight regulator, tertiary dodecyl mercaptan is mainly used, and the polymerization initiators include peroxides such as cumenehydro peroxide, diisopropylbenzenehydroperoxide, persulfate, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, Oxidation-reduction catalyst systems made of a mixture with a reducing agent such as ferrous sulfate, dextrose, sodium pyrolate, sodium sulfite and the like can be used.

The polymerization conversion rate of the latex obtained after the completion of the polymerization was 96% or more, and an antioxidant and a stabilizer were administered to the latex to coagulate with an aqueous sulfuric acid solution at a temperature of 80 ° C. or higher, followed by dehydration and drying to obtain a powder. The stability of the graft copolymer latex prepared above is determined by measuring the solidified solid content (%) as shown in Equation 1 below.

[Equation 1]

Solid coagulation (%) = (weight of coagulant produced in the reactor (g) / weight of total rubber and monomers) × 100

When the solidified solid content is 0.7% or more, latex stability is extremely low and a large amount of coagulated material makes it difficult to obtain a graft polymer suitable for the present invention.

Therefore, according to the present invention, since the solid solid content becomes 0.7% or less, a polymer suitable for the present invention can be obtained.

In addition, the graft ratio of the graft polymer is measured as follows. The graft polymer latex is coagulated, washed, and dried to obtain a powder form, 2 g of this powder is placed in 300 ml of acetone and stirred for 24 hours. The solution is separated using an ultracentrifuge, and then the separated acetone solution is dropped in methanol to obtain an ungrafted portion, which is dried and weighed. From these weights, the graft ratio is calculated according to the following equation.

[Equation 2]

Graft Rate (%) = (weight of grafted monomer / rubber weight) × 100

The graft rate of the graft ABS polymer used in the present invention is preferably 26% to 60%. If the graft ratio is less than 26%, the thermal stability is lowered. If it is 60% or more, the physical properties are lowered, which is not preferable.

 (B) α-methylstyrene copolymer

The α-methylstyrene copolymer may be prepared by controlling the α-methylstyrene (AMS) monomer and the acrylonitrile (AN) monomer in an appropriate ratio to copolymerize. As the polymerization method, bulk polymerization is preferable, toluene may be used as a solvent, and di-t-dodecyl mercaptan may be used as a molecular weight regulator. The reaction conditions maintain the input amount of the mixture of the reactants so that the average reaction time is 2 to 4 hours and the reaction temperature is maintained at 140 ℃ to 170 ℃.

The manufacturing process is according to the continuous process consisting of raw material input pump, continuous stirring bath, preheating bath and volatilization tank, polymer transfer pump and extrusion process.

In the composition according to the present invention, α-methylstyrene copolymer is included to improve the heat resistance of the composition, and includes 200 to 250 parts by weight based on 100 parts by weight of the graft ABS polymer. When the α-methylstyrene copolymer is included in less than 200 parts by weight, the heat resistance of the composition cannot be secured, and when included in excess of 250 parts by weight, there is a problem that the physical properties are lowered.

(C) Styrene acrylonitrile acrylate terpolymer

The terpolymer may be prepared by mixing and copolymerizing a styrene monomer, an acrylate monomer and an acrylonitrile monomer with a reaction medium.

Preferably, the acrylate monomer is at least one monomer selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl acrylate and ethyl acrylate. More preferably, it is methyl methacrylate.

Preferably, the acrylonitrile monomer is at least one monomer selected from the group consisting of acrylonitrile, methacrylonitrile and etaacrylonitrile.

While the monomer and the reaction medium mixture is introduced into the reactor, the monomer is bulk polymerized to prepare the styrene acrylonitrile acrylate terpolymer.

The styrene acrylonitrile acrylate terpolymer should be low in viscosity, and in this case, it is distributed outside of the resin during blending of the composition according to the present invention to increase the glossiness and surface energy, so that the deposition gloss is excellent. . Therefore, the terpolymer should be a low viscosity styrene acrylonitrile acrylate terpolymer having a fluidity of 45 ° C. to 65 g / 10 min at a load of 220 ° C. and 10 kg.

The amount of the molecular weight modifier is preferably used in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the mixed reaction mixture of the styrene monomer, the acrylate monomer, the acrylonitrile monomer and the reaction medium to control the viscosity of the resin. . More preferably, the content of the molecular weight regulator is 0.1 to 0.5 parts by weight. When it exceeds 1 part by weight, the molecular weight is low, there is a problem that the impact strength is lowered, and when added to less than 0.01 part by weight there is a problem in the operation difficult due to the high viscosity.

In the composition according to the present invention, a low viscosity styrene acrylonitrile acrylate terpolymer having a fluidity of 57 g / 10 min at a load of 220 ° C. and a 10 kg load is included to improve deposition gloss and scratch resistance of the composition. 5 to 50 parts by weight, based on 100 parts by weight of the ABS ABS polymer, but less than 5 parts by weight of scratch resistance is lowered, when included in excess of 50 parts by weight of physical properties is lowered.

(D) N-phenylmaleimide-based heat enhancer

The N-phenylmaleimide (PMI) -based heat enhancer refers to styrene / N-phenylmaleimide / maleic anhydride terpolymer, and may use the trade name DENKA-IP (MS-NB) produced by DENKA, Japan. . The heat-resistant reinforcing agent is a yellow powder having a glass transition temperature of 194 to 198 ℃, molecular weight of 150,000, fluidity (260 ℃ / 10 kg) of 2.4 to 4.4 (g / 10 minutes). In addition, the heat-resistant reinforcing agent is preferably composed of 45 to 55% by weight of N-phenylmaleimide, 40 to 50% by weight of styrene, 1 to 4% by weight of maleic anhydride, most preferably 50% of N-phenylmaleimide %, 45% styrene, 5% maleic anhydride.

The N-phenylmaleimide-based heat enhancer is added to further improve the heat resistance of the composition according to the present invention, based on 100 parts by weight of the graft ABS polymer, 50 to 75 parts by weight, preferably Preferably in an amount of 55 to 65 parts by weight. At this time, if the content of the heat-resistant reinforcing agent is less than 50 parts by weight, there is a problem of lowering the heat resistance, and if it exceeds 75 parts by weight, there is a problem in extrusion and flowability.

In addition, the thermoplastic resin composition of the present invention may further include an additive selected from the group consisting of antioxidants, stabilizers, and lubricants as necessary.

In the production of the heat-resistant thermoplastic resin composition of the present invention, the antioxidant serves to prevent oxidation that may occur during mixing, extrusion and injection molding. As antioxidants that can be used in the present invention, phenol-based primary antioxidants that act as chain inhibitors and phosphite secondary antioxidants that act as peroxide decomposers are used.

The antioxidant may be used 0.1 to 5 parts by weight, preferably 0.1 to 2 parts by weight based on 100 parts by weight of the graft ABS polymer. When the content of the antioxidant is less than 0.1 parts by weight, the effect of improving the thermal stability is less. When the content of the antioxidant is greater than 5 parts by weight, the thermal stability is rather deteriorated due to decomposition of the antioxidant and only the manufacturing cost is increased.

The lubricant acts to smooth the surface of the final product of the resin composition to improve processability. In the present invention, external lubricants and internal lubricants may be selectively used. The inner lubricant is present in the polymer to reduce the viscosity of the resin itself to improve the flow, the outer lubricant serves to reduce the extrusion load between the polymer melt in the extruder and the metal surface. As the lubricant in the present invention, it is preferable to use a stearamide-based lubricant.

In the present invention, the lubricant may be used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight based on 100 parts by weight of the (A) graft ABS polymer. If the amount of the lubricant is less than 0.1 part by weight, it is difficult to expect the rubber particles to be uniformly dispersed in the resin composition during the extrusion process, and the mold release property during the injection molding is lowered, resulting in release cracking or pin whitening. If the value is lowered and larger than 10 parts by weight, uniform dispersion of the rubber particles in the extrusion process, improvement of fluidity, impact resistance, and the like can be expected, but heat resistance is lowered, which is not preferable.

Stabilizers act to inhibit or block thermal decomposition of plastics. Stabilizers that can be used in the present invention include phosphite, stearate, phenol. The stabilizer content is preferably 0.1 to 5 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the graft ABS polymer. When the content is less than 0.1 parts by weight, thermal decomposition is effectively performed. If not more than 5 parts by weight, it is not preferable because the thermal stability is lowered by the self-decomposition rather than.

Thermoplastic resin compositions comprising graft ABS polymers, α-methylstyrene copolymers, styrene acrylonitrile methyl methacrylate terpolymers and optionally N-phenylmaleimide-based heat enhancers and optionally additives according to the invention are typically By extrusion molding, it can be widely used for various parts of automobiles, electric / electronics.

The present invention is described in detail through the following examples and comparative examples. However, an Example is for illustrating this invention and is not limited only to these.

Molding conditions and physical property evaluation conditions used in the present invention are as follows.

(1) Extrusion conditions: LEISTRITZ MICRO 27 GL-36D, 230 ~ 250 ℃

(2) Injection molding: ENGEL EC100 (80 TON), 230 ~ 250 ℃

(3) Heat Deflection Temperature (HDT): ASTM D-648

(4) Tensile Strength: ASTM D-638

(5) Flexural Strength: ASTM D-790

(6) Deposition Method: Sputtering Process

               Argon process pressure: 5 mTorr, thickness: 1 μm,

               Process time: 12 minutes 40 seconds

(7) Scratch resistance: measured by pencil hardness

Preparation Example 1 Preparation of Graft ABS Polymer

Manufacturing Process of Small Diameter Rubber Latex

100 parts by weight of ion-exchanged water, 100 parts by weight of 1,3-butadiene as monomer, 1.2 parts by weight of potassium rosin salt as emulsifier, 1.5 parts by weight of potassium oleate salt, and sodium carbonate (Na2CO3) as electrolyte in a nitrogen-substituted polymerization reactor (autoclave). ) 0.1 parts by weight, 0.5 parts by weight of potassium hydrogen carbonate (KHCO 3), 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) with a molecular weight modifier, the reaction temperature was raised to 55 ℃, 0.3 parts by weight of potassium persulfate as an initiator The batch was administered to initiate the reaction. After reacting for 10 hours, 0.05 parts by weight of tertiary dodecyl mercaptan was further administered again, and reacted at 65 ° C. for 8 hours to terminate the reaction, thereby preparing small-diameter rubber latex.

The gel content of the prepared small-diameter rubber latex was 90%, the swelling index was 18, and the particle size was about 1000Å.

<Manufacture of large diameter rubber latex (fusion of small diameter rubber latex)>

100 parts by weight of the small-diameter rubber latex prepared above was added to the reactor, the stirring speed was adjusted to 10 rpm, and the temperature was adjusted to 30 ° C., and then 3.0 parts by weight of 7% acetic acid aqueous solution was gradually added for 1 hour, and then the stirring was stopped. A large diameter conjugated diene rubber latex was prepared by fusing a small diameter rubber latex by allowing it to stand for 30 minutes. The large-diameter rubber latex prepared by the fusion process was analyzed in the same manner as the small-diameter rubber latex.

The rubber latex obtained at this time had a particle diameter of 3100 mm 3, a gel content of 90% and a swelling index of 17.

<Graft process (production of graft ABS copolymer)>

60 parts by weight of the large-diameter rubber latex prepared by the fusion method in the nitrogen-substituted polymerization reactor, 65 parts by weight of ion-exchanged water, 0.35 parts by weight of potassium rosinate emulsifier, 0.1 parts by weight of sodium ethylenediaminetetraacetate, 0.005 parts by weight of ferrous sulfate , 0.23 parts by weight of formaldehyde sodium sulfoxylate was administered to a batch reactor, and the temperature was raised to 70 ° C. In addition, 40 parts by weight of ion-exchanged water, 0.5 parts by weight of potassium rosinate, 19.2 parts by weight of styrene, 8.2 parts by weight of acrylonitrile, 0.3 parts by weight of T-dodecyl mercaptan, and 0.3 parts by weight of diisopropylene hydroperoxide were mixed. After continuous addition for 10 hours, 10 parts by weight of ion-exchanged water, 0.1 parts by weight of potassium rosinate, 9.6 parts by weight of styrene, 3.0 parts by weight of acrylonitrile, 0.1 parts by weight of T-dodecyl mercaptan, and diisopropylene hydride 0.1 parts by weight of the mixed emulsion of loperoxide was continuously added for 1 hour, and then heated to 80 ° C, and aged for 1 hour to terminate the reaction.

At this time, the polymerization conversion rate was 97.5% by weight, solid coagulation content was 0.2%, graft rate was 37%.

The latex was solidified with an aqueous sulfuric acid solution, washed, and then a powder was obtained.

Preparation Example 2 Preparation of α-Methylstyrene Copolymer

70 parts by weight of α-methylstyrene, 30 parts by weight of acrylonitrile, 30 parts by weight of toluene as a solvent, and 0.15 parts by weight of di-t-dodecylmercaptan with a molecular weight modifier were added to the reactor continuously so that the average reaction time was 3 hours. The reaction temperature was maintained at 148 ° C. The polymerization liquid discharged from the reaction tank is heated in a preheating tank, volatilizes unreacted monomer in a volatilization tank, and maintains the temperature of the polymer at 210 ° C. The SAN-based copolymer resin is processed into pellets using a polymer transfer pump extrusion machine. It was.

Preparation Example 3 Preparation of Low Viscosity Styrene Acrylonitrile Methyl Methacrylate Terpolymer

A mixed solution of 20% by weight of toluene, 17.48% by weight of styrene, 58.52% by weight of methyl methacrylate and 4% by weight of acrylonitrile was prepared, and 1,1-bis (t-butylperoxy) was added to 99.53% by weight of the mixed solution. 0.02% by weight of -3,3,5-trimethyl cyclohexane, 0.35% by weight of n-dodecyl mercaptan, and 1,3,5-tris (4-tert-butyl-3-hydroxy as a hindered phenolic antioxidant 26 L of a polymerization solution to which 0.1 weight% of -2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione was added at a rate of 14 L / hr Polymerization at 140 ° C. in the first reactor and polymerization at 150 ° C. in the second reactor while entering the reactor, when the polymerization conversion is about 60% or more, the unreacted monomer and reaction medium at 215 ° C. in a volatile bath Was removed to prepare a copolymer transparent resin in pellet form.

The polymer obtained was a low viscosity styrene acrylonitrile methyl methacrylate terpolymer having a flowability of 57 g / 10 min at a load of 220 ° C. and 10 kg.

Preparation Example 4 Preparation of High Viscosity Styrene Acrylonitrile Methyl Methacrylate Terpolymer

A mixed solution of 20% by weight of toluene, 17.48% by weight of styrene, 58.52% by weight of methyl methacrylate and 4% by weight of acrylonitrile was prepared, and 1,1-bis (t-butylperoxy) was added to 99.78% by weight of the mixed solution. 0.02% by weight of -3,3,5-trimethyl cyclohexane, 0.1% by weight of n-dodecyl mercaptan, and 1,3,5-tris (4-tert-butyl-3-hydroxy as hindered phenolic antioxidant 26 L of a polymerization solution to which 0.1 weight% of -2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione was added at a rate of 14 L / hr Polymerization at 140 ° C. in the first reactor and polymerization at 150 ° C. in the second reactor while entering the reactor, when the polymerization conversion is about 60% or more, the unreacted monomer and reaction medium at 215 ° C. in a volatile bath Was removed to prepare a copolymer transparent resin in pellet form.

The obtained polymer was a high viscosity styrene acrylonitrile methyl methacrylate terpolymer having a flowability of 10 g / 10 min at a load of 220 ° C. and 10 kg.

Example 1

100 parts by weight of graft ABS copolymer prepared according to Preparation Example 1, 230 parts by weight of α-methylstyrene copolymer prepared according to Preparation Example 2, low viscosity styrene acrylonitrile methyl methacrylate prepared according to Preparation Example 3 17 parts by weight of terpolymer, 1.0 part by weight of H-WAX 200P (polyethylene wax) as lubricant, 0.2 part by weight of diphenyl isodecyl phosphate as stabilizer, and 0.2 part by weight of di-t-butyl phenyl phosphate as antioxidant; Pellets were prepared using a twin screw extruder.

Example 2

100 parts by weight of the graft ABS copolymer prepared according to Preparation Example 1, 200 parts by weight of α-methylstyrene copolymer prepared according to Preparation Example 2, N- under the trade name DENKA-IP (MS-NB) produced by DENKA, Japan. 50 parts by weight of a phenylmaleimide (PMI) -based heat enhancer, 17 parts by weight of a low viscosity styrene acrylonitrile methyl methacrylate terpolymer prepared according to Preparation Example 3, and 1.0 weight of H-WAX 200P (polyethylene wax) Part, 0.2 parts by weight of diphenyl isodecyl phosphate as a stabilizer and 0.2 parts by weight of di-t-butyl phenyl phosphate as an antioxidant were mixed to prepare pellets using a twin screw extruder at 240 ° C.

Comparative Example 1

100 parts by weight of graft ABS copolymer prepared according to Preparation Example 1, 230 parts by weight of α-methylstyrene copolymer prepared according to Preparation Example 2, 1.0 part by weight of H-WAX 200P (polyethylene wax), and a stabilizer. 0.2 parts by weight of diphenyl isodecyl phosphate and 0.2 parts by weight of di-t-butyl phenyl phosphate were mixed with an antioxidant to prepare pellets using a twin screw extruder at 240 ° C.

Comparative Example 2

100 parts by weight of the graft ABS copolymer prepared according to Preparation Example 1, 193 parts by weight of α-methylstyrene copolymer prepared according to Preparation Example 2, N- under the trade name DENKA-IP (MS-NB) produced by DENKA, Japan. 43 parts by weight of a phenylmaleimide (PMI) -based heat enhancer, 1.0 part by weight of H-WAX 200P (polyethylene wax) as a lubricant, 0.2 part by weight of diphenyl isodecyl phosphate as a stabilizer, and 0.2 parts by weight of di-t-butyl phenyl phosphate as an antioxidant. The pellets were prepared by mixing the parts by weight at 240 ° C. using a twin screw extruder.

Comparative Example 3

100 parts by weight of the graft ABS copolymer prepared according to Preparation Example 1, 230 parts by weight of α-methylstyrene copolymer prepared according to Preparation Example 2, high viscosity styrene acrylonitrile methyl methacrylate prepared according to Preparation Example 4 17 parts by weight of copolymer, 1.0 part by weight of H-WAX 200P (polyethylene wax) as lubricant, 0.2 part by weight of diphenyl isodecyl phosphate as stabilizer, and 0.2 part by weight of di-t-butyl phenyl phosphate as antioxidant, were mixed at 240 ° C. Pellets were prepared using a twin screw extruder.

Comparative Example 4

100 parts by weight of the graft ABS copolymer prepared according to Preparation Example 1, 193 parts by weight of α-methylstyrene copolymer prepared according to Preparation Example 2, N- under the trade name DENKA-IP (MS-NB) produced by DENKA, Japan. 43 parts by weight of a phenylmaleimide (PMI) -based heat enhancer, 17 parts by weight of a high viscosity styrene acrylonitrile methyl methacrylate terpolymer prepared according to Preparation Example 4, and 1.0 part by weight of H-WAX 200P (polyethylene wax) as a lubricant , 0.2 parts by weight of diphenyl isodecyl phosphate as a stabilizer and 0.2 parts by weight of di-t-butyl phenyl phosphate as an antioxidant were mixed to prepare pellets using a twin screw extruder at 240 ° C.

The pellets prepared according to Examples 1 to 2 and Comparative Examples 1 and 4 were again injected at 250 ° C. to measure physical properties such as heat deformation temperature, tensile strength, flexural strength, and scratch resistance.

The ejected gloss specimen was deposited with aluminum according to the deposition method mentioned above to measure the deposition gloss.

The results are shown in Table 1 below.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Heat resistance degree (℃, 1/4) 99.3 103.2 99.1 103.1 99.2 103.0 Tensile Strength (㎏ / ㎠) 510 510 502 500 503 505 Flexural Strength (㎏ / ㎠) 805 820 790 800 795 803 Deposition Gloss (75) 130.2 115.8 112.0 89.8 110.4 93.3 Pencil strength B B 3B 3B 2B 2B

Example 1 improved deposition gloss and scratch resistance compared to Comparative Example 1, which did not use a low viscosity styrene acrylonitrile methyl methacrylate terpolymer. However, in Comparative Example 3 using the high viscosity styrene acrylonitrile methyl methacrylate terpolymer, the deposition gloss did not improve, and the improvement in scratch resistance was also weaker than in the case of low viscosity.

In Example 2, the N-phenylmaleimide-based copolymer was further added, whereby the heat resistance was further increased than in Example 1. In the case of not containing a low viscosity styrene acrylonitrile methyl methacrylate terpolymer, Comparative Example 2 has increased heat resistance compared to Comparative Example 1, but the deposition gloss is very low, so that the N-phenylmaleimide copolymer When added, the heat resistance is reinforced, but it can be confirmed that it has an adverse effect in terms of deposition gloss. However, Example 2, in which N-phenylmaleimide-based copolymer was added and low viscosity styrene acrylonitrile methyl methacrylate terpolymer was added, did not show much improvement in deposition gloss compared with Comparative Example 1. Compared with Example 2, it can be seen that the problem of lowering the gloss of deposition due to the addition of N-phenylmaleimide-based copolymer was effectively solved. Comparative Example 4 using a high viscosity styrene acrylonitrile methyl methacrylate terpolymer did not show an improvement in deposition gloss over Comparative Example 2. On the other hand, in Example 2, the improvement of the scratch resistance was confirmed.

As a result, it can be seen that the addition of low viscosity styrene acrylonitrile methyl methacrylate terpolymer maintains the heat resistance and improves the deposition appearance and the scratch resistance.

According to the present invention, it is possible to provide a thermoplastic resin composition having high heat resistance and excellent deposition gloss and scratch resistance.

Claims (9)

(A) 100 parts by weight of graft ABS polymer; (B) 200 to 250 parts by weight of α-methylstyrene copolymer; And (C) 5 to 50 parts by weight of a low viscosity styrene acrylonitrile acrylate terpolymer having a flowability of 45 to 65 g / 10 minutes at a load of 220 ° C. and 10 kg, The α-methyl styrene copolymer is prepared by copolymerizing α-methyl styrene and acrylonitrile. The thermoplastic resin composition of claim 1, wherein the graft ratio of the graft ABS polymer is 26 to 60%. delete The thermoplastic resin composition of claim 1, further comprising 50 to 75 parts by weight of the N-phenylmaleimide copolymer. The thermoplastic resin composition according to claim 4, wherein the N-phenylmaleimide copolymer is prepared by copolymerizing N-phenylmaleimide, styrene, and maleic anhydride. The method of claim 1, wherein the acrylate monomer in the styrene acrylonitrile acrylate terpolymer is methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl acrylate and ethyl Thermoplastic resin composition, characterized in that at least one monomer selected from the group consisting of acrylate. According to claim 1, wherein the acrylonitrile monomer in the styrene acrylonitrile acrylate terpolymer is at least one monomer selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile. Thermoplastic resin composition, characterized in that. The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition further comprises an additive selected from the group consisting of antioxidants, stabilizers, and lubricants. According to claim 8, wherein the content of the additive (A) based on 100 parts by weight of the graft ABS polymer, antioxidant is 0.5 to 12.5 parts by weight, stabilizer is 0.5 to 12.5 parts by weight and lubricant is 0.5 to 25 parts by weight. Thermoplastic resin composition.