KR20120021786A - Thermoplastic resin composition having improved aluminium deposition and adhesion strength - Google Patents

Abstract

The present invention is a thermoplastic resin composition excellent in aluminum deposition and adhesion, specifically, (a) 20 to 40 parts by weight of a graft copolymer grafted with an aromatic vinyl compound and a vinyl cyanide to a conjugated diene rubber polymer; (b) 20 to 50 parts by weight of a heat resistant copolymer including an imide group; (c) 10 to 50 parts by weight of methyl methacrylate copolymer; (d) 0.5 to 5 parts by weight of a compound containing a glycol group.

Description

Thermoplastic Resin Composition Having Improved Aluminum Deposition and Adhesion Strength}

The present invention relates to a thermoplastic resin composition excellent in aluminum vapor deposition property and adhesion.

Acrylonitrile-butadiene-styrene (hereinafter referred to as 'ABS') thermoplastic resins have excellent physical properties such as impact resistance, chemical resistance, and molding processability, and are widely used in various office equipment, electrical and electronic parts, automotive interior and exterior materials, etc. It is material.

In particular, ABS used as an automobile rear lamp housing is subjected to a base coating on the surface of the injection molded product after the injection process. Aluminum deposition step; Top coating to protect the aluminum film; And welding operations with polymethylmethyl acrylate resin (PMMA resin).

However, paint failure may occur during the coating process as described above, the health problems of workers due to the environmental damage and solvent toxicity and scattering due to the use of excess solvent has been pointed out.

Accordingly, in recent years, attention has been focused on a method of directly depositing aluminum in the chamber or by omitting the first base coating in the above-described coating process.

Therefore, research into a resin composition exhibiting excellent deposition properties and adhesion with aluminum, in addition to mechanical properties and thermal properties, has been focused on thermoplastic resins containing ABS used in such a process. Specifically, in order to improve aluminum deposition properties and adhesion of such a thermoplastic resin composition, Korean Patent No. 0446651 and Korean Patent No. 082438 use bimodal rubber or other types of rubber in ABS resin. A method of controlling rubber content by mixing is disclosed, and Korean Patent No. 0622365 and Korean Patent No. 08158151 use an additive such as a surfactant or polypropylene glycol to improve the paintability and paint spreadability. It is starting.

However, the method disclosed in the prior arts is not suitable for applying to the requirement to eliminate the painting process due to cost reduction and environmental issues. That is, when uncoated deposition is performed according to the prior art patent, the deposition gloss is degraded or when the reliability test is carried out after deposition, the adhesion strength between aluminum and plastic is poor and the aluminum deposition surface is often peeled off.

In order to solve the problems of the prior art, the inventors of the present invention completed the present invention while repeatedly studying a thermoplastic resin composition having excellent basic mechanical properties and thermal properties, and excellent deposition and adhesion properties with aluminum. .

The present invention is to provide a thermoplastic resin composition excellent in aluminum deposition property and adhesion and a product manufactured by molding such a thermoplastic resin composition.

In order to achieve the above object, the present invention (a) 20 to 40 parts by weight of a graft copolymer grafted with an aromatic vinyl compound and vinyl cyanide in a conjugated diene rubber polymer; (b) 20 to 50 parts by weight of a heat resistant copolymer including an imide group; (c) 10 to 50 parts by weight of methyl methacrylate copolymer; (d) It provides a thermoplastic resin composition comprising 0.5 to 5 parts by weight of a compound containing a glycol group.

In this case, the (b) the heat-resistant copolymer containing an imide group may be N-phenylmaleimide copolymer, more specifically 30 to 50 parts by weight of N-phenylmaleimide monomer, 0 to 20 parts by weight of acrylonitrile monomer Parts, and 20 to 50 parts by weight of the styrene monomer may be copolymerized.

In addition, the present invention provides a product manufactured by molding the thermoplastic resin composition as described above, such a product may be a vehicle rear lamp housing (rear lamp housing), or rear garnish (Rear Garnish).

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition having excellent aluminum deposition property and adhesion according to an embodiment of the present invention includes (a) 20 to 40 parts by weight of a graft copolymer grafted with an aromatic vinyl compound and a vinyl cyanide to a conjugated diene rubber polymer; (b) 20 to 50 parts by weight of a heat resistant copolymer including an imide group; (c) 10 to 50 parts by weight of methyl methacrylate copolymer; (d) 0.5 to 5 parts by weight of a compound containing a glycol group.

It will be described in detail for each composition contained in the thermoplastic resin composition as described above.

(a) Conjugated diene system  Aromatic vinyl compounds and vinyl cyanide Grafted Graft  Copolymer

The graft copolymer as described above is excellent in impact resistance, chemical resistance and molding processability. In this case, the graft copolymer is a conjugated diene rubber polymer to a polybutadiene rubber polymer; At least one member selected from the group of aromatic vinyl compounds consisting of styrene, alpha methyl styrene, alpha ethyl styrene and paramethyl styrene; And one or more vinyl cyanide compounds selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile, and may be grafted atrylonitrile-butadiene-styrene (hereinafter, “ABS” copolymer). .

In addition, the graft copolymer is a polybutadiene rubber polymer (hereinafter, referred to as "small diameter polybutadiene rubber polymer") having an average particle diameter of 800 to 1500 kPa, gel content of 80 to 90% by weight and an average particle diameter of 2500 to 3500 kPa In the form of a bimodal mixture of a polybutadiene rubbery polymer having a gel content of 80 to 90% by weight (hereinafter referred to as "a large diameter polybutadiene rubbery polymer") in order to optimize impact resistance, chemical resistance and molding processability. It can be used preferably.

At this time, the graft copolymer is 10 to 40 parts by weight of the small diameter polybutadiene rubber polymer and 15 to 40 parts by weight of the large diameter polybutadiene rubber polymer; 15 to 35 parts by weight of the aromatic vinyl compound; And 10 to 25 parts by weight of the vinyl cyan compound may be grafted, the thermoplastic resin composition comprising such a graft copolymer is excellent in fluidity during processing into a product, excellent impact strength after molding.

The particle size and gel content of the small-diameter polybutadiene rubber copolymer and the large-diameter polybutadiene rubber copolymer are closely related to the impact strength. If the particle diameter of the polybutadiene rubber polymer is small, the impact strength and fluidity are reduced, and the coating is large. The problem occurs that the property is inferior, and when the gel content is low, the monomer swells a lot in the rubber latex during the reaction, and when the gel content is high, the shock absorbing ability is lowered during external impact.

Therefore, preferably, as described above, 10 to 40 parts by weight of the small-diameter polybutadiene rubber copolymer and 15 to 40 parts by weight of the large-diameter polybutadiene rubber copolymer, 15 to 35 parts by weight of the aromatic vinyl compound and 10 to 25 parts by weight of the vinyl cyan compound The graft copolymer which grafted the part can be used. Meanwhile, the graft rate may be 40 to 60%.

In addition, the conjugated diene-based rubbery polymer, aromatic vinyl compound and vinyl cyan compound used to prepare the graft copolymer are preferably grafted in the above-mentioned amounts for proper fluidity, impact strength and gloss.

Meanwhile, in the preparation of the graft copolymer, an emulsifier, deionized water, a molecular weight regulator, a peroxide initiator and an activator may be used in addition to the conjugated diene rubber polymer, aromatic vinyl compound, and vinyl cyanide.

In this case, as the emulsifier, a general emulsifier or a reactive emulsifier which is generally used may be used, and specific examples thereof include alkyl aryl sulfonate, alkali methyl alkyl sulfate, sulfonated alkyl ester, soap of fatty acid and alkali of rosin acid. One or a mixture of two or more selected from salts and the like may be used, but the present invention is not limited to the above examples. In the case of using such an emulsifier, 0.6 to 2.0 parts by weight may be used based on 100 parts by weight of the reactant including a conjugated diene rubber polymer, an aromatic vinyl compound, and a vinyl cyan compound.

In addition, mercaptans may be used as the molecular weight regulator, and it is effective to use tertiary dodecyl mercaptan. In this case, the amount of the molecular weight modifier may be used in an amount of 0.1 to 1.0 parts by weight based on 100 parts by weight of the reactant including a conjugated diene rubber polymer, an aromatic vinyl compound, and a vinyl cyan compound.

In addition, when using as said peroxide initiator, for example, sodium persulfate, calcium persulfate, cumene hydroperoxide, diisopropyl benzenehydroperoxide, azobis isobutylnitrile, tertiary butyl hydroperoxide, paramethane One or a mixture of two or more selected from hydroperoxide, benzoyl peroxide, potassium persulfate salt, sodium persulfate salt, and the like may be used, but the present invention is not limited to the above examples. In this case, the amount of the peroxide initiator may be used in an amount of 0.05 to 0.5 parts by weight based on 100 parts by weight of the reactant including a conjugated diene rubber polymer, an aromatic vinyl compound, and a vinyl cyan compound.

In this case, the peroxide initiator may be added at the time of the graft polymer polymerization, but preferably with respect to 100 parts by weight of the total amount, 30 to 50 parts by weight at the start of polymerization, continuously administered together with the monomer emulsion after the start of polymerization. In the step 30 to 50 parts by weight, after the addition of the monomer emulsion is completed, the remaining amount of the peroxide initiator can be finally administered. When such a peroxide initiator is administered in steps, it is advantageous in that the molecular weight of the final graft copolymer can be easily controlled.

On the other hand, the graft copolymer grafted with the aromatic vinyl compound and vinyl cyanide in the conjugated diene rubber polymer as described above may be included in 20 to 40 parts by weight in the thermoplastic resin composition according to the above-described embodiment, such a ratio When used, it is possible to optimize the physical properties such as thermal properties and aluminum deposition properties and adhesion while showing a degree of impact strength suitable for use as a product.

(b) Imide  group( imide group Heat Resistant Copolymers

The inventors of the present invention, the thermoplastic resin composition comprising a heat-resistant copolymer containing an imide group, due to the imide group of the heat-resistant copolymer contained in the composition, while having high adhesiveness with aluminum, conventional heat resistance The present invention was completed by finding that the heat resistance was equal to or higher than that of the copolymer.

Such heat resistant copolymer may be used without particular limitation as long as it includes an imide group, but preferably a phenylmaleimide copolymer may be used. More preferably, such a phenylmaleimide copolymer may be copolymerized with 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. The heat-resistant copolymer in which the N-phenylmaleimide monomer, acrylonitrile monomer and styrene monomer are polymerized at the above ratio is excellent in heat resistance but also excellent in impact strength.

On the other hand, the process for the production of such a heat-resistant copolymer may be a continuous process leading to the raw material input pump, continuous stirring tank, preheating tank, volatilization tank, polymer transfer pump and extrusion process.

It was found that the heat resistant copolymer including such an imide group is excellent in adhesion to aluminum and also exhibits better heat resistance compared to the existing heat resistant copolymer, and in particular, a heat resistant air containing such an imide group The thermoplastic resin composition according to the embodiment of the present invention, including the coalescence, was found not only to exhibit excellent aluminum adhesion but also to exhibit excellent heat resistance.

On the other hand, the heat-resistant copolymer containing such an imide group may be included in 20 to 50 parts by weight in the thermoplastic resin composition according to the above-described embodiment of the present invention, when included in such a content range, thermal properties such as heat resistance and Physical properties such as impact strength can be used to optimize aluminum adhesion and deposition.

(c) Methyl methacrylate  Copolymer

The inventors of the present invention have found that the deposition gloss and aluminum deposition properties are improved by including the methyl methacrylate copolymer in the thermoplastic resin composition, thereby completing the present invention. On the other hand, such a methyl methacrylate copolymer in the thermoplastic resin composition according to the above-described embodiment may be included in 10 to 50 parts by weight, by including such a methyl methacrylate copolymer, the deposition gloss of the thermoplastic resin composition And while maximizing the aluminum deposition properties, it is possible to optimize the physical properties of impact strength and heat resistance.

In this case, the methyl methacrylate copolymer may preferably be a copolymer of methyl methacrylate and methacrylate. Methyl methacrylate contained in such a copolymer improves the mechanical properties of the copolymer, and methacrylate improves the flowability of the copolymer, thereby making it excellent in processability during molding processing. On the other hand, in order to optimize such mechanical properties and flow properties, preferably the methyl methacrylate copolymer may be used that the content of methacrylate is 30% by weight or less.

(d) Glycol group  Compound containing

The inventors of the present invention, when including a compound containing a glycol group in the thermoplastic resin composition, the glycol group contained in such a compound changes the resin surface, and the resin surface expressed after injection molding the thermoplastic resin composition with aluminum The present invention was completed by finding out that the evaporation and adhesion are improved.

That is, since the hydroxyl group present in the compound containing such a glycol group is expressed on the resin surface, it may help to increase the adhesion by causing a bond with aluminum. At this time, the compound containing such a glycol group may be included 0.5 to 5 parts by weight, more preferably 1 to 3 parts by weight may be included. When included in such a content, it is possible to optimize the effect of improving the adhesion with aluminum, while optimizing the thermal properties including the heat resistance and thermal stability of the thermoplastic resin composition.

On the other hand, the compound containing such a glycol group can be used without limitation in the configuration as long as it is a compound including a glycol group and can change the surface of the thermoplastic resin composition. Specifically, commercially available polyalkylene glycols can be used, and when such polyalkylene glycols are used, adhesion with aluminum can be optimized.

At this time, the polyalkylene glycol may be preferably a polypropylene glycol, polyethylene glycol or a block copolymer of polypropylene glycol and polyethylene glycol. In the case of using the polyalkylene glycol as described above, the adhesiveness with aluminum can be improved while optimizing the mechanical properties including the impact strength of the resin composition.

And the compound containing a glycol group, Preferably, a weight average molecular weight can use 500-5,000, More preferably, it can use 1,000-4,000. By adding a compound having a weight average molecular weight range as described above and containing a glycol group to the thermoplastic resin composition, it is possible to optimize the kneading property and fluidity during molding into a product while optimizing aluminum deposition properties.

(e) other additives

On the other hand, the thermoplastic resin composition according to the above-described embodiment may be used additives commonly used in the resin composition, if necessary. Specifically, it may further include at least one member selected from the group consisting of lubricants, antioxidants, antistatic agents, mold release agents and colorants.

 Specifically, the lubricant is not particularly limited as long as it is a kind usually added to the thermoplastic resin composition, but preferably at least one selected from the group consisting of ethylene bis stearamide, polyethylene oxide wax, and magnesium stearate may be used. . The amount of the lubricant added is preferably 0.1 to 5 parts by weight, and more preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the thermoplastic resin composition.

The antioxidant is not particularly limited as long as it is a kind usually added to the thermoplastic resin composition, but preferably a phenolic antioxidant can be used. Examples of phenolic antioxidants include bis- (3,3-bis- (4'-hydroxy-3'-tetra butylphenol) butanoic acid) -glycol esters, tetrakis methylene 3- (3,5-di-tert Butyl-4-hydroxyphenyl) propionic acid methane, 1,3,5-tris- (4-t-butyl-3-hydroxy-2,6-dimethyl benzyl) -1,3,5-triazine-2 , 4,6- (1H, 3H, 5H) -trione, and 1,3,5-tris- (3,5-di-t-butyl-4-hydroxybenzyl) -s-triazine One or more selected from -2,4,6- (1H, 3H, 5H) -trione can be used, but is not limited to the examples described above. A commercially available phenol-based antioxidant, such as IR1076, may be preferably used, and the amount of the antioxidant may be used in an amount of 0.5 to 2 parts by weight based on 100 parts by weight of the thermoplastic resin composition.

In addition, the antistatic agent may be used without any limitation as long as it is an antistatic agent usually used in a resin composition. Specifically, one or more kinds of anionic surfactants, nonionic surfactants and mixtures thereof can be used.

And, the release agent is an additive that can be added to facilitate the release from the mold during molding of the resin, and to maintain the morphology of the molded resin well, if the release agent used in the thermoplastic resin composition in general, the configuration is limited Can be selected without. Specifically, glycerin stirrate, polyethylene tetra stirrate, or the like may be used.

On the other hand, the colorant may also be used without limitation in the constitution if it is usually used in the resin composition. Specifically, an organic pigment, an inorganic pigment or a mixture of the organic pigment and the inorganic pigment may be used. On the other hand, the amount of the antistatic agent, the release agent, or the colorant may be selected and used within the range of 0.1 to 5 parts by weight based on the purpose of use with respect to 100 parts by weight of the thermoplastic resin composition.

On the other hand, the thermoplastic resin composition according to the above-described embodiment is excellent in mechanical properties such as impact strength, excellent moldability and flowability, and also excellent thermal properties including heat resistance, while at the same time deposition properties and The adhesion is excellent.

Specifically, the thermoplastic resin composition according to the embodiment described above has an impact strength of 10 Kg cm / cm or more measured according to ASTM D256, and a melt index of 5-7 g / 10 min measured according to ASTM D1238. In addition, the thermal deformation temperature measured in accordance with ASTM D648 is more than 100 ℃, not only excellent thermal properties, but also excellent in aluminum deposition gloss with a gloss measured according to ASTM D2457 after aluminum deposition is 100 or more. It could be seen that.

In addition to the basic physical properties, the aluminum adhesion to moisture-resistant water was also excellent. Specifically, after deposition of aluminum on the specimen of the thermoplastic resin composition according to the embodiments of the present invention after 240 hours at 50 ℃, 98% relative humidity, it was found that there is no peeling phenomenon observed with the naked eye. . In addition, it was found that after the specimen was left for 240 hours, even after adhesion and detachment with a commercial scotch tape or the like, there was no peeling phenomenon observed with the naked eye.

In addition, after depositing aluminum on the specimen of the thermoplastic resin composition according to the above embodiments, it was found that after 24 hours left in water at a temperature of 40 ℃, there is no peeling phenomenon observed with the naked eye. In addition, it was found that after the specimen was left in water at a temperature of 40 ° C. for 24 hours, even after adhesion and detachment with a commercial scotch tape or the like, there was no peeling phenomenon observed with the naked eye. The thermoplastic resin composition according to the above-described embodiments was found to be excellent in aluminum deposition and adhesion according to moisture and water resistance.

On the other hand, the present invention provides a product manufactured by molding the thermoplastic resin composition according to another embodiment. Such products exhibit excellent thermal, mechanical and aluminum deposition and adhesion properties and can be applied to various product groups. The product range to be applied is not limited as long as it requires a high level of heat resistance, mechanical properties and aluminum deposition and adhesion.

Specifically, it may be a product that requires a high level of aluminum deposition property such as an automobile rear lamp housing or a rear garnish.

The thermoplastic resin composition according to the present invention is excellent in thermal properties and mechanical properties, but also excellent in aluminum deposition property and adhesion, and is useful in fields related to automobile exterior materials, including automobile rear lamp housing, and various electric appliance parts. Can be used.

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

[ Manufacturing example ]

a) Graft ABS  Preparation of Polymer

V) 25 parts by weight of small-diameter polybutadiene rubber latex with an average particle diameter of 1000 kPa and 90% gel, 30 parts by weight of large-diameter polybutadiene rubber latex with an average particle diameter of 3000 kPa and 90% gel, 10 parts by weight of styrene and acryl After 10 parts by weight of ronitrile, 1 part by weight of potassium rosinate and 75 parts by weight of deionized water were added to the polymerization reactor, the temperature of the polymerization reactor was increased to 50 ° C., 0.1 part by weight of tertiary butyl hydroperoxide, and 0.001 weight of dextrose. Part 3, 0.3 parts by weight of tertiary dodecyl mercaptan was administered to initiate the polymerization reaction.

Ii) 30 minutes after the start of the polymerization, at the time when the monomer conversion rate in the above i) was 60%, 15 parts by weight of styrene, 10 parts by weight of acrylonitrile, 1 part by weight of potassium rosinate and 20 parts by weight of deionized water were mixed to prepare a monomer emulsion. It was prepared, and the temperature of the polymerization reactor was slowly raised to 60 ℃ while continuously input to the reaction of the above i) for 2 hours.

Iii) The monomer emulsion of ii) was continuously added, and 0.1 parts by weight of t-butylhydroperoxide was continuously added to the reaction product of i) for 2 hours.

V) After the monomer emulsion of ii) and the peroxide initiator of iii) have been added, 0.05 parts by weight of cumyl hydroperoxide, 0.001 parts by weight of dextrose and 0.002 parts by weight of ferrous sulfate are collectively administered, and the temperature of the polymerization reactor is 75%. The graft ABS polymer was prepared by raising the temperature to 2 ° C. for 2 hours.

b) Imide  Preparation of heat resistant copolymers containing groups

b-1) Preparation of Phenyl Maleimide (PMI) Copolymer

In the heat-resistant copolymer of the present invention, a copolymer was prepared by reacting 40 parts by weight of N-phenylmaleimide monomer and 15 parts by weight of acrylonitrile and 45 parts by weight of styrene monomer. Copolymers were prepared using a continuous process consisting of a raw material input pump, a continuous stirring tank, a preheating tank, a volatilization tank, a polymer transfer pump, and an extrusion process.

b-2) Preparation of AMS Copolymer

As the heat resistant copolymer included in the composition of the comparative example, the AMS copolymer was prepared by adjusting 50 to 80 parts by weight of α-methylstyrene (AMS) monomer and 20 to 50 parts by weight of acrylonitrile (AN) monomer in an appropriate ratio. Specifically, the AMS copolymer used in the comparative example reacted 67 parts by weight of α-methylstyrene (AMS) monomer and 27 parts by weight of acrylonitrile (AN) monomer to obtain a copolymer. Bulk polymerization was used as the polymerization method. 26 to 30 parts by weight of toluene was used as the solvent, and 0.1 to 1.0 parts by weight of di-t-dodecyl mercaptan was used as the molecular weight regulator. The mixed solution of these reactants was charged in an average reaction time of 2 hours to 4 hours, and the reaction temperature was maintained at 140 ° C to 170 ° C. The manufacturing process used a continuous process consisting of a raw material input pump, a continuous stirring tank, a preheating tank and a volatilization tank, a polymer transfer pump, and an extrusion process.

b-3) Preparation of SAN Copolymer

In the same manner as the preparation of the AMS copolymer, 72 parts by weight of a styrene copolymer was used instead of 67 parts by weight of α-methylstyrene (AMS), and copolymerized in the same manner to obtain a SAN copolymer.

c) Methyl methacrylate  Copolymer

A copolymer of methyl methacrylate and methacrylate was prepared. According to the content of methacrylate, three kinds of methyl methacrylate copolymers were prepared as follows.

division Methacrylate content (% by weight) Melt Index (MI)
(g / 10 min) Weight average molecular weight IH830 30 2.2 80,000 IF850 50 11.0 50,000 EG920 20 1.3 100,000

d) Glycol group  Including copolymer

Polypropylene glycol (molecular weight 1000) [Sigma Aldrich PPG 1000] was prepared as a copolymer including a glycol group used in the examples.

[ Example ]

Example  One

30 parts by weight of a) graft ABS copolymer prepared in Preparation Example, b-1) 30 parts by weight of phenylmaleimide copolymer, c) 40 parts by weight of methyl methacrylate copolymer (IH830) d) 1.0 weight of polypropylene glycol Part (molecular weight 1000), 0.5 part by weight of EBA (ethylene bis stearamide) and 0.4 part by weight of antioxidant were mixed with a lubricant, and pelletized using a twin screw extruder at 240 ° C.

Example  2

In Example 1 c) methyl methacrylate copolymer was prepared in the same manner as in Example 1 except for using EG920 having a methacrylate content of 20% instead of IH830 having a methacrylate content of 30% by weight It was.

[ Comparative example ]

Comparative example  One

In Example 1 was prepared in the same manner as in Example 1, except that 1.0 parts by weight of polypropylene glycol was not added.

Comparative example  2

30 parts by weight of the graft ABS copolymer prepared in the above preparation, 30 parts by weight of b-1) phenylmaleimide copolymer and b-3) 40 parts by weight of SAN (styrene acrylonitrile) copolymer, d ) 1.0 parts by weight of polypropylene glycol (molecular weight 1000), 0.5 parts by weight of EBA (ethylene bis stearamide) as a lubricant and 0.4 parts by weight of antioxidant were mixed and prepared into pellets at 240 ° C. using a twin screw extruder.

Comparative example  3

30 parts by weight of the graft ABS copolymer prepared in the preparation example, b-3) 70 parts by weight of the AMS copolymer, d) 1.0 parts by weight of polypropylene glycol (molecular weight 1000), EBA (ethylene bis stearamide) as a lubricant ) 0.5 parts by weight and 0.4 parts by weight of antioxidant were mixed and prepared into pellets at 230 ° C. using a twin screw extruder.

Comparative example  4

In Example 1, except that b-1) 30 parts by weight of the AMS copolymer instead of 30 parts by weight of the phenylmaleimide copolymer was prepared in the same manner as in Example 1.

Comparative example  5

15 parts by weight of the graft ABS copolymer prepared in the above preparation, heat resistant copolymer b-1) 15 parts by weight of phenylmaleimide copolymer and c) 60 parts by weight of methyl methacrylate copolymer (IH830) d) polypropylene glycol 0.3 parts by weight (molecular weight 1000), 0.5 parts by weight of EBA (ethylene bis stearamide) as a lubricant and 0.4 parts by weight of antioxidant were mixed and prepared into pellets at 240 ° C. using a twin screw extruder.

On the other hand, the configuration of the compositions of the above examples and comparative examples are summarized in Table 2 below.

division Example Comparative example One 2 One 2 3 4 5 a) graft ABS copolymer 30 30 30 30 30 30 15 b) heat resistant copolymer b-1) PMI copolymer 30 30 30 30 - - 15 b-2) AMS copolymer - - - - 70 30 - b-3) SAN copolymer - - - 40 - - - c) methyl methacrylate copolymer IH830 40 - 40 - - 40 60 EG920 - 40 - - - - - d) polypropylene glycol 1.0 1.0 - 1.0 1.0 1.0 0.3 Other additives Lubricant (EBA) * 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Antioxidants ** 0.4 0.4 0.4 0.4 0.4 0.4 0.4 (Note) The unit of content in each composition is parts by weight,
* The glidant EBA is ethylene bis stearamide,
** IR1076, IF168 [Ciba (now BASF)] was used as antioxidant.

[ Experimental Example ]

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

1. Impact strength

Measurement was made according to ASTM D 256.

2. Liquidity (melt index; MI )

It measured according to ASTM D1238.

3. Heat Deflection Temperature

It measured according to ASTM D648.

4. Aluminum Vapor deposition  evaluation

After depositing aluminum on the specimen surface in Lab vacuum evaporator, appearance evaluation and Gloss were measured according to ASTM D2457.

5. Aluminum Deposition Reliability Evaluation

After deposition of aluminum on specimens of size 10 * 10 cm, they were left under moisture (50 ℃, 98% relative humidity, 240 hours) and water (40 ℃, 24 hours) conditions. Adhesiveness was evaluated. The number of peeling parts observed with the naked eye was recorded, and good, some defective, and defective degrees were indicated by the following method.

(1) Aluminum adhesiveness (moisture resistance): Qualitative evaluation criteria

Good: visual observation 0 peeling parts

Some defects: less than 5 visual observation peeling parts

Poor: 5 or more visual peeling parts

(2) Aluminum adhesiveness (water resistance): Qualitative evaluation criteria

Good: visual observation 0 peeling parts

Some defects: less than 5 visual observation peeling parts

Poor: 5 or more visual peeling parts

division Example Comparative example One 2 One 2 3 4 5 Impact Strength (1/4 ")
(Kg? Cm / cm) 15 15.5 14.5 15.1 18.5 20.0 8.0 Melt index
(g / 10 min) 5.5 5 5.5 6.5 6.5 10.0 8.5 Heat Deflection Temperature (1/4 ")
(℃) 101.5 102 100 100.5 100 90 93 Aluminum Deposition Gloss 110 110 98 99 95 90 85 Aluminum adhesion (moisture resistance)
(Number of peeling parts) none
(Good) none
(Good) Three
(Some bad) Three
(Some bad) 5
(Bad) 6
(Bad) 6
(Bad) Aluminum adhesiveness (water resistant)
(Number of peeling parts) none
(Good) none
(Good) Three
(Some bad) Three
(Some bad) 5
(Bad) 6
(Bad) 6
(Bad)

As shown in the experimental results of Table 3, the thermoplastic resin composition of the embodiment including the heat-resistant copolymer containing an imide group was excellent in aluminum deposition and adhesion properties compared to the thermoplastic resin composition of the comparative example, It was confirmed that no degradation in mechanical properties was observed.

 On the other hand, even when using a heat-resistant copolymer containing an imide group, such as Comparative Example 5, when the content in the thermoplastic composition does not satisfy a certain level, it can be seen that the mechanical properties including the impact strength value is poor, as well as In addition, aluminum deposition gloss was also poor, and in particular, it was found that defects were observed even in the evaluation of aluminum deposition properties according to water and moisture resistance.

In addition, the composition and the type and content of the PMI copolymer, the graft ABS copolymer, and the methyl methacrylate polymer, which are the composition and the heat-resistant copolymer of Example 1, are the same, but in the case of Comparative Example 1 containing only polypropylene glycol, It was poor, and the aluminum adhesion due to the water resistance and moisture resistance was shown to be poor. And, in the case of Comparative Example 3 including 70 parts by weight of AMS copolymer instead of 30 parts by weight of PMI copolymer and 40 parts by weight of methyl methacrylate copolymer, the heat-resistant copolymer according to the water and moisture It was found that the aluminum adhesion appeared more poorly. Finally, in the composition of Example 1, in the case of Comparative Example 4 using the AMS copolymer as the heat resistant copolymer instead of the PMI copolymer, the heat resistance properties including the heat deformation temperature showed a value equivalent to the examples of the present application to some extent It was confirmed that the adhesion of aluminum due to aluminum deposition gloss, water resistance, and moisture resistance was very poor.

On the other hand, the thermoplastic resin composition according to the embodiments of the present invention exhibits excellent mechanical properties such as impact strength, heat resistance including heat deformation temperature and aluminum deposition gloss, as well as aluminum adhesion according to water and moisture resistance, automobile rear lamp housing It is expected to be useful for manufacturing for such products.

Claims (15)

(a) 20 to 40 parts by weight of a graft copolymer grafted with an aromatic vinyl compound and a vinyl cyanide to a conjugated diene rubber polymer;
(b) 20 to 50 parts by weight of a heat resistant copolymer including an imide group;
(c) 10 to 50 parts by weight of methyl methacrylate copolymer;
(d) A thermoplastic resin composition comprising 0.5 to 5 parts by weight of a compound containing a glycol group. The method of claim 1,
The (a) graft copolymer is a polybutadiene rubber polymer; At least one member selected from the group of aromatic vinyl compounds consisting of styrene, alpha methyl styrene, alpha ethyl styrene and paramethyl styrene; And at least one vinyl cyan compound selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile. The method of claim 1,
The graft copolymer may include 10 to 40 parts by weight of a small diameter polybutadiene rubber polymer and 15 to 40 parts by weight of a large diameter polybutadiene rubber polymer; 15 to 35 parts by weight of the aromatic vinyl compound; And 10 to 25 parts by weight of the vinyl cyan compound is grafted. The method of claim 3,
The small diameter polybutadiene rubber polymer has an average particle diameter of 800 to 1500 kPa, the gel content of 80 to 90% by weight, and the large diameter polybutadiene rubber polymer has an average particle diameter of 2500 to 5000 kPa, and a gel content of 80 to 90% by weight. Resin composition. The method of claim 1,
The thermoplastic resin composition of (b) the heat resistant copolymer containing an imide group is a phenylmaleimide copolymer. 6. The method of claim 5,
The (b) phenyl maleimide copolymer is a thermoplastic resin composition copolymerized 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. The method of claim 1,
The (c) methyl methacrylate copolymer is a thermoplastic resin composition of a copolymer of methyl methacrylate and methacrylate. The method of claim 7, wherein
The (c) methyl methacrylate copolymer has a content of methacrylate of 30% by weight or less. The method of claim 1,
The compound containing the (d) glycol group is a polyalkylene glycol thermoplastic resin composition. The method of claim 9,
(D) the polyalkylene glycol is a thermoplastic resin composition of polypropylene glycol, polyethylene glycol, or a block copolymer of polypropylene glycol and polyethylene glycol. The method of claim 1,
A thermoplastic resin composition having an impact strength of 10 Kg cm / cm or more measured according to ASTM D256 and a melt index of 5 to 7 g / 10 min measured according to ASTM D1238. The method of claim 1,
A thermoplastic resin composition having a heat deflection temperature of 100 ° C. or more, measured according to ASTM D648. The method of claim 1,
A thermoplastic resin composition having a gloss of 100 or more, measured according to ASTM D2457 after aluminum deposition. An article made by molding the thermoplastic resin composition according to claim 1. 15. The article of claim 14, wherein the article is an automotive rear lamp housing or rear garnish.