KR100662177B1 - Resin composition of polycarbonate for antistatic finish - Google Patents

Abstract

The present invention relates to an antistatic polycarbonate resin composition, and more particularly, to an antistatic agent represented by the following Chemical Formula 1, an antistatic agent represented by the following Chemical Formula 2, and UV represented by the following Chemical Formula 3 with respect to 100 parts by weight of the polycarbonate resin: It relates to an antistatic polycarbonate resin composition comprising a stabilizer.

The polycarbonate resin composition is characterized by having excellent weather resistance and excellent antistatic properties without reducing transparency and impact resistance.

[Formula 1]

RSO ₃ P (C _n H _{2n + 1} ) ₄

(In Formula 1, R represents a phenyl group substituted with an alkyl group having 1 to 18 carbon atoms, n is an integer of 1 to 4.)

[Formula 2]

RSO ₃ M

(In Formula 2, R represents a phenyl group substituted with an alkyl group having 1 to 18 carbon atoms, M represents an alkali metal or alkaline earth metal.)

[Formula 3]

(In Formula 3, R ₁ , R ₂ , R ₃ and R ₄ represent hydrogen or an alkyl group having 1 to 18 carbon atoms.)

Antistatic, polycarbonate, resin, composition, antistatic agent, transparency, impact resistance, weather resistance, antistatic.

Description

Antistatic polycarbonate resin composition {Resin composition of polycarbonate for antistatic finish}

The present invention relates to an antistatic polycarbonate resin composition.

The polycarbonate resin composition is widely used as a molding material for automobiles, electrical and electronic parts as engineering plastics, and should be excellent in weather resistance and antistatic property in order to be applied to a head lamp lens or a molded article which should not generate static electricity.

In general, most synthetic polymers are hydrophobic, and thus are susceptible to static electricity. Such physical properties can be a major obstacle to the material manufacturing process as well as to use the material. In particular, in the case of automotive headlamps, static electricity generated during processing attracts dust to molded products, which may cause product defects. Also, in the case of electronic materials, data loss may be caused by static electricity. Therefore, studies have been conducted in various places to impart some degree of conductivity to disperse and dissipate generated charges.                         

As a method of imparting conductivity, there is a method of imparting conductivity by first injecting a unique conductive material such as metal or carbon black into a polymer. This method has the advantage of controlling conductivity according to the dose of conductive material, while it is not suitable for producing transparent resins [R. Gilg, Kunststoffberater, p. 22, 1977; W.F. Verheist, Kunststoffe, p. 66, 1976]. In addition, there is a method of imparting conductivity by coating various antistatic agents on the outside of the polymer. However, this method may lose the antistatic properties if the process involves washing with water or high temperature drying [K. Polzhofer & H.D. Lehmann, Angew. Makromolekulare Chemie, p. 36, 1974].

Contrary to the above, as a method for imparting permanently controlled antistatic properties, cationic antistatic agents such as ammonium, phosphonium and sulfonium salts having long alkyl radicals or anionic antistatic agents such as sodium alkyl sulfate may be used in the polymer. There is a way to put in. At this time, the antistatic agent has a property of being driven from the inside of the polymer toward the surface, and even after the surface of the antistatic agent is washed off by washing with water, the antistatic agent flows out again from the inside to provide permanent antistatic property. However, when using the method as described above there is a disadvantage in reducing the mechanical properties such as impact strength during processing.

In addition, the added antistatic agent may react with other additives to reduce the weather resistance of the resin.

 Accordingly, the present inventors have endeavored to provide a polycarbonate resin composition having excellent weather resistance and excellent antistatic property without reducing transparency and mechanical properties, particularly impact resistance, in order to solve the above problems. Was completed.

Accordingly, an object of the present invention is to provide an antistatic polycarbonate resin composition having transparency, impact resistance and weather resistance.

In order to achieve the above object, the present invention is 0.1 to 5 parts by weight of an antistatic agent represented by the following formula (1) relative to 100 parts by weight of polycarbonate resin, 0.001 to 1 parts by weight of an antistatic agent represented by the following formula (2) and the following formula It provides an antistatic polycarbonate resin composition comprising 0.01 to 1 part by weight of a UV stabilizer represented by 3.

RSO ₃ P (C _n H _{2n + 1} ) ₄

(In Formula 1, R represents a phenyl group substituted with an alkyl group having 1 to 18 carbon atoms, n is an integer of 1 to 4.)

RSO ₃ M

(In Formula 2, R represents a phenyl group substituted with an alkyl group having 1 to 18 carbon atoms, M represents an alkali metal or alkaline earth metal.)

(In Formula 3, R ₁ , R ₂ , R ₃ and R ₄ represent hydrogen or an alkyl group having 1 to 18 carbon atoms.)

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

The polycarbonate resin composition of the present invention is intended to increase the weather resistance while maintaining antistatic properties while minimizing the high mechanical properties, in particular impact resistance and transparency of the polycarbonate, the formulas 1, 2 and 3 By including the compound to be displayed, compared with the polycarbonate resin composition containing the conventional antistatic agent and UV stabilizer, excellent weather resistance without deterioration of transparency and impact resistance, and exhibits an excellent antistatic property.

The polycarbonate resin used to prepare the antistatic polycarbonate resin composition of the present invention is an aromatic polycarbonate resin prepared by interfacial polycondensation of bisphenol A with dichlorocarbonate or melt polycondensation of bisphenol A with diphenyl carbonate. It is characterized in that the aromatic polycarbonate resin prepared by.

In addition, the polycarbonate resin is preferably characterized in that the viscosity average molecular weight of 20,000 to 32,000 by methylene chloride. This means that if the viscosity average molecular weight is less than 20,000, the brittleness of the polycarbonate is increased and the impact resistance is extremely lowered, so that the use of the product is inadequate, while if the viscosity average molecular weight exceeds 32,000 and the molecular weight becomes extremely high, This is because the melt viscosity rises rapidly and there is a problem that the molding of the product is difficult with a conventional molding method such as injection molding.

The biggest feature of the present invention is to include the compounds represented by the formula (1), (2) and (3) in the polycarbonate resin in order to impart antistatic function and weather resistance to the polycarbonate resin without deteriorating impact resistance and transparency. The compounds represented by the above formulas (1) and (2) are contained in the polycarbonate resin, and thus, the low molecular weight compounds represented by the above formulas (1) and (2) are distributed on the surface during molding or injection molding, thereby imparting polarity to the surface. By lowering the surface resistance to have an antistatic function, at the same time the compound structure represented by the formula (3) has the effect of improving the weather resistance.

In addition, the antistatic polycarbonate resin composition of the present invention contains 0.1 to 5 parts by weight of a charge control agent which is a compound represented by the formula (1) based on 100 parts by weight of the polycarbonate resin as a main component. If the amount is more than 5 parts by weight, the impact resistance is lowered and the resin adheres to the supply portion of the screw during injection molding, there is a problem that the molding is disadvantageous, while if less than 0.1 parts by weight, the antistatic function is very minimal Because it becomes.

In addition, the antistatic polycarbonate resin composition of the present invention contains 0.001 to 1 parts by weight of an antistatic agent, which is a compound represented by Formula 2, based on 100 parts by weight of the polycarbonate resin as a main component. This is because if the content exceeds 1 part by weight, the transparency is lowered, whereas if it is less than 0.001 part by weight, the antistatic synergistic effect is insignificant.

In addition, the antistatic polycarbonate resin composition of the present invention contains 0.01 to 1 part by weight of a UV stabilizer, which is a compound represented by Formula 3, based on 100 parts by weight of the polycarbonate resin as a main component. This is because if the content exceeds 1 part by weight, no further weather resistance improvement effect is exhibited, and if the content is less than 0.01 part by weight, the weather resistance is poor.                     

The UV stabilizer is the most effective when R ₁ and R ₃ is an alkyl group having 1 to 8 carbon atoms, R ₂ and R ₄ is hydrogen, for example, 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol {2- (2H-Benzotriazol-2-yl) -4,6-di-tert-pentylphenol}, 3- (2H-benzotriazol-2-yl) -4 -Hydroxyphenethyl-alcohol {3-2H-Benzotriazol-2-yl) -4-hydroxyphenethyl-alcohol}, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3 -Tetramethylbutyl) phenol {2- (2H-Benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol}, 2,4-di-tert-butyl-6- (5- Chlorobenzotriazol-2-yl) phenol {2,4-di-tert-butyl-6- (5-chlorobenzotriazol-2-yl) phenol}, 2- (2H-benzotriazol-2-yl) -4 -(Tert-butyl) -6- (cet-butyl) phenol {2- (2H-benzotriazol-2-yl) -4- (tert-butyl) -6- (sec-butyl) phenol}, 3- (3 -(2H-Benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl) propionate {3- (3- (2H-benzotriazole-2-yl) -5-t-butyl- 4-hydroxyphenyl) propionate}, 2-benzotriazol-2-yl-4,6-di-tert-butylphenol {2-benz otriazol-2-yl-4,6-di-tert-butylphenol} at least one selected from the group consisting of. Preferably 2- (2H-benzotriazol-2-yl) -4- (tert-butyl) -6- (cet-butyl) phenol and 2-benzotriazol-2-yl-4,6-di- A mixture of tert-butylphenol is used.

On the other hand, the resin composition of the present invention may further include additives such as antioxidants, lubricants, pigments, etc., according to the other needs, the amount of use thereof is usually in the range used.

In addition, in order to prepare an antistatic polycarbonate resin composition according to the present invention, the compound represented by the formula (1), (2) and (3) in the polycarbonate resin and antioxidants, such as phenolic or phosphite, commonly used Lubricants, such as a stearate or a stearate, are added together and melt mixed with a screw rotational speed at a temperature of 240 to 300 ° C. at a temperature of 240 to 300 ° C. using a double screw extruder or the like, and the molten mixture obtained is It is dried at 100 to 130 ℃ using a hot air dryer to obtain an antistatic polycarbonate resin composition as a final product.

The polycarbonate resin composition prepared as described above is excellent in antistatic function without reducing impact resistance and transparency, and thus is suitable for a head lamp lens or the like because it can prevent damage caused by static electricity or the like when applied to electrical and electronic products, and also has excellent weather resistance.

Accordingly, the present invention provides a head lamp lens, which is manufactured using the antistatic polycarbonate resin composition.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples, but the present invention is not limited only to these examples.

<Examples 1 to 5 and Comparative Examples 1 to 8>

In order to prepare an antistatic polycarbonate (hereinafter referred to as PC) resin composition, each of the contents shown in Table 1 was added to a twin screw extruder, and the extrusion temperature was 270 ° C., and the screw rotation speed was 200 rpm. After mixing and preparing in pellet form, the product was preliminarily dried at 130 ° C. for 4 hours in a hot air dryer, and then dried pellets were injection molded at a cylinder temperature of 280 ° C. to obtain a specimen. In this case, as the antistatic agent 1, in the compound represented by Chemical Formula 1, R is a phenyl group substituted with C ₁₂ H ₂₅ and n is 4 (C ₁₂ H ₂₅ (C ₆ H ₆ ) SO ₃ P (C ₄ H _{9 4} ) dodecylbenzenesulfonic acid tetrabutylphosphonium salt), and as the antistatic agent 2, in the compound represented by Formula 2, R is a phenyl group substituted with C ₁₂ H ₂₅ and M is sodium (C ₁₂ H ₂₅ (C ₆ H ₆ ) SO ₃ Na: sodium dodecylbenzenesulfonate) was used. As a UV stabilizer represented by the formula (3) in Examples 1 to 5 as 2-component (2H- benzotriazol-2-yl) -4- (tert-butyl) -6- (sec-butyl) as the A-1 component Phenolic {2- (2H-benzotriazol-2-yl) -4- (tert-butyl) -6-(sec-butyl) phenol} was used. In Comparative Examples 1 to 8, 2- (2) was used as the A-2 component. -Hydroxy-5-t-oxylphenyl) -benzotriazole {2- (2-hydroxy-5-t-ocylphenyl) -benzotriazole} was used. In addition, tris (2,4-di-tert-butyl (phenyl) phosphite)) {(Tris (2,4-di-tert-butyl (phenyl) phosphite))} as an antioxidant and pentaeryte as a lubricant Pitolerythritol tetra-stearate was used.

Furtherance PC (part by weight) Antistatic Agent 1 (part by weight) Antistatic Agent 2 (parts by weight) Antioxidant (parts by weight) Lubricant (parts by weight) UV stabilizer (parts by weight) A-1 A-2 Example 1 100 0.5 0.005 0.1 0.1 0.3 Example 2 100 One 0.01 0.1 0.1 0.3 Example 3 100 1.5 0.05 0.1 0.1 0.3 Example 4 100 2 0.1 0.1 0.1 0.3 Example 5 100 4 0.4 0.1 0.1 0.3 Comparative Example 1 100 One 0.1 0.1 0.3 Comparative Example 2 100 1.5 0.1 0.1 0.3 Comparative Example 3 100 2 0.1 0.1 0.3 Comparative Example 4 100 One 0.01 0.1 0.1 0.3 Comparative Example 5 100 1.5 0.05 0.1 0.1 0.3 Comparative Example 6 100 2 0.1 0.1 0.1 0.3 Comparative Example 7 100 - - 0.1 0.1 - Comparative Example 8 100 - - 0.1 0.1 0.3

Experimental Example 1

The specimens obtained by injection molding in Examples 1 to 5 and Comparative Examples 1 to 8 were subjected to surface resistance using a surface resistor (Advantest R8340A) and transparency using a haze meter (BYK-Gardner Gmbh 4725). , Impact strength using an impact strength measuring instrument (Dynatup 8250), and weather resistance change for 1000 hours using a weather-O-meter (Atlas 25/18 WT-2) is shown in Table 2 below. It was. The results are shown in Table 2 below.

Furtherance transparency(%) Surface resistance Impact strength Weather resistance  Example 1 87 4.0 × 10 ¹⁶ 80 1.3  Example 2 87 5.0 × 10 ¹⁵ 80 1.6  Example 3 87 5.0 × 10 ¹⁴ 80 1.8  Example 4 87 3.0 × 10 ¹³ 80 1.9  Example 5 87 3.0 × 10 ¹¹ 80 2.2  Comparative Example 1 87 1.0 × 10 ¹⁶ 80 3.3  Comparative Example 2 87 2.0 × 10 ¹⁵ 80 3.6  Comparative Example 3 87 2.0 × 10 ¹⁴ 80 3.8  Comparative Example 4 87 6.0 × 10 ¹⁵ 80 2.8  Comparative Example 5 87 7.0 × 10 ¹⁴ 80 3.0  Comparative Example 6 87 5.0 × 10 ¹³ 80 3.3  Comparative Example 7 87 9.0 × 10 ¹⁶ 80 9.3  Comparative Example 8 87 9.0 × 10 ¹⁶ 80 2.6

As a result, as shown in Table 2, it can be seen that the surface resistance decreases as the amount of antistatic agent increases. Dodecylbenzenesulfonic acid tetrabutylphosphonium salt (antistatic agent 1) was shown to be effective as an antistatic agent for transparent polycarbonate. It was confirmed that can be obtained. On the other hand, it was confirmed that the combination of the A-1 component has better weather resistance than the combination of the A-2 component as the UV stabilizer in the antistatic agents 1 and 2. On the other hand, it was found that 2- (2-hydroxy-5-t-oxylphenyl) -benzotriazole, which is the UV stabilizer A-2 used in Comparative Examples 1 to 8, reacted with the antistatic agent to reduce the weather resistance of the resin. .

As described above, the antistatic polycarbonate resin composition of the present invention includes a compound represented by the formula (1), (2) and (3) in the polycarbonate resin, thereby providing excellent weatherability without reducing impact resistance and transparency, It was found that it has an excellent antistatic function. Therefore, the resin composition is applicable to automotive parts such as headlamp lenses and electric and electronic parts such as dust covers of cleaners.

Claims (7)

0.1 to 5 parts by weight of an antistatic agent represented by the following Chemical Formula 1, 0.001 to 1 part by weight of an antistatic agent represented by the following Chemical Formula 2, and 0.01 to 1 parts by weight of UV stabilizer represented by the following Chemical Formula 3 based on 100 parts by weight of the polycarbonate resin: Antistatic polycarbonate resin composition, characterized in that. [Formula 1] RSO ₃ P (C _n H _{2n + 1} ) ₄ (In Formula 1, R represents a phenyl group substituted with an alkyl group having 1 to 18 carbon atoms, n is an integer of 1 to 4.) [Formula 2] RSO ₃ M (In Formula 2, R represents a phenyl group substituted with an alkyl group having 1 to 18 carbon atoms, M represents an alkali metal or alkaline earth metal.) [Formula 3]

(In Formula 3, R ₁ , R ₂ , R ₃ and R ₄ represent hydrogen or an alkyl group having 1 to 18 carbon atoms.) The method of claim 1, wherein the polycarbonate resin is an aromatic polycarbonate resin prepared by interfacial polycondensation of bisphenol A and dichlorocarbonate or An antistatic polycarbonate resin composition characterized in that the aromatic polycarbonate resin produced by melt polycondensation of bisphenol A and diphenyl carbonate. The antistatic polycarbonate resin composition according to claim 2, wherein the polycarbonate resin has a viscosity average molecular weight of 20,000 to 32,000 by methylene chloride. The method of claim 1, wherein the UV stabilizer is R ₁ and R ₃ is an alkyl group having 1 to 8, R ₂ and R ₄ the antistatic polycarbonate resin composition, characterized in that the hydrogen. 5. The UV stabilizer of claim 1, wherein the UV stabilizer is 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol {2- (2H-Benzotriazol-2-yl). -4,6-di-tert-pentylphenol}, 3- (2H-benzotriazol-2-yl) -4-hydroxyphenethyl-alcohol {3-2H-Benzotriazol-2-yl) -4-hydroxyphenethyl- alcohol}, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol {2- (2H-Benzotriazol-2-yl) -4- (1 , 1,3,3-tetramethylbutyl) phenol}, 2,4-di-tert-butyl-6- (5-chlorobenzotriazol-2-yl) phenol {2,4-di-tert-butyl-6- (5-chlorobenzotriazol-2-yl) phenol}, 2- (2H-benzotriazol-2-yl) -4- (tert-butyl) -6- (sec-butyl) phenol {2- (2H-benzotriazol- 2-yl) -4- (tert-butyl) -6- (sec-butyl) phenol}, 3- (3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxy Phenyl) propionate {3- (3- (2H-benzotriazole-2-yl) -5-t-butyl-4-hydroxyphenyl) propionate}, 2-benzotriazol-2-yl-4,6-di- At least one selected from the group consisting of 2-benzotriazol-2-yl-4,6-di-tert-butylphenol Antistatic polycarbonate resin composition according to claim. 6. The UV stabilizer according to claim 5, wherein the UV stabilizer is 2- (2H-benzotriazol-2-yl) -4- (tert-butyl) -6- (cet-butyl) phenol and 2-benzotriazol-2-yl An antistatic polycarbonate resin composition, characterized in that a mixture of -4,6-di-tert-butylphenol. It is manufactured using the antistatic polycarbonate resin composition of Claim 1, The head lamp lens characterized by the above-mentioned.