KR20100078847A - Polyester resin composition - Google Patents

Abstract

PURPOSE: A polyester resin composition is provided to secure the heat resistance at the high temperature for preventing the generation of gas from the resin, and to reduce the generation of a migration. CONSTITUTION: A polyester resin composition contains the following: 100 parts of polyester resin by weight including 50~90wt% of polybutylene terephthalate resin, and 10~50wt% of polyethylene terephthalate resin; 0.1~10 parts of inorganic filler by weight; 0.005~5 parts of stabilizer by weight; and 0.005~5 parts of fluorated olefin lubricant by weight. The inherent viscosity of the polybutylene terephthalate resin is 0.36~1.6 dL/g.

Description

Polyester resin composition {POLYESTER RESIN COMPOSITION}

The present invention relates to a polyester resin composition, and more particularly, it is possible to form a smooth metal deposited film by direct deposition of a metal, and also has excellent thermal stability at high temperature, so that gas generation and heat when left for a long time in a high temperature environment The present invention relates to a polyester resin composition capable of reducing the migration generation amount of a decomposed substance.

In the conventional process of forming a metal deposition reflector such as a headlamp bezel, a reflector, a luminaire for a vehicle, a metal is deposited after a primer is applied to increase the surface smoothness of a light reflection surface. However, in the conventional method, since the organic solvent is contained in the primer, it is harmful to the environment, and since the volatilization and the formation of the coating film take a long time, there are many problems in terms of cost and productivity.

Due to these problems, the direct deposition method of depositing a metal directly on a surface without applying a primer is increasing. High surface smoothness is required to enable direct deposition, and especially for automotive headlamp bezels or lighting fixtures, minimal gas generation and migration of pyrolysis materials are required at high temperatures.

On the other hand, the polyethylene terephthalate resin has a very good crystallization rate due to the high crystallization rate, but lack of releasability in the mold, the mold release defect phenomenon is prominent on the mold surface. Therefore, proper release of adhesives requires the use of suitable lubricants. Generally, however, these lubricants are a major cause of migration of gases and pyrolysis materials when the resin is given under high temperature environments. Therefore, in order to minimize these effects, it is important to select the appropriate lubricant.

For example, Korean Patent Publication No. 2002-0062403 discloses a thermoplastic polyester resin composition in which an inorganic filler and montan wax are added to a blend of polybutylene terephthalate and polyethylene terephthalate. However, the composition has excellent surface smoothness and the like, but due to the characteristics of montan wax, a large amount of gas and pyrolysates are generated when left at a high temperature for a long time.

One embodiment of the present invention can form a smooth metal deposited film by direct deposition of metal, and also excellent heat resistance at high temperature to reduce the amount of gas generation of resin and migration of pyrolysis material when left for a long time in a high temperature environment It is for providing the polyester resin composition which can be made.

Another embodiment of the present invention is to provide a molded article prepared from the polyester resin composition.

However, technical problems to be achieved by the present invention are not limited to the above-mentioned problems, and other technical problems will be clearly understood by those skilled in the art from the following description.

One embodiment of the present invention (A) 100 parts by weight of a polyester resin comprising (a-1) 50 to 90% by weight of a polybutylene terephthalate resin and (a-2) 10 to 50% by weight of a polyethylene terephthalate resin (B) 0.1 to 10 parts by weight of the inorganic filler; (C) 0.005 to 5 parts by weight of a stabilizer; And (D) provides a polyester resin composition comprising 0.005 to 5 parts by weight of a fluorinated olefin lubricant.

Another embodiment of the present invention provides a molded article prepared from the polyester resin composition.

Other specific details of embodiments of the present invention are included in the following detailed description.

Polyester resin composition according to an embodiment of the present invention can form a smooth metal deposited film by direct deposition of metal, and also has excellent heat resistance at high temperature, gas generation and thermal decomposition of the resin when left for a long time in a high temperature environment Since the migration of materials can be reduced, it is useful for manufacturing various molded articles such as metal deposition exterior parts such as automobile lamp housings, reflectors and housings of lighting fixtures.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless otherwise specified herein, 'polyethylene terephthalate resin' refers to both polyethylene terephthalate homopolymer and polyethylene terephthalate copolymer.

Polyester resin composition according to an embodiment of the present invention comprises (A) 50 to 90% by weight of (a-1) polybutylene terephthalate resin and (a-2) 10 to 50% by weight of polyethylene terephthalate resin (B) 0.1-10 parts by weight of inorganic fillers, based on 100 parts by weight of polyester resin; (C) 0.005 to 5 parts by weight of a stabilizer; And (D) 0.005 to 5 parts by weight of fluorinated olefin lubricant.

Hereinafter, each component included in the polyester resin composition according to one embodiment of the present invention will be described in detail.

(A) polyester resin

The polyester resin according to the embodiment of the present invention includes (a-1) polybutylene terephthalate resin and (a-2) polyethylene terephthalate resin.

(a-1) Polybutylene terephthalate resin

The polybutylene terephthalate resin may be a polybutylene terephthalate polymer which is condensation-polymerized by directly esterifying or transesterifying 1,4-butanediol with terephthalic acid or dimethyl terephthalate.

In addition, in order to increase the impact strength of the resin, the polybutylene terephthalate is copolymerized with an impact improving component such as polytetramethylene glycol (PTMG), polyethylene glycol (PEG), polypropylene glycol (PPG), aliphatic polyester, aliphatic polyamide, etc. One copolymer or modified polybutylene terephthalate, which is a blend blended with these impact enhancing components, may be used.

In addition, the polybutylene terephthalate resin is preferably intrinsic viscosity [η] measured according to ASTOM D2857 is 0.36 to 1.60 dl / g, more preferably 0.52 to 1.25 dl / g. When the intrinsic viscosity of the polybutylene terephthalate resin has the above range, it is possible to secure an excellent balance of mechanical properties and moldability of the resin.

The polybutylene terephthalate resin is contained in 50 to 90% by weight based on the total amount of the polyester resin. When polybutylene terephthalate resin is contained in the said range, the outstanding balance of the smoothness and heat resistance of the surface of resin can be ensured.

(a-2) Polyethylene terephthalate resin

The polyethylene terephthalate resin may be a linear polyethylene terephthalate polymer prepared by condensation polymerization of terephthalic acid and ethylene glycol.

Polyethylene terephthalate resin according to an embodiment of the present invention can be used that the intrinsic viscosity [η] measured according to ASTOM D2857 is 0.5 to 1 dl / g.

The polyethylene terephthalate resin is an amorphous polyethylene terephthalate copolymer comprising 1,4-cyclohexane dimethanol (CHDM) as a copolymerization component, and is composed of ethylene glycol components constituting the polyethylene terephthalate resin. The polyethylene terephthalate glycol resin which is a copolyester resin which replaced one part with 1, 4- cyclohexane dimethanol can also be used. At this time, the 1,4-cyclohexane dimethanol is preferably contained in 3 to 48 mol%, preferably 5 to 20 mol% relative to the ethylene glycol component. When 1, 4- cyclohexane dimethanol is contained in the said range, it is more preferable for maintaining the balance of the surface smoothness and heat resistance of a thermoplastic resin.

The polyethylene terephthalate resin is contained in 10 to 50% by weight based on the total amount of the polyester resin. When polyethylene terephthalate resin is contained in the said range, the outstanding balance of the surface smoothness and heat resistance of resin can be ensured.

(B) inorganic filler

The inorganic filler serves to improve the mechanical properties and heat resistance of the molded article. Such inorganic fillers may be used without particular limitation as long as they are commonly used in polyester resin compositions, and specifically, titanium-based whiskers, talc, wollastonite, bentonite, montmorillonite ( montmorillonite, calcium carbonate, clay, kaolin, and combinations thereof may be used. Of these, talc, clay, or kaolin can be preferably used.

The inorganic filler is preferably an average particle diameter of 0.1 to 2㎛, more preferably 0.5 to 1㎛. When the average particle diameter of the inorganic filler has the above range, it is possible to secure an excellent balance of heat resistance and surface smoothness of the paper.

The inorganic filler may be used by surface treatment with an organic material to improve the dispersibility with the polyester resin.

The inorganic filler according to one embodiment of the present invention is included in an amount of 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the polyester resin. When the inorganic filler is included in the above range it can ensure the heat resistance of the resin.

(C) stabilizer

The stabilizer stabilizes the polyester resins and prevents the resins from being decomposed (for example, thermal decomposition), and also serves to further improve various physical properties such as surface smoothness and heat resistance of the resins.

Such stabilizers can be used without particular limitation as long as they are typically usable in polyester resin compositions, specifically phosphoric acid; Phosphorous acid such as 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid; Phosphorous acid esters such as triphenyl phosphite, trimethyl phosphite, triisodecyl phosphite and tri- (2,4-di-t-butylphenyl) phosphite; Phosphorus compounds such as hypophosphorous acid and polyphosphoric acid; Acidic phosphoric acid esters such as methyl phosphate, dibutyl phosphate and monobutyl phosphate; And combinations thereof may be used.

Stabilizer according to an embodiment of the present invention is included in 0.005 to 5 parts by weight, preferably 0.01 to 2 parts by weight based on 100 parts by weight of the polyester resin. When the stabilizer is included in the above range, it is possible to ensure an excellent balance of the surface smoothness and heat resistance of the resin.

(D) fluorinated olefin type lubricant

The fluorinated olefin-based lubricant provides proper release property to the resin and at the same time has a low volatility at a high temperature, thereby suppressing the generation of gas and pyrolytic substances when the resin is left at a high temperature.

Specific examples of the fluorinated olefin lubricant include tetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / vinylidene fluoride copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, ethylene / tetrafluoroethylene Copolymer, and those selected from the group consisting of perfluoropolyether (PFPE) represented by the following formula (1), and combinations thereof may be used. Of these, perfluoropolyethers represented by the following formula (1) may be preferably used.

[Formula 1]

(Wherein n is an integer from 1 to 300).

According to one embodiment of the present invention, in order to improve the releasability of the polyester resin composition can be used in combination with the fluorinated olefin-based lubricant and other lubricant components.

As the other lubricant components, for example, montan waxes such as montanic acid ester waxes, metal salts of montanic acid, polyethylene waxes, silicone oils, metal salts of stearyl acid, etc. may be used, and preferably montan waxes may be used. Can be.

In the case where the fluorinated olefin lubricant and other lubricant components are mixed and used, it is preferably mixed in a weight ratio of 1 to 10: 1. When mixing in the above range it can be ensured an excellent balance of the releasability and heat resistance of the resin.

The fluorinated olefin lubricant is included in an amount of 0.005 to 5 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the polyester resin. When the fluorinated olefin type lubricant is included in the above range, it is possible to secure an excellent balance of the releasability and heat resistance of the resin.

The polyester resin composition according to an embodiment of the present invention may be prepared by a known method for preparing a resin composition, for example, by mixing the components and then melt extrusion in an extruder in a conventional manner It can be prepared in pellet or chip form.

The polyester resin composition may be used for molding a variety of products, in particular, it is possible to form a smooth metal deposited film by direct deposition of metal, automotive lamp housings, reflectors, lighting fixtures that require excellent heat resistance at high temperatures It can be usefully applied to the production of various molded articles, such as metal deposition exterior parts, such as the housing of the.

Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

EXAMPLE

Each component of the polyester resin composition used in the Example and comparative example of this invention is as follows.

(A) polyester resin

(a-1) Polybutylene terephthalate resin

As the polybutylene terephthalate resin, PBT shinite K006 ^® (intrinsic viscosity [η] = 1.0 dl / g) manufactured by Shinkong Corporation was used.

(a-2) Polyethylene terephthalate resin

As the polyethylene terephthalate resin, SKYPET BR8040 ^® (intrinsic viscosity [η] = 0.8 dl / g) manufactured by SK Chemical was used.

(B) inorganic filler

Kaolin having an average particle diameter of 1.0 mu m was used.

(C) stabilizer

Asahi Denka's ADK STAB PEP-36 ^® was used.

(D) fluorinated olefin type lubricant

As perfluoropolyether (PFPE), DuPont's FLUOROGUARD ^® PCA was used.

(D ') montan type lubricant

As Montan-based lubricant used as a comparative example, LICOWAX ^® OP of Clariant was used.

Examples 1 to 3 and Comparative Examples 1 to 4

Each of the above components were mixed according to the composition ratio shown in Table 1, and melt-kneaded in a twin screw melt extruder heated to 240 to 280 ℃ to prepare a chip. In Table 1, the content units of (a-1) and (a-2) are in weight%, and the content units of (B), (C), (D), and (D ') are (A) polyester resin 100 Parts by weight relative to parts by weight.

TABLE 1

 
Example
Comparative example One 2 3 One 2 3 4 (A)
Polyester resin (a-1) Polybutylene terephthalate resin 52 52 52 52 52 52 52 (a-2) Polyethylene terephthalate resin 48 48 48 48 48 48 48 (B) inorganic filler 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (C) stabilizer 0.1 0.1 0.1 0.1 0.1 0.1 0.1 (D) fluorinated olefin type lubricant 2.0 2.0 4.0 - - 6.0 0.003 (D ') montan type lubricant 0.2 - - 0.2 0.5 - -

[Test Example]

After the chips prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were dried at 130 ° C. or more for 5 hours or more, physical property measurement specimens were prepared using a screw injection machine heated to 240 to 280 ° C., respectively. Physical properties of the prepared specimens were measured by the following method, and the results are shown in Table 2 below.

(1) Evaluation of migration occurrence due to gas generation and pyrolysis under high temperature environment: The specimen produced by the screw injection machine was cut to 15 mm by 15 mm X length. The glass is then placed in a 100 mm diameter glass chaile container with a glass cover, and the temperature is set to 165 ° C. on a hot plate, and is kept for 5 hours. Then, the haze meter is used to measure the amount of migration material condensed on the glass glass cover. Measured using. The injection molding conditions were set at an injection temperature of 240-250-250-260 (° C).

(2) Mold release: It was measured by visual observation and ejector pin marks during molding.

TABLE 2

Example Comparative example One 2 3 One 2 3 4 Haze (%) 3.2 2.2 2.8 3.1 6.7 8.6 2.0 Release (○: Excellent, X: Poor) ○ ○ ○ × ○ ○ ×

From the results in Table 2, the polyester resin compositions of Examples 1 to 3 according to the present invention simultaneously satisfied the low haze value and the appropriate release property in comparison with Comparative Examples 1 and 2 without the addition of a fluorinated olefin lubricant.

On the other hand, Comparative Example 3 in which the fluorinated olefin lubricant was used in an amount out of the lubricant content range in the present invention showed a high haze value. In addition, in the case of Comparative Example 4, it can be seen that the fluorinated olefin lubricant does not impart adequate release property to the resin.

As can be seen from the above, when the fluorinated olefin type lubricant is added as a lubricant in the range defined by the present invention, gas generation amount and pyrolysis migration substance generation can be reduced in a high temperature environment of the resin, and excellent molded article can be provided through appropriate release property. Can be obtained.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (10)

(A) To 100 parts by weight of a polyester resin containing 50 to 90% by weight of (a-1) polybutylene terephthalate resin and 10 to 50% by weight of (a-2) polyethylene terephthalate resin, (B) 0.1 to 10 parts by weight of the inorganic filler; (C) 0.005 to 5 parts by weight of a stabilizer; And (D) 0.005 to 5 parts by weight of fluorinated olefin lubricant Polyester resin composition comprising a. The method of claim 1, The intrinsic viscosity [?] Of the polybutylene terephthalate resin (a-1) is 0.36 to 1.60 dl / g, the polyester resin composition. The method of claim 1, The intrinsic viscosity [?] Of the polyethylene terephthalate resin (a-2) is 0.5 to 1 dl / g, a polyester resin composition. The method of claim 1, (B) the inorganic filler is selected from the group consisting of titanium whiskers, talc, wollastonite, bentonite, montmorillonite, calcium carbonate, clay, kaolin, and combinations thereof. The method of claim 1, The inorganic filler (B) is a polyester resin composition having an average particle diameter of 0.1 to 2㎛. The method of claim 1, The stabilizer (C) is a polyester resin composition selected from the group consisting of phosphoric acid, phosphorous acid, phosphorous acid esters, phosphorus compounds, acidic phosphoric acid esters, and combinations thereof. The method of claim 1, The (D) fluorinated olefin lubricant is tetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / vinylidene fluoride copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, ethylene / tetrafluoro A polyester resin composition selected from the group consisting of an ethylene copolymer, a perfluoropolyether represented by the following formula (1), and a combination thereof. [Formula 1]

(Where n is an integer from 1 to 300). The method of claim 1, The thermoplastic resin composition is selected from the group consisting of the (D) fluorinated olefin lubricant and (D ') montan wax, metal salt of montanic acid, polyethylene wax, silicone oil, metal salt of stearyl acid, and combinations thereof. A polyester resin composition comprising a mixture of lubricants. The method of claim 8, The mixture of the lubricant is a polyester resin composition (D) fluorinated olefin-based lubricant and (D ') other lubricant is mixed in a weight ratio of 1 to 10: 1. The molded article manufactured from the polyester resin composition of any one of Claims 1-9.