KR100566910B1 - Polycarbonate/polyester resin composition containing uv absorbers - Google Patents

Abstract

The present invention relates to a polycarbonate / polyester or copolyester resin composition comprising an ultraviolet absorber. When the ultraviolet absorbent having a phenolic ester structure is added to the polycarbonate / polyester or copolyester mixture, the yellowing phenomenon is greatly reduced under high temperature processing conditions, unlike the conventional benzotriazole-based or triazine-based ultraviolet absorbents. It was found that the weather resistance was improved at the same time. Such a resin composition of the present invention is (A) 9 to 90% by weight of an aromatic polycarbonate resin, (B) 90 to 9% by weight of at least one resin selected from the group consisting of polyester resin and copolyester resin, (C) phenolic 0.05 to 2 wt% of an ultraviolet absorber having an ester structure, and (D) 0.05 to 2 wt% of an aromatic phosphite or aliphatic phosphite compound may be further included.

Polycarbonate, Polyester, Copolyester, Ultraviolet Absorber, Color Stability, Weather Resistance

Description

Polycarbonate / polyester resin composition containing ultraviolet absorber {POLYCARBONATE / POLYESTER RESIN COMPOSITION CONTAINING UV ABSORBERS}

The present invention relates to a polycarbonate / polyester resin composition, and in detail, it is possible to colorize in various colors without coloring such as yellowing during high temperature processing while maintaining inherent transparency of polycarbonate, and improved weatherability. It relates to a polyester resin composition. The resin composition of the present invention may include a polycarbonate / polyester or copolyester mixture, a ultraviolet absorber having a phenolic ester structure, and may further include a phosphite compound used as an antioxidant and a reaction inhibitor.

Representative polycarbonate resins are general purpose thermoplastic engineering plastics prepared by polycondensation of bisphenol A with phosgene and having a glass transition temperature of around 150 ° C. The polycarbonate resin is a high heat-resistant engineering plastic that replaces glass because of excellent mechanical properties such as tensile strength and impact strength, and excellent numerical stability, heat resistance, and optical transparency, such as housing of electrical and electronic products, or for building and advertising plates. The field of use is increasing day by day. The physical properties of the polycarbonate resin as described above are derived from the phenyl group and the carboxyl group, and the molecular structural properties such as the rigidity of the molecular chain and the bondage of rotation affect the physical properties. However, polycarbonate resins have limited chemical resistance and require caution when used for contact with organic solvents, certain detergents, strong alkalis, certain fatty acids, oils and greases.

In the past, efforts have been made to blend polycarbonate with other thermoplastic resins, such as polyester resins, to improve the properties of the polycarbonate. For example, US Pat. No. 3,218,372 discloses resin compositions in which polycarbonate and polyalkylene terephthalate are mixed to lower melt viscosity and improve ductility than polyalkylene terephthalate. U. S. Patent 4,391, 954 discloses a resin composition consisting of a copolyester consisting essentially of repeating units derived from a mixture of polycarbonate with isophthalic acid, terephthalic acid and 1,4-cyclohexanedimethanol. U.S. Patent No. 4,634,737 discloses a copolyester and olefin acrylate copolymer consisting of isophthalic acid, terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol, with copolymerized polycarbonates having 25 to 90 mole percent ester bonds. The composition is disclosed. US Pat. No. 4,188,314 also discloses sheet moldings with improved chemical resistance, including polycarbonates and copolyesters derived from isophthalic acid, terephthalic acid and 1,4-cyclohexanedimethanol.

However, the polycarbonate resin has a disadvantage in that it is easily yellowed by ultraviolet rays and its weather resistance is not sufficient, so that the use of the polycarbonate resin is significantly limited when it is used outdoors or indoors under fluorescent lamp irradiation. In addition, the polycarbonate resin is damaged by the strong ultraviolet irradiation, the surface is easily cracked to occur, there is a problem that the gloss (gloss) of the polycarbonate resin is reduced and the haze (haze) is increased.

Polyesters (polyalkylene terephthalates, copolyesters, or copolyester elastomers, etc.) are also known to decompose when exposed to ultraviolet light. The degradation effect of ultraviolet light on polyester resins is typically manifested by a dramatic change in color of the resin. That is, when exposed to ultraviolet rays, the yellowing of the polyester occurs. Therefore, polycarbonate and polyester are very important for protection against ultraviolet rays in terms of mechanical properties and optical.

Various methods have conventionally been used to improve the ultraviolet stability of polycarbonates and polyesters. The conventional method is a method of using an ultraviolet absorber as an additive in a resin, and attempted to overcome problems such as yellowing or weather resistance by using various types of ultraviolet absorbers alone or in combination. UV absorbers typically used in polycarbonates and polyesters are benzotriazole-based, triazine-based, and HLS-based hindered Amine Light Stabilizer (HALS) compounds and the like, and various types of ultraviolet absorbers are well known. For example, US Pat. No. 3,215,725 discloses the use of bis cyano-diphenyl-acrylic acid esters, US Pat. No. 4,812,498 uses bis benzotriazole, and UK Pat. No. 2,290,745 uses triazine compounds as ultraviolet absorbers. Doing.

However, when benzotriazole- or triazine-based UV absorbers are added to the polycarbonate / polyester or copolyester mixture as UV absorbers, the resistance to UV rays is somewhat improved, but yellowing occurs at high temperatures, resulting in a change in base color. There is a problem of sudden deterioration. As such, when the basic color is lowered, there is a problem in that it is difficult to color to various colors and thus the merchandise is inferior.

Accordingly, the inventors have found that the use of an ultraviolet stabilizer having a phenolic ester structure in a polycarbonate / polyester or copolyester mixture significantly improves yellowing during weathering, basic color and high temperature processing, and prevents oxidation and reaction. The use of phosphite compounds as inhibitors has been found to significantly reduce yellowing and further improve the underlying color.

Accordingly, an object of the present invention is to provide a polycarbonate / polyester or copolyester resin composition having excellent resistance to ultraviolet rays and having improved color stability at basic colors and at high temperatures.

The present invention relates to a polycarbonate / polyester or copolyester resin composition comprising a ultraviolet absorber having a phenolic ester structure, and more specifically, (A) 9 to 90% by weight of an aromatic polycarbonate resin, ( B) 90 to 9% by weight of at least one resin selected from the group consisting of a polyester resin and a copolyester resin, (C) 0.05 to 2% by weight of an ultraviolet absorber having a phenolic ester structure, and (D) an aromatic phosphite Or it is a resin composition further comprising 0.05 to 2% by weight of an aliphatic phosphite compound and relates to a resin composition characterized in that the basic color is extremely improved and weather resistance is improved without problems such as coloring at high temperature processing conditions.

Referring to the present invention in more detail as follows.

(A) aromatic polycarbonate (hereinafter 'PC')

Thermoplastic aromatic PC resins can be prepared by polymerizing a dihydric phenol monomer and a carbonate precursor monomer in the presence of a molecular weight modifier to control the molecular weight.

The dihydric phenols may be any substance derived from the structure of Formula 1 below.

Wherein X is a straight, branched or cyclic aliphatic alkylene having no functional group, or is a straight, branched or cyclic containing functional group such as sulfide, ether, sulfoxide, sulfone, phenyl, naphthyl and isobutylphenyl Aliphatic alkylene, preferably straight, branched or cyclic alkylene containing 1 to 10 carbons,

R ₁ and R ₂ represent a halogen atom, a straight, branched or cyclic alkyl group,

n and m independently represent the integer of 0-4.

Examples of the dihydric phenols include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) naphthylmethane and bis (4-hydroxyphenyl). )-(4-isobutylphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1-ethyl-1,1-bis (4-hydroxyphenyl) propane, 1-phenyl-1,1 -Bis (4-hydroxyphenyl) ethane, 1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, 1,10-bis ( 4-hydroxyphenyl) decane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane, or 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and the like But not representative of these are bisphenol A described above.

The carbonate precursor is another monomer of the PC resin, including but not limited to, for example, carbonyl chloride, carbonyl bromide, bis halo formate, diphenyl carbonate or dimethyl carbonate, and the like, and phosgene (carbonyl chloride). Is preferably used.

As the molecular weight modifier, a monofunctional compound similar to a known material, that is, a monomer used in PC production, may be used. Such monofunctional materials are based on, for example, phenols such as para-isopropylphenol, para-t-butylphenol, para-cumylphenol, para-isooctylphenol, and para-isononylphenol. Derivatives or aliphatic alcohols may be used, but is not limited thereto. Among them, para-t-butylphenol (PTBP) is most preferably used.

The copolycarbonate resin according to the present invention can be synthesized by using aliphatic dibasic acids as comonomers in the synthesis of PC to react dihydric phenols and carbonate precursors as described above. Such aliphatic dibasic acids may be a substance derived from the structure of Formula 2 below.

Wherein A may be a straight, branched or cyclic aliphatic alkylene having no functional group or a straight, branched or cyclic aliphatic alkylene containing functional groups such as sulfide, ether, sulfoxide and sulfone. In the present invention, the structure of A is preferably a linear aliphatic alkyl group having 6 to 20 carbon atoms.

The aliphatic dibasic acid is, for example, adipic acid, suberic acid, subzelic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, dodecanedioic acid. Linear saturated aliphatic dibasic acids, branched saturated aliphatic dibasic acids, cyclic saturated aliphatic dibasic acids such as dodecanedioic acid, hexadecanedioic acid, decanedioic acid, and tetracosanedioic acid And unsaturated aliphatic dibasic acids, but may be used by mixing these materials. In order to meet the object of the present invention, sebacic acid and dodecanedioic acid are preferable.

On the other hand, it is preferable that the aromatic PC resin which can be used for this invention uses the thing whose viscosity average molecular weights (Mv) measured in the methylene chloride solution are 17,000-40,000, and it is more preferable to use 20,000-30,000 things. When the average molecular weight is less than 17,000, mechanical properties such as impact strength and tensile strength are significantly lowered. When the average molecular weight is more than 40,000, there is a problem in processing of the resin due to an increase in melt viscosity.

In addition, the aromatic PC resin usable in the present invention may use one or more PC resins including monomers of the above-mentioned dihydric phenols and carbonate precursors, preferably linear, branched, or cyclic polycarbonates and copolys. One or more resins selected from the group consisting of carbonate resins can be used.

As the aromatic PC resin, which may be used in the present invention, 9 to 90 wt% may be used based on the total resin composition. If the aromatic PC resin is less than 9% by weight can not exhibit the inherent physical properties of the PC resin, such as impact resistance, if more than 90% by weight has a disadvantage of poor chemical resistance.

(B) at least one resin selected from the group consisting of polyester resins and copolyester resins

The polyesters or copolyesters of the present invention consist of at least one aromatic, aliphatic, or cycloaliphatic dicarboxylic acid compound and at least one aliphatic or cycloaliphatic glycol moiety. Preferably the aromatic dicarboxylic acid consists of 6 to 20 carbon atoms and the aliphatic or cycloaliphatic dicarboxylic acid consists of 3 to 20 carbon atoms. Aliphatic or cycloaliphatic glycols consist of 2 to 20 carbon atoms.

Polyester and copolyester can be synthesize | combined using a dicarboxylic acid compound and a glycol compound.

Dicarboxylic acid compounds that can be used in the present invention include terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, seba Acid, 1,4-, 1,5-, 2,3-, 2,6-, or 2,7-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, or 4,4 ' Dibenzyldi carboxylic acid and the like, but not limited thereto, and preferred dicarboxylic acid compounds are terephthalic acid, isophthalic acid or mixtures thereof.

Glycol compounds include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1, 2-, 1,3-, or 1,4-cyclohexanedimethanol, neopentyl glycol, or 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and the like, but are not limited thereto. The glycol compound is ethylene glycol, cyclohexanedimethanol or mixtures thereof.

Preferred polyesters for the present invention are polyalkylene terephthalates, more preferably polyethylene terephthalate (PET) or polybutylene terephthalate (PBT). Further preferred copolyesters of the present invention are copolyesters wherein the dicarboxylic acid moiety is terephthalic acid and the glycol moiety contains 30 to 50 mole% ethylene glycol and 50 to 70 mole% cyclohexanedimethanol. When cyclohexanedimethanol is 50 mol% or less, there is a problem of opacity when blending with polycarbonate, and when cyclohexanedimethanol exceeds 70 mol%, impact strength is lowered when blending with polycarbonate and when used at high temperature Occurs due to crystallization.

Processes for preparing polyesters and copolyesters using dicarboxylic acids and glycol compounds usually proceed in two steps: ester reactions and polycondensation reactions. Copolyesters are used with terephthalic acid, cyclohexanedimethanol, and ethylene glycol. The method for preparing an ester is as follows.

In the first step, the ester reaction is carried out so that the total glycol component including ethylene glycol and cyclohexane dimethanol is 1.05 to 2.5 in molar ratio with respect to dicarboxylic acid components such as terephthalic acid and the like at 230 to 260 ° C and 0.1 to 0.3 kg / cm 2. Carry out under the following conditions. In this case, the cyclohexanedimethanol to be used has isomers of cis- and trans-, but preferably the amount of trans isomer is 60% or more, and the reaction temperature is preferably 240 to 260 ° C, more preferably. Is 245-255 degreeC. In addition, the esterification reaction time usually takes about 100 to 300 minutes, which is affected by the reaction temperature, the pressure and the molar ratio of the monomers used.

In the ester reaction, conventional stabilizers and coloring agents can be used as other additives. Stabilizers can generally be used phosphoric acid, trimethyl phosphate or triethyl phosphate and the like, the content of the stabilizer is 10 to 200ppm relative to the weight of the final polymer based on the amount of phosphorus element. If the addition amount of the stabilizer is less than 10ppm, the effect of stabilization is insignificant, and if it exceeds 200ppm, there is a problem that the desired degree of polymerization cannot be reached. In addition, examples of the colorant added to improve the color include conventional colorants such as cobalt acetate and cobalt propionate, and the addition amount thereof is preferably 10 to 100 ppm relative to the weight of the final polymer. In addition to the colorant, it is also possible to use an organic compound as the colorant.

The second step, the polycondensation step is usually carried out under reduced pressure conditions of 250 ~ 290 ℃ and 400 ~ 0.1mmHg. This polycondensation step is carried out for the required time until the desired intrinsic viscosity is reached, the reaction temperature is preferably 260 ~ 280 ℃. In addition, the polycondensation reaction can be carried out under reduced pressure of 400 ~ 0.1mmHg in order to remove the glycol produced as a by-product to obtain a copolyester copolymerized with cyclohexane dimethanol.

On the other hand, the above (B) resin component that can be used in the present invention can be used 90 to 9% by weight relative to the total resin composition. If the resin component (B) is less than 9% by weight, the chemical resistance is lowered, and if it exceeds 90% by weight, the impact resistance is inferior.

(C) UV absorber having phenolic ester structure

The ultraviolet absorbent having a phenolic ester structure has the structure of Formula 3 as follows.

In Formula 3, R ₃ to R ₆ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Of the ultraviolet absorbers having such a phenolic ester structure having the structure of [Formula 2], in particular, tetraethyl 2,2 '-(1,4-phenylenedimethylidine) bis in which R ₃ to R ₆ are substituted with an ethyl group Preference is given to applying malonate (Tetraethyl 2,2 '-(1,4-phenylenedimethylidyne) bismalonate). At this time, the addition amount of the ultraviolet absorber is preferably applied at 0.05 to 2% by weight, more preferably at 0.1 to 1% by weight. When the amount of the ultraviolet absorber is less than 0.05% by weight, it is difficult to achieve a sufficient effect for improving the weather resistance of the resin composition, and when the amount of the ultraviolet absorber exceeds 2% by weight, problems such as bleeding and gas generation are caused. There is a problem that the surface of the molded article is poor.

(D) phosphite compounds

The resin composition according to the present invention further comprises an aromatic phosphite or aliphatic phosphite as an antioxidant and reaction inhibitor.

Typically the polycarbonate and polyester mixture composition is slightly yellowish. The degree of discoloration is affected by the composition, processing temperature and processing conditions. The higher the processing temperature, the longer the residence time, the worse the yellowing phenomenon. This yellowing occurs because the esterification reaction occurs between the polycarbonate and the polyester by the catalyst remaining during the synthesis of the polyester. This yellowing phenomenon can be reduced by adding aromatic phosphite or aliphatic phosphite compounds during processing.

In the case of the aromatic phosphite that can be used in the composition of the present invention, it usually has a structure represented by the following formula (4).

In Formula 4, at least one of R ₇ , R _8, and R ₉ is an aryl radical, preferably phenyl or phenyl substituted with linear or branched alkyl having 1 to 8 carbon atoms.

In the case of aliphatic phosphites that can be used in the composition of the present invention, it has a structure of general formula (5) as follows.

In Formula 5, R ₁₀ , R _11, and R ₁₂ are all aliphatic radicals, preferably linear or branched alkyl having 1 to 18 carbon atoms. Examples of such linear or branched alkyls include methyl, ethyl, propyl, isopropyl, pentyl, hexyl, isohexyl, allyl, isonolyl, t-butyl, lauryl, or stearyl.

Preferred phosphite compounds for the present invention are selected based on the combination of the effects of reduced pigmentation, bleed, reduced smoke and known secondary antioxidant properties.

Preferred phosphite compounds of the present invention are as follows.

Triga (2,4-di-t-butylphenyl) phosphite under the trade name Irgafos 168 sold by Ciba specialty chemicals.

Bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite under the trade name Ultranox 626 sold by Crompton.

Distearyl pentaerythritol diphosphite under the trade name Weston 619F available from Crompton.

Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite under the trade name ADK STAB PEP-36 available from Asahi Denka.

Tetrakis (2,4-di-t-butylphenyl) -4-4'biphenylene-diphosphite under the tradename Irgafos P-EPQ sold by Ciba specialty chemicals.

At this time, the addition amount of the phosphite compound is preferably applied at 0.05 to 2% by weight, more preferably at 0.1 to 1% by weight. When the addition amount of the phosphite compound is less than 0.05% by weight, the addition effect is hardly exhibited, and when the addition amount of the phosphite compound exceeds 2% by weight, there is a problem such as gas generation during molding.

On the other hand, the resin composition of the present invention may additionally include a variety of additives for various purposes, the type and content thereof is according to those skilled in the art. For example, impact modifiers and nucleating agents to improve mechanical properties, lubricants and anti-separation agents to improve surface properties, flame retardants to improve chemical properties, colorants (dyes) to improve aesthetic properties, deodorants and deodorants, and It may further include a fluidizing agent, a release agent and the like for improving the processing properties.

The method for producing a resin composition of the present invention by kneading and extruding with a twin screw melt kneading extruder at a temperature of 240 ~ 280 ℃ by a commonly used blending method to produce a pellet for molding, the pellet at 90 ~ 120 ℃ 4 hours or more It is prepared by hot air drying. As described above, various molded articles may be manufactured using a resin composition prepared as described above through a processing method such as injection molding.

Hereinafter, the present invention will be described in more detail by describing preferred embodiments of the present invention and comparative examples for this purpose. However, the present invention is not limited to the following examples, and various forms of embodiments can be implemented within the scope of the appended claims, and the following examples are only common in the art while making the disclosure of the present invention complete. It is intended to facilitate the implementation of the invention to those with knowledge.

Examples 1-2 and Comparative Examples 1-7

Typically, titanium-based metal catalysts are used in the polymerization of polyesters and copolyesters. Such a catalyst may not be practically removed and may remain in polyester and copolyester, thereby promoting a reaction when blending with another resin or reacting with an additive, which may cause problems such as yellowing. In order to confirm the discoloration caused by the reaction between the ultraviolet absorber and the titanium-based metal catalyst, a titanium metal catalyst and an ultraviolet absorber were added to a 10 ml solution of methylene chloride in a transparent glass test tube at 25 ° C. and sufficiently stirred as shown in Table 1 below. Color change was visually observed. The composition of each Example and Comparative Example and the color of the experimental results are shown in Table 1 below.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Composition (ppm) catalyst TBT ¹ 100 - 100 100 100 100 - - - TPT ² - 100 - - - - 100 100 100 UV absorbers UVA1 ³ 500 500 - - - - - - - UVA2 ⁴ - - 500 - - - 500 - - UVA3 ⁵ - - - 500 - - - - - UVA4 ⁶ - - - - 500 - - 500 - UVA5 ⁷ - - - - - 500 - - 500 color color Colorless Colorless yellow yellow yellow yellow yellow yellow yellow 1.TBT: tetrabutyl titanate 2. TPT: tetraisopropyl titanate 3. UVA1: tetraethyl 2,2 '-(1,4-phenylenedimethylidine) bismalonate 4. UVA2: 2- (2H- Benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol trade name of Ciba Specialty Chemical Tinuvin 329 5. UVA3: 2- (2H-benzotriazol-2-yl) Trade name Tinuvin 234 of Ciba specialty chemical with -4,6-bis (1-methyl-1 phenylethyl) phenol 6. UVA4: 2,2'- methylenebis (6- (2H- benzotriazol-2-yl)- Trade Names of Asahi Denka as 4-1,1,3,3-tetramethylbutyl) phenol LA 31 7. UVA5: 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-tri Ajin-2-yl) -5-octyloxyl-phenolo brand name UV1164 of Cytec Industries

As shown in Table 1, Examples 1 and 2 to which a UV absorber having a phenolic ester structure were added do not form a complex with TBT and TPT, which are titanium metal catalysts commonly used in polyester polymerization. In contrast, the colorless color was shown, but Comparative Examples 1 to 7, in which benzotriazole or triazine-containing ultraviolet absorbers were added, were all formed with a metal catalyst and were discolored to yellow.

Examples 3 to 10 and Comparative Examples 8 to 13

Next, the compositions shown in Tables 2 and 3 were mixed and uniformly dispersed in a Henschel mixer, and then extruded at a temperature of 250 to 280 ° C. using a biaxial melt-mixing extruder having L / D = 40 and φ = 25 mm to form pellets. Prepared. The prepared pellets were dried in a hot air dryer at 90 to 120 ° C. for at least 4 hours, and then injection molded to form a 3 mm thick specimen. Using this test piece, the yellowness index (YI) was measured by permeation according to ASTM D1925. At this time, in order to evaluate the color stability in the basic color and high temperature processing conditions, the injection molding conditions were set to 280 ℃ and 320 ℃ injection molding. The basic color was evaluated by the yellow index of the specimen molded _{at 280 ℃} and the color stability was evaluated from the change of the yellow index (ΔYI _{320 ℃-280 ℃} ) of the specimen formed at 280 ℃ and 320 ℃.

In addition, ΔYI after 1,000 hours of ultraviolet irradiation was measured using a weather-O-meter (Atlas Model Ci65) to evaluate the weather resistance of the injection molded specimen at 280 ° C. The weather resistance test was performed using a xenon lamp, the amount of light at a wavelength of 340 nm was set to 0.35 W / m 2, the black panel temperature was set to 63 ° C., and the rain and ultraviolet irradiation 18 minutes and the ultraviolet irradiation 102 minutes were repeated for 1,000 hours. . The smaller the ΔYI, the better the weather resistance. Table 2 and Table 3 show the compositions and experimental results of Examples and Comparative Examples, respectively.

Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Composition (wt%) Polycarbonate ¹ 49.75 49.75 49.8 49.8 49.9 79.75 19.75 49.85 Copolyester ² 49.75 49.75 49.8 49.8 49.9 19.75 79.75 49.85 UVA1 0.3 0.3 0.3 0.2 0.1 0.3 0.3 0.3 PO1 ³ 0.2 - 0.1 0.2 0.1 0.2 0.2 - PO2 ⁴ - 0.2 - - - - - - Yellow index Yellow Index (YI _{280 ℃} ) 1.29 1.32 1.32 1.25 1.26 1.17 1.42 1.85 Yellow Index (YI _{320 ℃} ) 1.48 1.50 1.53 1.42 1.44 1.33 1.68 2.23 ΔYI _{320 ℃ -280 ℃} 0.19 0.18 0.21 0.17 0.18 0.16 0.26 0.38 Weather Resistance (ΔYI) Yellow Index (YI _Initial ) 1.29 1.32 1.32 1.25 1.26 1.17 1.42 1.85 Yellow Index (YI _{1000 hours} ) 6.55 6.73 6.7 7.08 7.8 6.31 7.35 7.17 ΔYI 5.26 5.41 5.38 5.83 6.54 5.14 5.93 5.32 1. Polycarbonate: linear polycarbonate derived from bisphenol-A, intrinsic viscosity 0.55 dl / g at 25 ° C. in methylene chloride 2. copolyester: 100 mol% terephthalic acid, 60 mol% 1,4-cyclo Consisting of hexanedimethanol and 40 mol% ethylene glycol, intrinsic viscosity 0.75 dl / g (25 ° C., in 50/50 solution of phenol / tetrachloroethane) 3. PO1: bis (2,4-di-t-butyl Phenyl) pentaerythritol diphosphite, trade name Ultranox 626 sold by Crompton. PO2: Distearyl pentaerythritol diphosphite, trade name Weston 619F sold by Crompton.

Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Composition (wt%) Polycarbonate 49.75 49.75 49.85 50 79.75 19.75 Copolyester 49.75 49.75 49.85 50 19.75 79.75 UVA1 - - - - - - UVA2 0.3 - 0.3 - 0.3 0.3 UVA5 - 0.3 - - - - PO1 0.2 0.2 - - 0.2 0.2 PO2 - - - - - - Yellow index Yellow Index (YI _{280 ℃} ) 2.54 3.45 2.95 1.78 2.31 3.23 Yellow Index (YI _{320 ℃} ) 4.26 4.40 5.27 3.13 3.96 5.08 ΔYI _{320 ℃ -280 ℃} 1.72 0.95 2.32 1.35 1.65 1.85 Weather Resistance (ΔYI) Yellow Index (YI _Initial ) 2.54 3.45 2.95 1.78 2.31 3.23 Yellow Index (YI _{1000 hours} ) 9.79 9.82 10.49 11.2 9.44 11.01 ΔYI 7.25 6.37 7.54 9.42 7.13 7.78 * The resin and ultraviolet absorber used in Comparative Examples 8 to 14 are the same as those used in Table 1 and Table 2, respectively.

As shown in Table 2 and Table 3, Examples 3 to 10 according to the present invention is excellent in the basic color and color stability compared to Comparative Examples 8 to 13 and can be seen that the yellowing phenomenon is reduced even under long-term ultraviolet irradiation. there was. Specifically, in comparison with Examples 3 and Comparative Examples 8 to 9, it can be seen that the ultraviolet absorbent of the phenolic ester structure is superior in the basic color and color stability and also excellent in weather resistance compared to the benzotriazole or triazine-based ultraviolet absorber. Could. However, it could be seen that in Comparative Example 11, in which the ultraviolet absorbent was not added, the yellowing phenomenon was large. In addition, when comparing the comparative example 8 which added the benzotriazole type ultraviolet absorber and the comparative example 9 which added the triazine type ultraviolet stabilizer, the basic color is excellent in the benzotriazole type ultraviolet absorber, but the weatherability under ultraviolet irradiation is excellent. Triazine-based UV absorbers were found to be excellent. In comparison with Example 4, Comparative Example 8, Example 10 and Comparative Example 10, it was found that the addition of the phosphite compound improves the basic color and color stability without significantly affecting the weather resistance. As in Example 3 and Example 5, it was found that addition of a small amount of phosphite compound has an effect on the basic color and color stability. In addition, as in Examples 3 to 4, the aromatic phosphite compound and the aliphatic phosphite compound had no significant difference in the effects on the basic color, color stability, and weather resistance.

The polycarbonate / polyester or copolyester resin composition and the resin molded product using the same according to the present invention are subjected to a high temperature processing condition unlike the case where a conventional benzotriazole-based or triazine-based ultraviolet absorber is applied by applying an ultraviolet absorber having a phenolic ester structure. The color is extremely improved and the weather resistance is improved without problems such as coloring in the present invention, and thus it can be used for applications such as housings of electrical and electronic materials, medical supplies, sheets, films, and the like used in outdoor environments or under ultraviolet irradiation.

Claims (8)

(A) 9 to 90% by weight of aromatic polycarbonate resin (B) a group consisting of a polyester resin and a copolyester resin     90 to 9% by weight of one or more resins selected from (C) 0.05 to 2% by weight of a ultraviolet absorber having a phenolic ester structure of the formula Thermoplastic resin composition comprising a. [Formula 3]

In the above formula, R ₃ to R ₆ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The resin composition according to claim 1, further comprising 0.05 to 2% by weight of (D) an aromatic phosphite or aliphatic phosphite compound. The thermoplastic resin composition of claim 1, wherein the aromatic polycarbonate resin of (A) is at least one selected from the group consisting of linear, branched, or cyclic polycarbonates and copolycarbonate resins. The resin composition according to claim 1 or 3, wherein the aromatic polycarbonate resin of (A) has a viscosity average molecular weight (Mv) of 17,000 to 40,000. The method of claim 1, wherein the polyester of (B) is a polyalkylene terephthalate, and the copolyester is 50 to 70 mol% of cyclohexanedimethanol and 30 to 50 mol of dicarboxylic acid portion and terephthalic acid. A resin composition comprising% ethylene glycol. The resin composition according to claim 1, wherein the ultraviolet absorber of (C) is tetraethyl 2,2 '-(1,4-phenylenedimethylidine) bismalonate. The method of claim 2, wherein the aromatic phosphite compound or aliphatic phosphite compound of (D) is tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) penta Erythritol diphosphite, distearyl pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, and tetrakis (2,4-di-t It is at least one phosphite compound selected from the group consisting of -butylphenyl) -4-4'biphenylene-diphosphite. The resin composition of claim 1, further comprising an additive selected from the group consisting of colorants, impact modifiers, mold release agents, nucleating agents, flame retardants, deodorants, deodorants, anti-separation agents, glidants and lubricants.