JP2008127557A - Polycarbonate resin composition containing red dyestuff, and molded article made from the resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition containing a red dyestuff which is excellent in thermal stability and weatherability without damaging the characteristics of polycarbonate resins, and to provide a molded article molded from the resin composition. <P>SOLUTION: The polycarbonate resin composition containing the red dyestuff is characterized by blending 0.0001-0.5 pt.wt. of a perinone type red dyestuff (b component) comprising a compound represented by structural formula (I) as a main component and 0.001-1 pt.wt. of a phosphorus type stabilizer (c component) to 100 pts.wt. of the polycarbonate resin (a component). The molded article is characterized by being manufactured from the polycarbonate resin composition as a raw material. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a polycarbonate resin composition containing a red dye, and a molded article made of the resin composition. More specifically, the present invention relates to a polycarbonate resin composition containing a red dye excellent in thermal stability and weather resistance without impairing the characteristics of the polycarbonate resin, and a molded article produced by molding from this resin composition.

Polycarbonate resin is excellent in mechanical strength, electrical properties, heat resistance, dimensional stability, transparency, etc., so electrical / electronic equipment parts, OA equipment, machine parts, vehicle parts, building members, various containers, leisure Used in a wide range of fields such as goods and miscellaneous goods. Among these uses, particularly in the case of parts exposed to the human eye, the raw material resin is often colored in various colors for the purpose of enhancing the decorativeness and design. In some cases, one type of dyed pigment is used for coloring the polycarbonate resin, but two or more types of dyed pigment are often used in combination, and red dyes are also frequently used for coloring the polycarbonate resin.

By the way, since the melting temperature at the time of molding polycarbonate resin is considerably high at around 300 ° C., anthraquinone type, indigoid type, perinone type, phthalocyanone type, etc. with good thermal stability are used for coloring polycarbonate resin. A dye / pigment comprising the above compound is used. On the other hand, since the weather resistance of dyes and pigments is hardly considered, when resin molded products colored with dyes and pigments are exposed to various rays of light such as sunlight and lighting for a long time, the product value is remarkably increased due to fading of the resin molded products. In many cases, the dye and pigment for polycarbonate resin is required to have excellent weather resistance as well as thermal stability.

For example, as a dye for polycarbonate resin, a dye in which anthraquinone green dye, perinone red dye and quinophthalone yellow dye are mixed in a specific ratio has been proposed (Patent Document 1), anthraquinone dye, perinone dye, Colored master pellets for optical molded articles made of thermoplastic resins such as quinoline dyes, perylene dyes, coumarin dyes or thioindico dyes and polycarbonate resins have also been proposed (for example, Patent Documents 2 to 5). There is no description about improving the weather resistance in any patent document.

Furthermore, thermoplastic resin molding materials such as specific graft copolymers, vinyl copolymers, and polycarbonate resins, and anthraquinone synthetic dyes, perinone synthetic dyes, azo synthetic dyes, methine synthetic dyes, and quinoline synthetic compounds A resin composition is proposed in which two or more primary color synthetic dyes selected from the group consisting of dyes are blackened (Patent Document 5), and also comprises a specific polycarbonate resin and a perinone dye. A polycarbonate resin composition excellent in impact resistance has been proposed (Patent Document 6), but any patent document completely describes the influence of weather resistance due to the presence of a dye blended in the resin composition. Absent.
Japanese Patent Laid-Open No. 9-3311 JP 2002-138208 A JP 2002-138209 A JP 2002-322290 A JP 2005-132970 A JP 2005-298615 A

The objective of this invention is providing the polycarbonate resin composition which eliminated the fault of the said prior art, and this resin composition molded article. That is, the object of the present invention is as follows.
1. To provide a polycarbonate resin composition containing a red dye having excellent thermal stability and weather resistance without impairing the characteristics of the polycarbonate resin.
2. To provide a colored molded article produced from a polycarbonate resin composition containing a red dye having excellent thermal stability and weather resistance without impairing the characteristics of the polycarbonate resin.

In the present invention, in order to solve the above-mentioned problems, in the first invention, a perinone red dye (component b) containing as a main component a compound represented by the following structural formula (I) with respect to 100 parts by weight of a polycarbonate resin (component a) ) 0.0001 to 0.5 parts by weight and a phosphorous heat stabilizer (component c) 0.001 to 1 part by weight, respectively, to provide a polycarbonate resin composition.

In 2nd invention, 0.0001-0.5 weight part of perinone type red dye (b component) which has as a main component the compound shown by following structural formula (I) with respect to 100 weight part of polycarbonate resin (a component). And a molded product characterized in that it is produced from a polycarbonate resin composition containing 0.001 to 1 part by weight of a phosphorous heat stabilizer (component c).

The present invention is as described in detail below, and has the following particularly advantageous effects, and its industrial utility value is extremely large.
1. In the polycarbonate resin composition according to the present invention, since the perinone red dye (component b) containing a specific compound as a main component is blended with the polycarbonate resin (component a), the polycarbonate resin composition is 300 at the time of thermoforming. Even when heated to a high temperature of around 0 ° C., the color of the polycarbonate resin composition does not fade and the thermal stability is excellent.
2. Since the polycarbonate resin composition according to the present invention contains a perinone red dye (component b) containing a specific compound as a main component in the polycarbonate resin (component a), it may be exposed to sunlight or the like. The colored molded product made of this resin composition is difficult to fade and has excellent weather resistance.
3. Since the molded article made of the polycarbonate resin composition according to the present invention has excellent thermal stability and weather resistance, electrical / electronic equipment parts, OA equipment, machine parts, heated by heat generated from the surroundings during use, It is also suitable as a vehicle part, building member, leisure article, etc. used outdoors.
4). Since the colored molded product made of the polycarbonate resin composition according to the present invention has excellent weather resistance, the colored molded product is difficult to fade even when exposed to light for a long period of time, and has high commercial value.

Hereinafter, the present invention will be described in more detail. [1] Aromatic polycarbonate resin (component a) In the resin composition according to the present invention, a polycarbonate resin (component a) as a base resin (hereinafter simply referred to as “polycarbonate resin” or “component a”) may be used. ) Is, for example, a linear or branched thermoplastic aromatic polycarbonate polymer obtained by reacting an aromatic dihydroxy compound and a carbonate precursor, or a small amount of a polyhydroxy compound in combination therewith, or a copolymer. It is a polymer. The method for producing the polycarbonate resin (component a) is not particularly limited, and can be produced by a conventionally known method. Examples of the production method include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.

As aromatic dihydroxy compounds used as raw materials, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane (= Tetrabromobisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy) Phenyl) octane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-) 3,5-dimethylphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis ( , 5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1- Bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxyphenyl) -1,1,1-trichloropropane, 2,2-bis (4 -Hydroxyphenyl) -1,1,1,3,3,3-hexachloropropane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, etc. Bis (hydroxyallyl) alkanes; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydro) Bis (hydroxyaryl) cycloalkanes exemplified by ciphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and the like; 9,9-bis (4-hydroxyphenyl) fluorene , 9,9-bis (4-hydroxy-3-methylphenyl) fluorene and the like, cardio structure-containing bisphenols; 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether Dihydroxydiaryl ethers exemplified by 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide and the like; 4,4′-dihydroxy Diphenyls Dihydroxydiaryl sulfoxides exemplified by sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, etc .; 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenyl Examples include dihydroxydiaryl sulfones exemplified by sulfone; hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, and the like.

Among these, bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A] is particularly preferable from the viewpoint of impact resistance. . These aromatic dihydroxy compounds may be used alone or in combination of two or more.

Examples of the carbonate precursor to be reacted with the aromatic dihydroxy compound include carbonyl halide, carbonate ester, haloformate and the like. Specific examples include phosgene; diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; and dihaloformates of dihydric phenols. These carbonate precursors may also be used alone or in combination of two or more.

The polycarbonate resin may be a branched aromatic polycarbonate resin that is copolymerized in the presence of a small amount of a trifunctional or higher polyfunctional aromatic compound. Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6- Tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3, 1,3,5-tri (4-hydroxyphenyl) benzene, 1, Polyhydroxy compounds exemplified by 1,1-tri (4-hydroxyphenyl) ethane and the like, or 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chloroisatin, 5, Examples thereof include 7-dichloroisatin and 5-bromoisatin. Among these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferable. The polyfunctional aromatic compound can be used by substituting a part of the aromatic dihydroxy compound, and the amount used is preferably in the range of 0.01 to 10 mol% with respect to the aromatic dihydroxy compound, The range of 0.1-2 mol% is more preferable.

Next, the manufacturing method of polycarbonate resin is demonstrated. First, in the interfacial polymerization method, in the presence of an organic solvent inert to the reaction, an aqueous alkaline solution, the pH is usually kept at 9 or higher, an aromatic dihydroxy compound, and a molecular weight modifier (terminal stopper) as necessary, In addition, an antioxidant is used for the purpose of preventing oxidation of the aromatic dihydroxy compound, and after reacting with phosgene, a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt is added to perform interfacial polymerization. Can give polycarbonate. The timing of adding the molecular weight modifier to the polymerization system is not particularly limited as long as it is between the time of phosgenation and the time of initiation of the polymerization reaction. In addition, reaction temperature is 0-40 degreeC, for example, and reaction time is several minutes (for example, 10 minutes)-several hours (for example, 6 hours), for example.

Examples of the organic solvent inert to the reaction used in the interfacial polymerization method include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene, and aromatic hydrocarbons such as benzene, toluene and xylene. Etc. Examples of the alkali compound for preparing the alkaline aqueous solution include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Examples of the molecular weight regulator include compounds having a monovalent phenolic hydroxyl group. Examples of the compound having a monovalent phenolic hydroxyl group include m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, pt-butylphenol, and p-long chain alkyl-substituted phenol. The addition amount of the molecular weight modifier is preferably 0.5 to 50 mol, more preferably 1 to 30 mol, per 100 mol of the aromatic dihydroxy compound.

Polymerization catalysts include tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine, pyridine, and quaternary compounds such as trimethylbenzylammonium chloride, tetramethylammonium chloride, and triethylbenzylammonium chloride. Ammonium salts are mentioned.

Next, the melt transesterification method is, for example, a transesterification reaction between a carbonic acid diester and an aromatic dihydroxy compound. Examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate, and substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate. Among the carbonic acid diesters, diphenyl carbonate or substituted diphenyl carbonate is preferable, and diphenyl carbonate is more preferable.

In this production method, generally, a polycarbonate having a desired molecular weight and a terminal hydroxyl group amount is obtained by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound or adjusting the degree of vacuum during the reaction. A resin is obtained. As a more aggressive method, it can be adjusted by adding a terminal terminator separately during the reaction. In this case, examples of the terminal terminator include monohydric phenols, monohydric carboxylic acids, and carbonic acid diesters. The amount of terminal hydroxyl groups greatly affects the thermal stability, hydrolysis stability, color tone, etc. of the aromatic polycarbonate resin which is the A1 component. The amount of the terminal hydroxyl group is preferably 1000 ppm or less, more preferably 700 ppm or less in order to provide practical physical properties, although it depends on the use of the resin composition finally obtained. Moreover, in the polycarbonate resin manufactured by the transesterification method, the amount of terminal hydroxyl groups is preferably 100 ppm or less. By setting it as the amount of such terminal hydroxyl groups, the fall of molecular weight can be suppressed and a color tone can also be made more favorable. Accordingly, it is more preferable to use the carbonic acid diester in an amount of equimolar amount or more, for example, 1.01 to 1.30 mol with respect to 1 mol of the aromatic dihydroxy compound.

When producing a polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. As the transesterification catalyst, those conventionally used can be used without particular limitation. Specific examples include alkali metal compounds and alkaline earth metal compounds. In addition, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound can be used in combination. As the transesterification reaction using the above raw materials, the reaction is usually carried out at a temperature of 100 to 320 ° C., and finally, melt polycondensation is performed while removing by-products such as aromatic hydroxy compounds under a reduced pressure of 300 Pa or less. The method of performing reaction is mentioned.

Although the melt transesterification method can be carried out batchwise or continuously, it is preferably carried out continuously in view of the stability of the resin composition finally obtained. The aromatic polycarbonate resin obtained by the melt transesterification method contains a residual catalyst, and this residual catalyst adversely affects the thermal stability during the molding of the aromatic polycarbonate resin. It is preferable to add an agent. The deactivator is preferably a compound that neutralizes the used catalyst, for example, a sulfur-containing acidic compound or a derivative formed therefrom. The compound that neutralizes such a catalyst is preferably added in the range of 0.5 to 10 equivalents, more preferably 1 to 5 equivalents, relative to the alkali metal contained in the used catalyst. In addition, the compound that neutralizes such a catalyst is preferably added in the range of 1 to 100 ppm, more preferably 1 to 20 ppm, based on the aromatic polycarbonate resin.

In the present invention, the molecular weight of the polycarbonate resin is not particularly limited as long as it is in a range that can be used as a molding material, and the viscosity average molecular weight [Mv] converted from the solution viscosity is in the range of 10,000 to 50,000. preferable. When the viscosity average molecular weight of the polycarbonate resin is 10,000 or more, the mechanical strength is improved, and it is more suitable for use in applications requiring high mechanical strength. On the other hand, when the viscosity average molecular weight is 50,000 or less, a decrease in fluidity can be improved, which is preferable from the viewpoint of moldability. A more preferable range of the viscosity average molecular weight is 12,000 to 40,000, and a further preferable range is 14,000 to 30,000. Moreover, the mixture of 2 or more types of polycarbonate resin from which a viscosity average molecular weight differs may be sufficient. If the viscosity average molecular weight of the mixture is within the above range, the viscosity average molecular weight of each polycarbonate resin may exceed the above range.

In the present invention, the viscosity average molecular weight [Mv] means methylene chloride as a solvent, an Ubbelohde viscometer, an intrinsic viscosity [η] (unit dl / g) at a temperature of 20 ° C., and a Schnell viscosity. It means a value calculated from the equation, that is, η = 1.23 × 10 ⁻⁴ M ^0.83 . Here, the intrinsic viscosity [η] is a value calculated from the following formula (II) by measuring the specific viscosity [ηsp] at each solution concentration [C] (g / dl).

The component a may contain an aromatic polycarbonate oligomer in order to improve fluidity during thermoforming and appearance of the molded product. The aromatic polycarbonate oligomer has a viscosity average molecular weight [Mv] of preferably 1,500 to 9,500, more preferably 2,000 to 9,000. The aromatic polycarbonate oligomer is preferably contained in the range of 30% by weight or less of the component a.

The component a may be not only a so-called virgin raw material but also an aromatic polycarbonate resin regenerated from a used product, a so-called recycled aromatic polycarbonate resin. Used products include optical recording media such as optical discs, light guide plates, vehicle transparent parts such as automobile window glass, automobile headlamp lenses and windshields, containers such as water bottles, eyeglass lenses, soundproof walls and glass windows, These include building materials such as corrugated plates, and safety equipment such as helmets and bulletproof shields. Further, it may be a non-conforming product, a pulverized product obtained from a sprue, a runner or the like, or a pellet obtained by melting them. The regenerated aromatic polycarbonate resin is preferably 80% by weight or less of the component a, more preferably 50% by weight or less.

[2] Perinone red dye (component b)
The perinone red dye (component b) used in the resin composition of the present invention (hereinafter sometimes simply referred to as “component b”) is Solvent.
A compound mainly composed of a compound represented by the following structural formula (I) commercially available with a color index of Red 179 (hereinafter referred to as “CI Solvent”).
Red 179 ". ).

Perinone-based red dyes are mainly composed of a compound represented by the following structural formula (III) commercially available under the color index of Solvent Red 135 (hereinafter sometimes referred to as “CI Solvent Red 135”). In the present invention, CI Solvent Red 135 is not used as a perinone red dye (component b). In an experiment conducted by the present inventor, a polycarbonate resin composition in which CI Solvent Red 135 is blended with polycarbonate resin is inferior in thermal stability and heat resistance to a polycarbonate resin composition in which CI Solvent Red 179 is blended. This is because it has been clarified that the molded product obtained in the above is easily discolored.

The amount of component b is in the range of 0.0001 to 0.5 parts by weight (1 to 5000 ppm) with respect to 100 parts by weight of component a. If it is less than 0.0001 part by weight, it is difficult to color the polycarbonate resin in a desired color tone, and the final molded article has poor decorativeness and design, and if it exceeds 0.5 part by weight, the thermal stability decreases. And, since the manufacturing cost rises, neither is preferable. The preferred amount is 0.0002 to 0.3 parts by weight, and more preferably 0.0003 to 0.1 parts by weight.

[3] Phosphorus heat stabilizer (component c)
The polycarbonate resin composition according to the present invention is blended with a phosphorus compound (component c) (hereinafter sometimes simply referred to as “component c”). The component c in the present invention functions to improve the thermal stability of the polycarbonate resin composition, suppress gas generation and discoloration, and prevent a decrease in mechanical strength. Examples of phosphorus heat stabilizers include phosphites and phosphates.

Phosphites include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, trinonyl phosphite, tridecyl phosphite, trioctyl phosphite, tri Octadecyl phosphite, distearyl pentaerythritol diphosphite, tricyclohexyl phosphite, monobutyl diphenyl phosphite, monooctyl diphenyl phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butyl Phenyl) pentaerythritol phosphite, bis (2.6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-tert-butyl) Eniru) triesters of phosphorous acid, such as octyl phosphite, diesters, such as mono-ester.

Examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethylphenyldiphenyl phosphate, tetrakis (2,4-di-). tert-butylphenyl) -4,4-diphenylene phosphonite.

Of the above phosphorus heat stabilizers, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol phosphite, bis (2.6-di-tert-butyl) are preferable. -4-methylphenyl) pentaerythritol phosphite, tris (2,4-di-tert-butylphenyl) phosphite, particularly preferably bis (2,6-di-tert-butyl-4 -Methylphenyl) pentaerythritol phosphite and tris (2,4-di-t-butylphenyl) phosphite. In addition, the phosphorus heat stabilizer can also use together 1 type, or 2 or more types.

The amount of component c is in the range of 0.001 to 1 part by weight per 100 parts by weight of component a. If it is less than 0.001 part by weight, the heat stabilizer of the polycarbonate resin composition is inferior, and if it exceeds 1 part by weight, the effect of thermal stability according to the blending amount is not exhibited and hydrolysis tends to occur. Since the molded product finally obtained becomes cloudy, it is not preferable. A preferred blending amount is 0.005 to 0.3 part by weight.

[4] Phenolic heat stabilizer (d component)
If necessary, the polycarbonate resin composition according to the present invention can be blended with a phenol-based heat stabilizer (d component) (hereinafter sometimes referred to as “d component”). The d component in the present invention functions to improve the thermal stability of the finally obtained polycarbonate resin composition, suppress gas generation and discoloration, and prevent a decrease in mechanical strength.

Examples of the phenol-based heat stabilizer include hindered phenol-based compounds. Specific examples include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxy Phenyl) propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di -Tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxy Phenyl] methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene -2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy -M-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert-butyl) -4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) ) -1,3,5-triazin-2-ylamino) phenol, etc. Among these compounds, pentaerythritol tetrakis [3- (3,5-di-) is preferred. ert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate These two phenolic heat stabilizers are Ciba Specialty. -It is commercially available from Chemicals under the names Irganox 1010 and Irganox 1076.

The amount of component d is preferably selected in the range of 0.001 to 1 part by weight per 100 parts by weight of component a. If it is less than 0.001 part by weight, the heat stabilizer of the polycarbonate resin composition is inferior, and if it exceeds 1 part by weight, the effect of thermal stability according to the blending amount is not exhibited and hydrolysis tends to occur. Since the molded product finally obtained becomes cloudy, it is not preferable. A more preferable blending amount is 0.005 to 0.3 part by weight.

[5] Weather resistance improver (component e)
If necessary, the polycarbonate resin composition according to the present invention can be blended with a weather resistance improver (e component) (hereinafter sometimes referred to as “e component”). The e component in the present invention functions to further improve the weather resistance of the polycarbonate resin composition. Examples of the weather resistance improver include benzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzoate compounds, triazine compounds, hindered amine compounds, cinnamyl compounds, and the like. These weather resistance improvers can be used alone or in combination of two or more.

Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octa Decyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4 -Methoxybenzophenone-5-sulfonic acid trihydrate, bis (2-hydroxy-3-benzoyl-6-methoxyphenyl) methane and the like.

Examples of benzotriazole compounds include 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) -2H-benzotriazole, 2 -(2-hydroxy-3-tert-butyl-5-methylphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole, 2- (3,5- Di-t-octyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3-lauryl-5 Methyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chloro 2H-benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-bis (1-methyl-1-phenylethyl) ) -2-hydroxyphenyl) -2H-benzotriazole, bis (3- (2H-benzotriazol-2-yl) -2-hydroxy-5-methylphenyl) methane, bis (3- (2H-benzotriazole-2) -Yl) -2-hydroxy-5- (1,1,3,3-tetramethylbutyl) phenyl) methane, bis (3- (2H-benzotriazol-2-yl) -2-hydroxy-5-cumylphenyl) Methane, bis (3- (2H-benzotriazol-2-yl) -2-hydroxy-5-octylphenyl) methane, 1,1-bis (3- (2H Benzotriazol-2-yl) -2-hydroxy-5-methylphenyl) octane, 1,1-bis (3- (2H-5-chlorobenzotriazol-2-yl) -2-hydroxy-5-methylphenyl) Octane, 1,2-ethanediylbis (3- (2H-benzotriazol-2-yl) -2-hydroxybenzoate), 1,12-dodecandiylbis (3- (2H-benzotriazol-2-yl) -4- Hydroxybenzoate), 1,3-cyclohexanediylbis (3- (5-chloro-2H-benzotriazol-2-yl) -2-hydroxybenzoate), 1,4-butanediylbis (3- (2H-benzotriazole-2) -Yl) -4-hydroxy-5-methylphenylethanoate), 3,6-dioxa-1,8-oct Tandiylbis (3- (5-methoxy-2H-benzotriazol-2-yl) -4-hydroxyphenylethanoate), 1,6-hexanediylbis (3- (3- (2H-benzotriazol-2-yl) -4-hydroxy-5-t-butylphenyl) propionate), p-xylenediylbis (3- (3- (2H-benzotriazol-2-yl) -4-hydroxyphenyl) propionate), bis (3- ( 2H-benzotriazol-2-yl) -4-hydroxytoluyl) malonate, bis (2- (3- (2H-benzotriazol-2-yl) -4-hydroxy-5-octylphenyl) ethyl) terephthalate, bis ( 3- (2H-benzotriazol-2-yl) -4-hydroxy-5-propyltoluyl) octadio 2- (2H-benzotriazol-2-yl) -6-phthalimidomethyl-4-methylphenol, 2- (2H-benzotriazol-2-yl) -6-phthalimidoethyl-4-methylphenol, 2 -(2H-benzotriazol-2-yl) -6-phthalimidooctyl-4-methylphenol, 2- (2H-benzotriazol-2-yl) -6-phthalimidomethyl-4-tert-butylphenol, 2- (2H -Benzotriazol-2-yl) -6-phthalimidomethyl-4-cumylphenol, 2- (2H-benzotriazol-2-yl) -4,6-bis (phthalimidomethyl) phenol and the like.

Examples of the salicylic acid ester compounds include phenylsulcylate, 2,4-ditertiary butylphenyl 3,5-ditertiary butyl 4-hydroxybenzoate, and the like. Examples of the benzoate compound include 2,4-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate. Examples of the triazine compound include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol.

Examples of hindered amine compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and bis (1-octyloxy). -2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6, -pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl) -4-hydroxybenzyl) -2-n-butylmalonate, dimethyl succinate 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly (( 6- (1,1,3,3, -tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl) ((2,2,6,6-tetramethyl-4-piperidyl) imino ) Hexa Tylene ((2,2,6,6, -tetramethyl-4-piperidyl) imino)), N, N′-bis (3-aminopropyl) ethylenediamine · 2,4-bis (N-butyl-N- ( 1,2,2,6,6-pentamethyl-4-piperidyl) amino) -6-chloro-1,3,5-triazine condensate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) Examples include 1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate.

Other weather resistance improvers include 2-ethoxy-2′-ethyl-oxalic acid bisanilide, ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate Etc.

The amount of component e is preferably selected in the range of 0.01 to 3 parts by weight per 100 parts by weight of component a. If it is less than 0.01 part by weight, the weather resistance of the molded product obtained from the polycarbonate resin composition is insufficient, and if it exceeds 3 parts by weight, the yellow level of the molded product obtained from the polycarbonate resin composition becomes strong. Neither is desirable because it becomes difficult to adjust to a desired color tone or the e component tends to bleed out on the surface of the molded product. A more preferable blending amount is 0.05 to 1 part by weight.

[6] Release agent (component f)
If necessary, the polycarbonate resin composition according to the present invention may contain a mold release agent (component f) (hereinafter sometimes referred to as “component f”). The component f in the present invention increases the fluidity of the polycarbonate resin composition at the time of melting when the polycarbonate resin composition is thermoformed, and makes it easy to release the molded product from the mold or roll during molding. It functions to make it less likely to cause dirt and poor appearance of the molded product. Examples of the release agent include at least one compound selected from esters of aliphatic carboxylic acids having 6 to 30 carbon atoms and alcohols having 30 or less carbon atoms.

Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic carboxylic acid, dicarboxylic acid, and tricarboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among the aliphatic carboxylic acids, preferred are mono- or dicarboxylic acids having 6 to 30 carbon atoms, and more preferred are aliphatic saturated monovalent carboxylic acids having 6 to 30 carbon atoms, such as palmitic acid, stearin. Examples include acids, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, melicin, tetrariacontanoic acid, montanic acid, glutaric acid, adipic acid, and azelaic acid.

Examples of the alcohol having 30 or less carbon atoms that reacts with the aliphatic carboxylic acid to form an ester include saturated or unsaturated monohydric alcohols and saturated or unsaturated polyhydric alcohols. These alcohols may have a substituent such as a halogen group. Of these alcohols, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 or less carbon atoms are more preferable. The aliphatic alcohol includes alicyclic alcohol. Examples of the aliphatic saturated monohydric alcohol or polyhydric alcohol having 30 or less carbon atoms include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, and neopentylene. Examples include glycol, ditrimethylolpropane, and dipentaerythritol.

Specific examples of the ester of an aliphatic carboxylic acid having 6 to 30 carbon atoms and an alcohol having 30 or less carbon atoms include beeswax (mixture mainly composed of myristyl palmitate), stearyl stearate, behenyl behenate, and behenine. Octyldodecyl acid, glycerol monopalmitate, glycerol monostearate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol Examples include tetrastearate. These release agents may be used alone or in combination of two or more.

The amount of component f is preferably selected in the range of 0.01 to 1 part by weight per 100 parts by weight of component a. If it is less than 0.01 parts by weight, the releasability is insufficient, the mold cavity surface and the molded product are likely to be fused at the time of thermoforming, and when the mold is released from the mold, a mold release mark is generated. , The appearance of the molded product is deteriorated and the commercial value is lowered. On the other hand, if it exceeds 1 part by weight, the thermal stability is lowered during thermoforming, and silver streaks are likely to occur in the molded product, which is not preferable. A more preferable blending amount is 0.05 to 0.5 part by weight.

[7] Other components The polycarbonate resin composition according to the present invention can be blended with other components within a range not impairing the object of the present invention in order to exhibit desired physical properties. Examples of other components include thermoplastic resins other than polycarbonate resins, rubbery polymers, inorganic fillers, and resin additives. These other components may be used alone or in combination of two or more.

As thermoplastic resins other than polycarbonate resin, polystyrene resin, ABS resin, AES resin, AS resin, olefin resin, methacrylic resin, polyamide resin, polyacetal resin, polyphenylene ether resin (PPE resin), modified PPE resin, polyester resin, Thermoplastic resins such as polysulfone resin, polyimide resin, polyphenylene sulfide resin, polyarylate resin, polyether sulfone resin, polyether ketone resin, polyether ether ketone resin, polyester carbonate resin, amorphous polyamide resin, liquid crystal polymer, or the like The alloy resin composition which consists of 2 or more types of resin is mentioned.

Examples of rubber polymers include styrene-butadiene block copolymers, hydrogenated styrene-butadiene block copolymers in which part or all of the butadiene portion is hydrogenated, styrene-isoprene block copolymers, hydrogenated styrene- Examples include isoprene block copolymers, ethylene propylene elastomers, thermoplastic polyester elastomers, thermoplastic polyamide elastomers, and core-shell polymers having a rubbery core. Examples of the core-shell polymer having a rubber-like core include butadiene-based rubber and acrylate-based rubber as the core polymer, and examples of the shell polymer include meth- acrylate-based polymer and styrene-based polymer. .

Inorganic fillers include glass fiber, glass flakes, glass beads, carbon, silica, silica / alumina, zirconia, boron, boron nitride, silicon nitride, potassium titanate, stainless steel, aluminum, titanium, copper, brass, talc, mica, Inorganic fibers such as kaolin, wollastonite, calcium carbonate, titanium oxide, graphite, zinc oxide, barium sulfate, potassium titanate whisker, aluminum borate whisker, metal fiber, etc., surface treatment agents (for example, epoxy compounds) , Functional compounds such as acrylic compounds, isocyanate compounds, silane compounds, and titanate compounds) may be used.

Examples of the resin additive include dyes and pigments other than red, antistatic agents, antifogging agents, lubricants / antiblocking agents, fluidity improvers, flame retardants, plasticizers, dispersants, antibacterial agents, and the like.

[8] Manufacturing Method of Resin Composition The thermoplastic resin composition according to the present invention can be prepared by a conventionally known method. Specifically, the a component to the c component, and the d component to the f component blended as necessary, and other components are weighed in predetermined amounts and mixed in advance using various mixers such as a tumbler and a Henschel mixer. Thereafter, a melt kneading method using a Banbury mixer, a heating roll, a Brabender, a single-screw kneading extruder, a twin-screw kneading extruder, a kneader or the like can be mentioned. In addition, it is also possible to prepare a resin composition without mixing each component in advance, or by mixing only a part of the components in advance and supplying them to the extruder in the middle of the extruder using a feeder, and melt-kneading. it can. Furthermore, when the inorganic filler is an inorganic filler that is easily destroyed by melt-kneading, there is also a method in which components other than the inorganic filler are collectively added to the upstream portion of the extruder, and the inorganic filler is added after the middle stream and melt-kneaded with the resin component. From the viewpoint of mechanical properties of the resulting resin composition.

[9] Method for producing molded product The thermoplastic resin composition according to the present invention is used as a resin material for production (molding) of various products (molded products). As a molding method, a conventionally known method of molding a molded product from a thermoplastic resin material can be applied without limitation. Specifically, general injection molding methods, ultra-high speed injection molding methods, injection compression molding methods, two-color molding methods, hollow molding methods such as gas assist, molding methods using heat insulating molds, rapid heating molds Molding method used, foam molding (including supercritical fluid), insert molding, in-mold coating (IMC) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method Etc.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to a following example, unless the summary is exceeded. As the raw material, a commercially available product having the following characteristics is used, and the evaluation items of the polycarbonate resin composition and the molded product made of this resin composition are as follows.

<Characteristics of raw materials>
(1) a component a-1: an aromatic polycarbonate resin having a viscosity average molecular weight of 22,000 (trade name: Iupilon S-3000, manufactured by Mitsubishi Engineering Plastics).
(2) b component / b-1: CI Solvent Red 179 (Arimoto Chemical Co., Ltd., trade name: Plastread 8370).
B-2: CI Solvent Red 135 (manufactured by Mitsubishi Chemical Corporation, trade name: Diamond Resin R-HS).
B-3: CI Solvent Red 52 (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumiplast R-HL5B, anthraquinone red dye).
(3) c component. C-1: Tris (2,4-di-tert-butylphenyl) phosphite (Asahi Denka Kogyo Co., Ltd., trade name: ADK STAB 2112).

(4) d component d-1: pentaerythritol-tetrakis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate} (Ciba Geigy, trade name: Irganox 1010) is there.
(5) e component · e-1: 2- (2-hydroxy-5-t-octylphenyl) -2H-benzotriazole (manufactured by Cypro Kasei Co., Ltd., trade name: SESORB709).
(6) f component · f-1: glycerin monostearate (manufactured by Riken Vitamin Co., Ltd., trade name: Riquemar S-100A).
F-2: Pentaerythritol tetrastearate (manufactured by NOF Corporation, trade name: Unistar H-476).

<Evaluation Test Method> (1) Thermal Stability: For disc-1 to disc-3 obtained by the method described later, a spectrocolorimeter (manufactured by Nippon Denshoku Industries Co., Ltd., model: according to ASTM-E1925) The hue (E: L, a, b) was measured by SE-2000). Heat retention molding: Hue of disc-2 (hue after residence molding, E ₂ : L ₂ , a ₂ , b ₂ ) and hue of disc-1 (hue before residence molding, E ₁ : L ₁ , The difference (ΔE _1a ) from a ₁ , b ₁ ) is expressed as follows: ΔE _1a = {(L ₁ −L ₂ ) ² + (a ₁ −a ₂ ) ² + (b ₁ −b ₂ ) ² } ^1/2 . Thermal Aging: (hue after thermal _{aging, E 3: L 3, a} 3, b 3) Hue disc -3 and disc -1 hue (thermal aging previous _hue, E _{1: L 1,} a ₁ , b ₁ ) (ΔE _1b ) is expressed by the following formula, that is, ΔE _1b = {(L ₁ −L ₃ ) ² + (a ₁ −a ₃ ) ² + (b ₁ −b ₃ ) ² } ^1/2 . It can be determined that the smaller the numerical values of ΔE _1a and ΔE _1b, the better the thermal stability.

(2) Weather resistance: Disc-1 obtained by the method described later was irradiated with irradiance 156 W / m by a sunshine super long life weather meter (model: SX75-AP) according to SAE J1960. ² , treatment was performed for 500 hours under conditions of a black panel temperature of 63 ° C. and a water spray cycle of 18 minutes in 120 minutes. About the disk -1 before and after the treatment, the hue (E: L, a, b) was measured by a spectroscopic colorimeter (manufactured by Nippon Denshoku Industries Co., Ltd., model: SE-2000), and the disk -1 before and after the treatment the hue differences _{(△ E 1c), (E} 1: L 1, a 1, b 1) represents the hue before the weather resistance _{test, (E 4: L 4,} a 4, b 4) is weather resistance The hue after the test is calculated by the following formula: ΔE _1c = {(L ₁ −L ₄ ) ² + (a ₁ −a ₄ ) ² + (b ₁ −b ₄ ) ² } ^1/2 did. It can be determined that the smaller the numerical value of ΔE _1c, the better the weather resistance.

[Example 1 to Example 4, Comparative Example 1 to Comparative Example 6] (1) <Production of Polycarbonate Resin Composition> Raw materials were weighed at a ratio described in Table 1 and mixed by a tumbler. The mixture is supplied to a hopper of a vent type single screw extruder (manufactured by Tanabe Plastic Machine Co., Ltd., model: VS-40), melted and kneaded under the conditions of a cylinder set temperature of 270 ° C., a screw rotation speed of 54 rpm, and a vacuum degree of 740 mmHg to form a pellet A polycarbonate resin composition was obtained.

(2) <Manufacture of molded product made of polycarbonate resin composition> Disc 1: The pellet-shaped polycarbonate resin composition was dried at 120 ° C. for 5 hours with a hot air circulation dryer, and then an injection molding machine (name Machine-1, Model: M150AII-SJ) was used to mold Disc-1 having a diameter of 100 mm and a thickness of 3.2 mm under conditions of a cylinder temperature of 320 ° C., a mold temperature of 80 ° C., and a molding cycle of 60 seconds. did. Disc-2: A diameter of 100 mm and a thickness of 3.2 mm under the same conditions as the disc-1, except that the polycarbonate resin composition was retained in the cylinder of the injection molding machine for 30 minutes and then molded. Disk-2 was formed. Disc-3: Obtained by subjecting Disc-1 obtained by the above method to heat aging at 130 ° C. for 500 hours with a hot air circulation dryer. (3) <Evaluation of molded product> The obtained molded product was subjected to the above evaluation test, and the evaluation results are shown in Table 1.

From Table 1 above, the following becomes clear.
(1) The polycarbonate resin composition in which the component a, component b, and component c all satisfy the requirements defined in claim 1 are excellent in both thermal stability and weather resistance (Examples 1 to (See Example 4). In addition, what increased the compounding quantity of b component is further excellent in thermal stability and weather resistance (refer Example 3 and Example 4).

(2) On the other hand, what mixed the perinone-type red dye which does not correspond to b component of Claim 1 in a component and c component compared with the polycarbonate resin composition of Example 1, and heat resistance and weather resistance Is inferior (see Comparative Example 1). Moreover, what mix | blended the anthraquinone type | system | group red dye which does not correspond to b component is remarkably inferior in heat stability and weather resistance compared with the polycarbonate resin composition of Example 1 (refer the comparative example 2).
(3) The one containing the component a and the component b but not containing the component c is significantly inferior in weather resistance compared to the polycarbonate resin composition of Example 1 (see Comparative Example 3). Moreover, although the polycarbonate resin composition of the comparative example 4 mix | blends d component thru | or f component in addition to b-2 component, since it does not contain b-1 component, compared with the polycarbonate resin composition of Example 2. Inferior in thermal stability and weather resistance. Furthermore, although the polycarbonate resin composition of Comparative Example 5 and Comparative Example 6 has increased the compounding quantity of b-2 component, since it does not contain b-1 component, the polycarbonate resin composition of Example 3 and Example 4 Thermal stability and weather resistance are inferior compared to products.

Since the polycarbonate resin composition according to the first invention of the present invention is excellent in thermal stability and weather resistance without impairing the features of the polycarbonate resin, it can produce various products (molded products) such as electrical and electronic equipment parts. It is suitably used as a resin material for (molding). In addition, the molded product made of the polycarbonate resin composition according to the second invention of the present invention is excellent in the thermal stability and weather resistance of the molded product molded from the resin composition of the present invention having such features. Therefore, it is suitably used as electrical / electronic equipment parts, OA equipment, machine parts, vehicle parts, building members, and various containers that are heated from the surroundings or exposed to the outdoors for a long time.

Claims (5)

0.0001 to 0.5 parts by weight of a perinone-based red dye (component b) mainly composed of a compound represented by the following structural formula (I) with respect to 100 parts by weight of a polycarbonate resin (component a), and phosphorus heat A polycarbonate resin composition comprising 0.001 to 1 part by weight of a stabilizer (component c).

The polycarbonate resin composition of Claim 1 formed by mix | blending 0.001-1 weight part of phenol-type heat stabilizers (d component) with respect to 100 weight part of polycarbonate resin (a component). The polycarbonate resin composition of Claim 1 or Claim 2 which mix | blends 0.01-3 weight part of weather resistance improving agents (e component) with respect to 100 weight part of polycarbonate resin (a component). The polycarbonate resin composition according to any one of claims 1 to 3, wherein 0.01 to 1 part by weight of a release agent (f component) is blended with 100 parts by weight of the polycarbonate resin (a component). object. 0.0001 to 0.5 parts by weight of a perinone-based red dye (component b) mainly composed of a compound represented by the following structural formula (I) with respect to 100 parts by weight of a polycarbonate resin (component a), and phosphorus heat A molded article characterized by being produced from a polycarbonate resin composition containing 0.001 to 1 part by weight of a stabilizer (component c).