JP2018178019A - Aromatic polycarbonate resin composition, and molded article thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin composition suitable as a molding material of a light guiding member, and excellent in color tone, weather resistance and yellow discoloration inhibitory effect.SOLUTION: There is provided an aromatic polycarbonate resin composition containing, based on 100 pts.mass of an aromatic polycarbonate resin (A), 0.001 to 0.1 pts.mass of a phosphite-based stabilizer (B-I) having a spiro ring skeleton containing bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 0.01 to 0.5 pts.mass of a triphenyl phosphite stabilizer (B-II) represented by the formula (II), 0.05 to 2 pts.mass of a polybutylene glycol compound having number average molecular weight of 200 to less than 1,000, and 0.01 to 1 pts.mass of an ultraviolet absorber (D). Rto Rare each independently H, a C6 to 20 aryl group or a C1 to 20 alkyl group.SELECTED DRAWING: None

Description

  The present invention relates to an aromatic polycarbonate resin composition and a molded article thereof. More specifically, the present invention provides an aromatic polycarbonate resin composition excellent in color tone, weather resistance and yellowing suppression effect, which is suitable as a molding material for a light guide member, and a molding obtained by molding this aromatic polycarbonate resin composition. Relating to goods.

  In recent years, in Europe, North America, etc., the daylighting of automobiles has progressed by increasing the visibility from pedestrians and oncoming vehicles in the daytime by installing daylights that are always on the headlights and rear lamps of automobiles. . The daylight generally comprises a light guide member and a light source for causing light to enter the light guide member. Since an incandescent lamp such as a halogen lamp is generally provided as a general light source for nighttime in the vicinity of the daylight of a car, the light guide member is an incandescent lamp in addition to the heat generated from the light source of the daylight. It is also heated by the heat generated from Furthermore, since an ultraviolet-ray generate | occur | produces from an incandescent lamp and an ultraviolet-ray generate | occur | produces although it is slight also from the LED lamp mainly used as a light source of daylight, anti-ultraviolet measures are also required. Therefore, the light guide member is required to have excellent heat resistance durability and weather resistance.

  Conventionally, as a constituent material of a light guide member, for example, the following Patent Document 1 discloses an aromatic polycarbonate resin composition in which a phosphorus-based stabilizer and a fatty acid ester are mixed with an aromatic polycarbonate resin. When a light guide member of a lighting device for an automobile is molded using a resin composition, the heat received in the molding process may deteriorate the aromatic polycarbonate resin, and the molded article obtained may have a slight yellowish color. Moreover, even if it does not have a yellowish color at the time of molding, the light guide member is deteriorated and yellowed by being exposed to the heat of the light source around the light guide member and the ultraviolet light emitted from the light source for a long time.

  In Patent Document 2, two types of aromatic polycarbonate resins are used as an aromatic polycarbonate resin composition which improves yellowing resistance and reduces the problem of yellowing even when exposed to heating conditions for a long time. Although the aromatic polycarbonate resin composition which mix | blended the phosphite type | system | group stabilizer and the fatty acid ester is disclosed, examination about a weather resistance is not made | formed.

JP 2007-204737 A JP, 2015-189879, A

  If the weather resistance of the aromatic polycarbonate resin composition is not sufficient, the use of the composition can not be continued due to the deterioration of the molded product, and the molecular weight is reduced due to the decomposition of the aromatic polycarbonate resin. However, the aromatic polycarbonate resin composition which improved not only the yellowing suppression effect but also the weather resistance is not provided.

  The present invention relates to an aromatic polycarbonate resin composition having extremely excellent hue and yellowing suppression effects and high weather resistance, which is suitable for light guide member applications incorporated in automobile lighting devices, and to this aromatic polycarbonate resin composition It is an object of the present invention to provide a molded article obtained by molding an article.

  In order to solve the above problems, the inventor of the present invention has conducted intensive studies on additives to be added to the aromatic polycarbonate resin, and as a result, two specific phosphite-based stabilizers are used in combination and a relatively low molecular weight polybutylene glycol is obtained. It discovered that the said subject could be solved by mix | blending a cycloaliphatic epoxy compound as a compound, a ultraviolet absorber, and also an epoxy compound.

  The present invention has been achieved based on such findings, and the gist of the present invention is as follows.

[1] A phosphite-based stabilizer (B-I) having a spiro ring skeleton as a phosphorus-based stabilizer (B) with respect to the aromatic polycarbonate resin (A) and 100 parts by mass of the aromatic polycarbonate resin (A) 0.001 to 0.1 parts by mass, and 0.01 to 0.5 parts by mass of a phosphite stabilizer (B-II) represented by the following general formula (II), and a number average molecular weight of 200 or more 1, Phosphite-based stabilizer having a spiro ring skeleton containing 0.05 to 2 parts by mass of the polybutylene glycol compound (C) which is less than 000 and 0.01 to 1 parts by mass of the ultraviolet absorber (D) An aromatic polycarbonate resin composition, wherein 1) contains bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.

(In formula (II), R ^{21 to} R ²⁵ each independently represent a hydrogen atom, an aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms.

[2] In [1], an aromatic epoxy resin (E) containing 0.0005 to 0.2 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). Polycarbonate resin composition.

[3] The aromatic polycarbonate resin composition as described in [2], wherein the alicyclic epoxy compound (E) is 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate.

The molded article formed by shape | molding the aromatic polycarbonate resin composition in any one of [4] [1] thru | or [3].

[5] The molded article according to [4], which is a light guide member.

[6] The molded article according to [5], which is a light guide member incorporated in an automobile lighting device.

  The aromatic polycarbonate resin composition of the present invention is excellent in weatherability as well as having a good hue and a good yellowing suppression effect without any deterioration in the original characteristics of the polycarbonate resin, and therefore the polycarbonate for a light guide member It is suitable as a resin material, and in particular, it can be suitably used as a light guide member incorporated in an automobile lighting device, in particular, as a long or thick light guide member.

  Embodiments of the present invention will be described in detail below.

[Aromatic polycarbonate resin composition]
The aromatic polycarbonate resin composition of the present invention comprises an aromatic polycarbonate resin (A) and a phosphite having a spiro ring skeleton as a phosphorus-based stabilizer (B) with respect to 100 parts by mass of the aromatic polycarbonate resin (A) 0.001 to 0.1 parts by mass of a system stabilizer (B-I), and 0.01 to 0.5 parts by mass of a phosphite stabilizer (B-II) represented by the following general formula (II), Containing 0.05 to 2 parts by mass of a polybutylene glycol compound (C) having a number average molecular weight of 200 or more and less than 1,000, and 0.01 to 1 parts by mass of an ultraviolet absorber (D), and having a spiro ring skeleton The phosphite stabilizer (B-1) is characterized by containing bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.

(In formula (II), R ^{21 to} R ²⁵ each independently represent a hydrogen atom, an aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms.

  In the present invention, the hue immediately after molding of a molded article obtained by molding an aromatic polycarbonate resin composition is referred to as "initial color", and yellowing occurs when the resulting molded article is irradiated with ultraviolet light for a long time The effect of suppressing the is referred to as "yellowing suppression effect".

<Aromatic polycarbonate resin (A)>
The aromatic polycarbonate resin (A) is an aromatic polycarbonate polymer obtained by reacting an aromatic hydroxy compound with phosgene or a diester of carbonic acid. The aromatic polycarbonate polymer may have a branch. The method for producing the aromatic polycarbonate resin is not particularly limited, and may be a conventional method such as a phosgene method (interfacial polymerization method) or a melting method (ester exchange method).

  Representative examples of the aromatic dihydroxy compound include, for example, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxy-3-methylphenyl). ) Propane, 2,2-bis (4-hydroxy-3-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy) 3,5-Dibromophenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxybiphenyl, 3,3 ', 5 , 5'- tetramethyl-4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) Le) sulfide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone.

Among the above aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is particularly preferable.
The above aromatic dihydroxy compounds may be used alone or in combination of two or more.

  When producing the aromatic polycarbonate resin (A), a small amount of polyhydric phenol having three or more hydroxy groups in the molecule may be added in addition to the above-mentioned aromatic dihydroxy compound. In this case, the aromatic polycarbonate resin (A) has a branch.

  Examples of polyhydric phenols having three or more hydroxy groups include phloroglucin, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-2,4,6-dimethyl-2,4. 6,6-tris (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-3,1,3,5-tris (4-hydroxyphenyl) benzene, Polyhydroxy compounds such as 1,1,1-tris (4-hydroxyphenyl) ethane, or 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chloroisatin, 5,7-dichloroicetin , 5-bromomysatin and the like. Among these, 1,1,1-tris (4-hydroxyphenyl) ethane or 1,3,5-tris (4-hydroxyphenyl) benzene is preferable. The amount of the polyhydric phenol used is preferably 0.01 to 10 mol%, more preferably 0.1 to 2 mol% based on the aromatic dihydroxy compound (100 mol%). It is.

  In the transesterification polymerization, carbonic diester is used as a monomer instead of phosgene. Representative examples of diester carbonates include substituted diaryl carbonates represented by diphenyl carbonate, ditolyl carbonate and the like, and dialkyl carbonates represented by dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate and the like. These carbonic acid diesters can be used alone or in combination of two or more. Among these, diphenyl carbonate and substituted diphenyl carbonate are preferable.

  The above-mentioned diester of carbonic acid may preferably be substituted with a dicarboxylic acid or a dicarboxylic acid ester in an amount of 50 mol% or less, more preferably 30 mol% or less. Representative dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate and diphenyl isophthalate. When a part of carbonic diester is substituted by such dicarboxylic acid or dicarboxylic acid ester, polyester carbonate is obtained.

  When producing an aromatic polycarbonate resin by a transesterification method, a catalyst is usually used. There is no limitation on the type of catalyst, but generally, basic compounds such as alkali metal compounds, alkaline earth metal compounds, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, amine compounds and the like are used. Among them, alkali metal compounds and / or alkaline earth metal compounds are particularly preferable. One of these may be used alone, or two or more may be used in combination. In the transesterification method, it is general to deactivate the above-mentioned catalyst with p-toluenesulfonic acid ester or the like.

  The aromatic polycarbonate resin (A) can be copolymerized with a polymer or oligomer having a siloxane structure for the purpose of imparting flame resistance and the like.

The viscosity average molecular weight of the aromatic polycarbonate resin (A) is preferably 10,000 to 22,000. If the viscosity average molecular weight of the aromatic polycarbonate resin (A) is less than 10,000, the mechanical strength of the resulting molded article may be insufficient, and a product having sufficient mechanical strength may not be obtained. In addition, when the viscosity average molecular weight of the aromatic polycarbonate resin (A) exceeds 22,000, the melt viscosity of the aromatic polycarbonate resin (A) becomes large, so, for example, the aromatic polycarbonate resin composition may be injection-molded or the like Excellent fluidity can not be obtained when molding and manufacturing a long-shaped molded product such as a light guide member, and the amount of heat generated by shearing of the resin becomes large, and the resin is degraded by thermal decomposition In some cases, it is not possible to obtain a molded article having an excellent hue.
The viscosity average molecular weight of the aromatic polycarbonate resin (A) is more preferably 12,000 to 18,000, and still more preferably 14,000 to 17,000.

In addition, with viscosity average molecular weight [Mv], using methylene chloride as a solvent, the intrinsic viscosity [ロ ー] (unit dl / g) at a temperature of 20 ° C. is determined using a Ubbelohde viscometer, and Schnell's viscosity formula, ie, , = 1 = 1.23 × 10 ⁻⁴ Mv ^0.83 . In addition, the intrinsic viscosity [η] is a value calculated by measuring the specific viscosity [で_sp ] at each solution concentration [C] (g / dl) according to the following equation.

  The aromatic polycarbonate resin (A) may be a mixture of two or more kinds of aromatic polycarbonate resins having different viscosity average molecular weights, or may be mixed with an aromatic polycarbonate resin having a viscosity average molecular weight outside the above range. It may be in the range of the viscosity average molecular weight.

<Phosphorus-based stabilizer (B)>
The aromatic polycarbonate resin composition of the present invention comprises, as a phosphorus-based stabilizer (B), a phosphite-based stabilizer (BI) having a spiro ring skeleton (hereinafter simply referred to as "phosphite-based stabilizer (BI) Phosphite stabilizer (B-II) (hereinafter referred to simply as "phosphite stabilizer (B-II)") represented by the following general formula (II): And (d)).

(In formula (II), R ^{21 to} R ²⁵ each independently represent a hydrogen atom, an aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms.

<Phosphite stabilizer (BI)>
The phosphite stabilizer (B-I) may be a phosphite compound having a spiro ring skeleton and is not particularly limited, and examples thereof include those represented by the following general formula (I).

(In formula (I), R ^10A and R ^10B each independently represent an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms.)

In the general formula (I), the alkyl groups represented by R ^10A and R ^10B are preferably each independently a linear or branched alkyl group having 1 to 10 carbon atoms. When R ^10A and R ^10B are aryl groups, aryl groups represented by any of the following general formulas (I-a), (I-b), or (I-c) can be mentioned.

(In the formula (I-a), R ^A represents an alkyl group having 1 to 10 carbon atoms. In the formula (I-b), R ^B represents an alkyl group having 1 to 10 carbon atoms.)

  Among these, the phosphite stabilizers (B-I) used in the present invention are preferably bis (2,6-di-tert-butyl-4-methylphenyl) penta represented by the following structural formula (I-A) It is essential to include erythritol diphosphite.

  One of the above phosphite stabilizers (B-I) may be used alone, or two or more thereof may be used in combination. However, in the phosphite stabilizers (B-I), bis (2) may be used. It is preferable to contain 50 mass% or more of 6,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and it is more preferable to contain 70 mass% or more.

<Phosphite stabilizer (B-II)>
The phosphite stabilizer (B-II) is represented by the above general formula (II).

Examples of the alkyl group represented by R ^{21 to} R ²⁵ in the general formula (II) include methyl group, ethyl group, propyl group, n-propyl group, n-butyl group, tert-butyl group, hexyl group, and the like An octyl group etc. are mentioned.

  As the phosphite stabilizer (B-II), in particular, tris (2,4-di-tert-butylphenyl) phosphite represented by the following structural formula (II-A) is preferable.

  The phosphite stabilizers (B-II) may be used alone or in combination of two or more.

<Content of phosphorus stabilizer (B)>
In the aromatic polycarbonate resin composition of the present invention, the content of the phosphite stabilizer (B-I) is 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A) It is. When the content of the phosphite stabilizer (B-I) is less than 0.001 parts by mass, a sufficient yellowing suppression effect can not be obtained. Even if the content of the phosphite stabilizer (B-I) exceeds 0.1 part by mass, the yellowing suppressing effect tends to be reduced, and the amount of gas at the time of molding increases, and transfer failure due to mold deposit As a result, the light transmittance of the resulting molded article may be reduced. The content of the phosphite stabilizer (B-I) is preferably 0.002 parts by mass or more, more preferably 0.003 parts by mass or more, preferably 100 parts by mass of the aromatic polycarbonate resin (A), and preferably Is at most 0.09 parts by mass, more preferably at most 0.07 parts by mass, particularly preferably at most 0.06 parts by mass.

  In the aromatic polycarbonate resin composition of the present invention, the content of the phosphite stabilizer (B-II) is 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). It is. If the content of the phosphite stabilizer (B-II) is less than 0.01 parts by mass, further improvement of the initial hue and the yellowing inhibitory effect by blending the phosphite stabilizer (B-II) I can not get enough effects. When the content of the phosphite stabilizer (B-II) exceeds 0.5 parts by mass, the gas at the time of molding increases and transfer defects due to mold deposition occur, so that the light transmission of the obtained molded article The rate may decrease. The content of the phosphite stabilizer (B-II) is preferably 0.03 to 0.3 parts by mass, more preferably 0.05 to 0 based on 100 parts by mass of the aromatic polycarbonate resin (A). .2 parts by mass.

  In order to more effectively obtain the effect of using the phosphite stabilizer (BI) and the phosphite stabilizer (B-II) in combination, the phosphite system in the aromatic polycarbonate resin composition of the present invention The mass ratio of the stabilizer (B-I) to the phosphite stabilizer (B-II) is preferably 1: 1 to 30, more preferably 1: 1 to 20, still more preferably Is an amount such that it is 1: 1 to 15, particularly preferably 1: 2 to 10, particularly preferably 1: 3 to 7. The total content of the phosphite stabilizer (B-I) and the phosphite stabilizer (B-II) is 0.05 to 0.2 based on 100 parts by mass of the aromatic polycarbonate resin (A). It is preferable that it is a mass part, and it is more preferable that it is 0.1-0.16 mass part.

<Polybutylene glycol compound (C)>
The polybutylene glycol compound (C) used in the present invention is a branched glycol compound represented by the following general formula (III).

(In formula (III), R represents an ethyl group, and X and Y each independently represent a hydrogen atom, an aliphatic acyl group having 1 to 23 carbon atoms, or an alkyl group having 1 to 23 carbon atoms, n Represents the degree of polymerization, and is an integer of 2 or more.)

  As the branched polybutylene glycol compound, polybutylene glycol in which X and Y are hydrogen atoms in general formula (III) is preferable.

  Even if one end or both ends of a polybutylene glycol compound (C) is blocked with a fatty acid or alcohol, its performance will not be affected, and fatty acid esterification products or etherification products can be used similarly. X and / or Y in the general formula (III) may be an aliphatic acyl group having 1 to 23 carbon atoms or an alkyl group.

As the fatty acid esterified product, any of linear or branched fatty acid esters can be used, and the fatty acid constituting the fatty acid ester may be a saturated fatty acid or an unsaturated fatty acid. Also, those in which a part of hydrogen atoms are substituted by a substituent such as a hydroxyl group can be used.
The fatty acid constituting the fatty acid ester is a monovalent or divalent fatty acid having 1 to 23 carbon atoms, for example, a monovalent saturated fatty acid, specifically, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid Enanthate, caprylic acid, caprylic acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, and monovalent unsaturated fatty acids, specifically, Unsaturated fatty acids such as oleic acid, elaidic acid, linoleic acid, linolenic acid, arachidonic acid, and divalent fatty acids having 10 or more carbon atoms, specifically, sebacic acid, undecanedioic acid, dodecanedioic acid, tetradecanedioic acid , Tapsia acid and decenoic acid, undecenoic acid and dodecenoic acid.
These fatty acids can be used alone or in combination of two or more. The fatty acids also include fatty acids having one or more hydroxyl groups in the molecule.

  Preferred specific examples of the fatty acid ester of polybutylene glycol are polybutylene glycol stearates in which X and Y are aliphatic acyl groups having 18 carbon atoms in the general formula (III), and aliphatics wherein X and Y have 22 carbon atoms The polybutylene glycol behenate which is an acyl group is mentioned.

  The alkyl group constituting the alkyl ether of polybutylene glycol may be linear or branched and has, for example, a carbon number such as methyl group, ethyl group, propyl group, butyl group, octyl group, lauryl group and stearyl group. Examples of such a polybutylene glycol compound (C) include methyl ether, ethyl ether, butyl ether, lauryl ether and stearyl ether of polybutylene glycol.

In the present invention, as such a polybutylene glycol compound (C), one having a number average molecular weight of 200 or more and less than 1,000 is used. The number average molecular weight of the polybutylene glycol compound (C) is preferably 300 or more, more preferably 500 or more, preferably 900 or less, and more preferably 800 or less. If the upper limit of the above range is exceeded, the compatibility is lowered, which is not preferable. If the lower limit of the above range is not reached, the amount of gas generation at the time of molding increases, and molding defects by gas, for example, unfilled, gas burn, transfer failure Is not likely to occur. The number average molecular weight of the polybutylene glycol compound (C) as referred to herein is a number average molecular weight calculated based on the hydroxyl value measured according to JIS K1577.
As the number average molecular weight of the polybutylene glycol compound (C) is lower, there is an effect of reducing the mold contamination (mold adhesion) at the time of molding.

  The polybutylene glycol compound (C) may be used alone or in combination of two or more.

  In the aromatic polycarbonate resin composition of the present invention, the content of the polybutylene glycol compound (C) is 0.05 to 2 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). Even if the content of the polybutylene glycol compound (C) is less than 0.05 parts by mass or more than 2 parts by mass, the initial hue of the resulting molded article tends to be inferior. The content of the polybutylene glycol compound (C) is preferably 0.1 to 1.5 parts by mass, more preferably 0.2 to 1.2 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). More preferably, it is more than 0.5 parts by mass and not more than 1.0 parts by mass.

[UV absorber (D)]
The aromatic polycarbonate resin composition of the present invention contains a UV absorber (D) in order to absorb UV light and to improve the weatherability. As the UV absorber (D), benzotriazole-based UV absorbers, benzoxazine-based UV absorbers, triazine-based UV absorbers and malonic acid ester-based UV absorbers are mentioned as preferable ones, and others, benzophenone-based UV absorbers Also, phenyl salicylate type ultraviolet absorbers, cyanoacrylate type ultraviolet absorbers and the like can be used.

  As a benzotriazole type ultraviolet absorber, for example, 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, 2- (2-hydroxy-3,5-di-tert-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-tert-octyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-tert-amyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3- Lauryl-5-methyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-te) 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-benzotriazol-2-yl) -2-hydroxy-5- (1,1,3,3-tetramethylbutyl) phenyl) methane, bis (3- (2H-benzotriazole) -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-ethanediyl bis (3- (2H-benzotriazol-2-yl) -2-hydroxybenzoate), 1,12-dodecane Diylbis (3- (2H-benzotriazol-2-yl) -4-hydroxybenzoate), 1,3-cyclohexanediylbis (3- (5-chloro-2H-benzotriazol-2-yl) -2-hydroxy Benzoate), 1,4-butanediylbis (3- (2H-benzotriazol-2-yl) -4-hydroxy-5-methyl) Phenyl ethanoate), 3,6-dioxa-1,8-octanediyl bis (3- (5-methoxy-2H-benzotriazol-2-yl) -4-hydroxyphenylethanoate), 1,6-hexane Diylbis (3- (3- (2H-benzotriazol-2-yl) -4-hydroxy-5-tert-butylphenyl) propionate), p-xylenediylbis (3- (3- (2H-benzotriazole-) 2-yl) -4-hydroxyphenyl) propionate), bis (3- (2H-benzotriazol-2-yl) -4-hydroxytoluyl) malonate, bis (2- (3- (2H-benzotriazole-2-) ) -4-Hydroxy-5-octylphenyl) ethyl) terephthalate, bis (3- (2H-benzotriazole) 2-yl) -4-hydroxy-5-propyl toluyl) octadioate, 2- (2H-benzotriazol-2-yl) -6-phthalimidomethyl-4-methylphenol, 2- (2H-benzotriazole-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. Among these, 2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole is preferable.

  As the benzoxazine-based ultraviolet absorber, 2,2 ′-(1,4-phenylene) bis (4H-3,1-benzoxazin-4-one) (2,2′-p-phenylene bis (3,1) -Benzoxazin-4-one), 2,2'-p-phenylenebis (3,1-benzoxazin-4-one), 2,2'-m-phenylenebis (3,1-benzoxazine-4-) On), 2,2- (4,4'-diphenylene) bis (3,1-benzoxazin-4-one), 2,2 '-(2,6-naphthalene) bis (3,1-benzoxazine- 4-one), 2,2- (1,5-naphthalene) bis (3,1-benzoxazin-4-one), 2,2 '-(2-methyl-p-phenylene) bis (3,1-benzo) And oxazin-4-one) etc. Among these. Also, 2,2 '- (1,4-phenylene) bis (4H-3,1-benzoxazin-4-one) are preferred.

  The triazine-based UV absorbers include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine and 2,4-diphenyl-6- (2-hydroxy-4-) Ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-) Butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2- Hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triadidi 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1 And 3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyethoxy) -1,3,5-triazine and the like.

  As the malonic acid ester-based ultraviolet light absorber, any conventionally known malonic acid esters can be used, among which 2- (alkylidene) malonic acid esters, particularly 2- (1-arylalkylidene) malonic acid esters are preferable. .

  As the 2- (1-arylalkylidene) malonic acid esters, those represented by the following general formula (IV) are particularly preferable.

In (formula (IV), Q is a hydrogen atom, which may have a substituent group, having 1 to 8 carbon atoms, an alkyl group, an alkoxy group or an alkenyl group having 2 to 10 carbon atoms, R ¹¹ and Each R ¹² independently represents an alkyl group having 1 to 6 carbon atoms.)

  In the general formula (IV), Q is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, an alkoxy group or an alkenyl group. The alkyl group in the alkyl group or alkoxy group represented by Q may be linear or branched, and specifically, methyl group, ethyl group, n-propyl group, i-propyl group Groups, n-butyl group, i-butyl group, s-butyl group, t-butyl group and the like. Moreover, as an alkenyl group, what has an ester group as a substituent is preferable, and the carbon number is 3-10 normally, Preferably it is 4-8 including carbon number in a substituent.

  As the malonic acid ester type ultraviolet light absorber, those which are 2- (alkylidene) malonic acid esters in which Q itself is a malonic acid ester moiety of the above general formula (IV) are preferable, and in particular, general formula (IV) Preferred are those having the same malonic acid ester residue (especially those having these in the para position) with the benzene ring of

In formula ^(IV), examples of ^{R 11} and ^{R 12,} preferably an alkyl group having 1 to 4 carbon atoms, respectively. The alkyl group represented by R ¹¹ and R ¹² may be linear or branched, and specifically, methyl group, ethyl group, n-propyl group, i-propyl group, The n-butyl group, i-butyl group, s-butyl group, t-butyl group etc. are mentioned. More preferably, R ¹¹ and R ¹² are each a methyl group.

  The molecular weight of the above-mentioned malonic acid ester type ultraviolet absorber is usually 220 to 500, preferably 240 to 450. If the molecular weight is less than 220, the amount of mold deposits may be increased, which may cause appearance defects of the resulting molded article. On the other hand, when the molecular weight exceeds 500, the bleeding property to the surface of the molded article may be reduced, and the effect of improving the weather resistance may be reduced.

  As a commercial item of the above malonic acid ester type ultraviolet absorbers, for example, products "PR-25" (maximum absorption wavelength: 308 nm) and "B-CAP" (maximum absorption wavelength: 320 nm) manufactured by Clariant Japan Ltd. Etc.

  Examples of benzophenone-based UV absorbers include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2- Hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2 ', 4,4'-tetra And hydroxy-benzophenone and the like.

  Examples of phenyl salicylate UV absorbers include phenyl salicylate, 2- (4-) tertiary butylphenyl-3,5-di-tertiary butyl-4-hydroxybenzoate and the like.

  These ultraviolet absorbers (D) may be used alone or in combination of two or more.

  In the aromatic polycarbonate resin composition of the present invention, the content of the ultraviolet absorber (D) is 0.01 to 1 part by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). If the content of the ultraviolet absorber (D) is less than 0.01 parts by mass, sufficient weather resistance can not be obtained, and even if the amount exceeds 1 part by mass, no further effect can be obtained. The content of the ultraviolet absorber (D) is preferably 0.03 to 0.7 parts by mass, more preferably 0.05 to 0.5 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). is there.

[Alicyclic epoxy compound (E)]
The aromatic polycarbonate resin composition of the present invention preferably contains an alicyclic epoxy compound (E) in order to enhance color tone and heat resistance and obtain a more excellent yellowing suppression effect.

As an alicyclic epoxy compound (E), the alicyclic compound which has 1 or more of epoxy groups in 1 molecule is used. Specifically, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3', 4'-epoxy-6'-methylcyclohexylcarboxy , 2,3-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate, 4- (3,4-epoxy-5-methylcyclohexyl) butyl-3', 4'-epoxycyclohexylcarboxylate, 3, 4-Epoxycyclohexylethylene oxide, cyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6'-methylcylohexyl carboxylate, bis-epoxydicyclopentadienyl ether, bis - Epoxycyclohexyl adipate, 3,4-dimethyl-1,2-epoxycyclohexane, 3,5-dimethyl-1,2-epoxycyclohexane, 3-methyl-5-t-butyl-1,2-epoxycyclohexane, octadecyl-2 , 2-Dimethyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2,2-dimethyl-3,4-epoxycyclohexylcarboxylate, cyclohexyl-2-methyl-3,4-epoxycyclohexylcarboxylate, N- Butyl-2-isopropyl-3,4-epoxy-5-methylcyclohexylcarboxylate, octadecyl-3,4-epoxycyclohexylcarboxylate, 2-ethylhexyl-3 ', 4'-epoxycyclohexylcarboxylate, 4,6-dimethyl 2,3-Epoxycyclohexyl-3 ', 4'-epoxycyclohexylcarboxylate, diethyl-4,5-epoxy-cis-1,2-cyclohexyldicarboxylate, di-n-butyl-3-t-butyl-4 Preferred examples include 5-epoxy-cis-1,2-cyclohexyl dicarboxylate and the like. Among these, in particular, an alicyclic epoxy compound having two or more epoxy groups in one molecule is preferable, and in particular, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexyl carboxylate is preferable.
The alicyclic epoxy compounds (E) may be used alone or in combination of two or more.

  When the aromatic polycarbonate resin composition of the present invention contains the above-mentioned alicyclic epoxy compound (E), the content of the alicyclic epoxy compound (E) is 100 parts by mass of the polycarbonate resin (A), The amount is preferably 0.0005 to 0.2 parts by mass, more preferably 0.001 parts by mass or more, still more preferably 0.003 parts by mass or more, particularly preferably 0.005 parts by mass or more, and particularly preferably 0.01 It is preferably at least 0.03 parts by mass, more preferably at most 0.15 parts by mass, still more preferably at most 0.1 parts by mass, particularly preferably at most 0.07 parts by mass. When the content of the alicyclic epoxy compound (E) is less than 0.0005 parts by mass, the hue and yellowing suppression effect becomes insufficient, and when it exceeds 0.2 parts by mass, the yellowing suppression effect is rather deteriorated Not only that, but also the hue may be reduced.

<Other ingredients>
In the aromatic polycarbonate resin composition of the present invention, as an optional component, an antioxidant, a mold release agent, a fluorescent whitening agent, a dye, a flame retardant, an impact modifier, and the like as long as the object of the present invention is not impaired. Antistatic agents, lubricants, plasticizers, compatibilizers, fillers and the like may be blended.

<Method of producing aromatic polycarbonate resin composition>
The method for producing the aromatic polycarbonate resin composition of the present invention is not particularly limited. For example, the components are collectively or divided and compounded, and melt-kneaded in any stage until the final molded product is formed. The method is mentioned. As a method of blending each component, for example, a method using a tumbler, a Henschel mixer or the like, a method of quantitatively supplying to an extruder hopper by a feeder and mixing, etc. may be mentioned. Examples of the method of melt-kneading include methods using a single-screw kneading extruder, a twin-screw kneading extruder, a kneader, a Banbury mixer, and the like.

[Molding]
The molded article of the present invention is formed by molding the above-mentioned aromatic polycarbonate resin composition of the present invention.

  The molding method of the aromatic polycarbonate resin composition of the present invention is not particularly limited, and examples thereof include an injection molding method, a compression molding method, an injection compression molding method and the like, and preferably an injection molding method.

  When the aromatic polycarbonate resin composition of the present invention is molded in order to suppress thermal deterioration of the resin during molding and obtain an excellent initial color, the resin composition is molded under an inert gas atmosphere such as nitrogen. It is preferable to

  The molded article of the present invention formed by molding the aromatic polycarbonate resin composition of the present invention is superior to the conventional product in weatherability and has mechanical properties such as clouding of the molded article, foaming and decomposition of the aromatic polycarbonate resin. There is no problem of deterioration, and the degree of yellowing when exposed to ultraviolet light for a long time is small, and the initial hue is good. It can be suitably used as a light guiding member of a lighting device for an automobile exposed to heat or ultraviolet radiation or a moist heat environment by heat generated from an incandescent lamp, and due to its excellent initial hue and yellowing suppression effect, The light transmission efficiency of the light guide member can be maintained high for a long time, and the frequency of replacement of the light guide member can be significantly reduced.

  EXAMPLES Although an Example is given to the following and this invention is more concretely demonstrated to it, this invention is not limited to a following example, unless the summary is exceeded.

  The materials used in the examples and comparative examples are as follows.

<Aromatic polycarbonate resin (A)>
Bisphenol A-type aromatic polycarbonate resin manufactured by interfacial polymerization: viscosity average molecular weight 19,000, manufactured by Mitsubishi Engineering Plastics Co., Ltd.

<Phosphorus-based stabilizer (B)>
<Phosphite stabilizer (BI)>
ADEKA “ADEKA Stub PEP-36”: bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite represented by the above structural formula (IA) (in Table 1, “ Described as PEP-36.)

<Phosphite stabilizer (B-II)>
Adeka company "ADEKA STAB AS 2112": Tris (2,4-di-tert-butylphenyl) phosphite represented by the above structural formula (II-A) (denoted as "AS 2112" in Table 1)

<Polybutylene glycol compound (C)>
NOF Corporation "Uniol PB-500": polybutylene glycol (number average molecular weight 500) (in Table 1, described as "PB-500")

<UV Absorbent (D)>
Cipro Chemical "Seasorb 709": 2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole represented by the following structural formula (described as "709" in Table 1)
Cytec “Cyasorb UV 3638”: 2,2 ′-(1,4-phenylene) bis (4H-3,1-benzoxazin-4-one) represented by the following structural formula (in Table 1, “UV3638” And write.)

<Alicyclic epoxy compound (E)>
Daicel "Ceroxide 2021P": 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate (described as "2021P" in Table 1)

<Hindered amine light stabilizer>
BASF "Tinuvin PA 144": bis (1,2,2,6,6-pentamethyl-4-piperidyl) represented by the following structural formula [[3,5-bis (1,1-dimethylethyl) -4-4] Hydroxyphenyl] methyl] butyl malonate (described as "PA 144" in Table 1)
ADEKA “LA-81”: bis (1-undecanoxy-2,2,6,6-tetramethyl-4-piperidinyl) carbonate represented by the following structural formula (described as “LA-81” in Table 1 Do.)

[Examples 1 to 5 and Comparative Examples 1 to 5]
<Production of Aromatic Polycarbonate Resin Composition>
The components shown in Table 1 were blended in proportions shown in Table 1 and uniformly mixed with a tumbler mixer to obtain a mixture. This mixture is supplied to a single-screw extruder ("VS-40" manufactured by Isuzu Kako Co., Ltd.) equipped with a full flight screw and a vent, and the condition of screw rotation speed 80 rpm, discharge amount 20 kg / hour, barrel temperature 250 ° C. And the mixture was extruded in the form of a strand from the tip of the extrusion nozzle. The extrudate was quenched in a water bath, cut into pellets using a pelletizer, and pellets of the aromatic polycarbonate resin composition were obtained.
The following evaluation was performed on the obtained aromatic polycarbonate resin composition, and the results are shown in Table 1.

<Early Hue (YI) Evaluation>
After drying the pellet of the aromatic polycarbonate resin composition at 120 ° C. for 4 to 8 hours with a hot air circulating drier, the injection molding machine (“EC 100” manufactured by Toshiba Machine Co., Ltd.) forms a 300 mm long light path at a temperature of 280 ° C. The product (6 mm × 4 mm × 300 mm, L / d = 50) was obtained. For this molded product, a YI value of 300 mm was measured using a long path spectral transmission colorimeter (“ASA1” manufactured by Nippon Denshoku Kogyo Co., Ltd.). The smaller the YI value, the better the initial hue.

<Weatherability evaluation>
<Weather test>
After the pellets of the aromatic polycarbonate resin composition are dried at 120 ° C. for 4 to 8 hours with a hot air circulating drier, an injection temperature 280 is obtained using an injection molding machine (“ROBOSHOT-S-2000i 150B” manufactured by FANUC). A molded article 70 mm × 40 mm × 2 mm thick was molded at a temperature of 80 ° C. and a mold temperature of 80 ° C. The molded product was subjected to weathering test under the following conditions using a xenon weather meter ("Ci4000" manufactured by Atlas Corporation).
Black panel temperature: 63 ° C
Humidity: 50%
Irradiance: 0.55 W / m ² (340 nm, continuous illumination)
Irradiation time: 250 hours Total energy: 495 kJ / m ²
Filter combination: inner / quartz
Outer / type S borosilicate Condition of 1 cycle: 18 minutes water spray + 102 minutes no spray = 120 minutes total

<Measurement of color difference ΔE>
The hue of the molded product before and after the weathering test was measured using a D65 light source in accordance with JIS Z8730, and the color difference ΔE was determined by the following equation. As the ΔE is smaller, the weather resistance is better.
ΔE = {(L−L ′) ² + (a−a ′) ² + (b−b ′) ² } ^1/2

Hue of molded product before weathering test: L, a, b
Hue of molded product after weathering test: L ', a', b '

<Measurement of weathering change ΔYI>
The hue change (ΔYI) of the molded product before and after the weathering test is based on ASTM-E1925 from the X, Y and Z values obtained by measuring the transmitted light using Nippon Denshoku Co., Ltd. “SE-2000”. , It calculated | required by the following formula. The smaller the ΔYI, the better the yellowing resistance.
YI = [100 (1.28X-1.06Z)] / Y
ΔYI = YI of molded article after weathering-YI of molded article before weathering

From Table 1, it contains bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite as a phosphorus-based stabilizer (B) and a specific phosphite-based stabilizer (B-II) In addition, by containing the polybutylene glycol compound (C) having a number average molecular weight of 200 or more and less than 1,000 and the ultraviolet light absorber (D), the coloration, weather resistance, and yellowing suppression effect become excellent. It became clear.
On the other hand, in Comparative Examples 1 and 2 which do not contain the ultraviolet absorber (D), the weather resistance is inferior.
Also in Comparative Examples 3 to 5 in which a hindered amine light stabilizer was added instead of the ultraviolet light absorber (D), the weather resistance was poor, and the initial hue was greatly reduced.

Claims (6)

An aromatic polycarbonate resin (A) and 100 parts by mass of the aromatic polycarbonate resin (A),
Phosphate-based stabilizer (B-I) having a spiro ring skeleton as a phosphorus-based stabilizer (B) 0.001 to 0.1 parts by mass, and phosphite-based stabilizer represented by the following general formula (II) (B-II) 0.01 to 0.5 parts by mass,
0.05 to 2 parts by mass of a polybutylene glycol compound (C) having a number average molecular weight of 200 or more and less than 1,000,
Phosphite-based stabilizer (B-1) containing 0.01 to 1 part by mass of an ultraviolet absorber (D) and having a spiro ring skeleton is bis (2,6-di-tert-butyl-4-methylphenyl) An aromatic polycarbonate resin composition comprising pentaerythritol diphosphite.

(In formula (II), R ^{21 to} R ²⁵ each independently represent a hydrogen atom, an aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms.   The aromatic polycarbonate resin composition according to claim 1, further comprising 0.0005 to 0.2 parts by mass of an alicyclic epoxy compound (E) per 100 parts by mass of the aromatic polycarbonate resin (A). object.   The aromatic polycarbonate resin composition according to claim 2, wherein the alicyclic epoxy compound (E) is 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate.   A molded article obtained by molding the aromatic polycarbonate resin composition according to any one of claims 1 to 3.   The molded article according to claim 4, which is a light guide member.   The molded article according to claim 5, wherein the molded article is a light guide member built in a lighting device for a car.