TWI667284B - Polycarbonate resin composition and molded product - Google Patents

Abstract

The present invention relates to a polycarbonate resin composition containing a polycarbonate resin (A), a phosphorus-based antioxidant (B), a fatty acid ester (C), and ultraviolet absorption, and a molded article containing the same. Agent (D), and the amounts of the phosphorus-based antioxidant (B), fatty acid ester (C), and ultraviolet absorber (D) are 0.04 to 0.1 parts by weight, and 0.03 parts with respect to 100 parts by weight of the polycarbonate resin (A). ~ 0.5 parts by weight and 0 ~ 1 parts by weight, the phosphorus-based antioxidant (B) is at least two compounds, of which one is a phosphite-based compound, and the amount of the phosphite-based compound is the total of the phosphorus-based antioxidant (B) 40 ~ 80% by weight.

Description

Polycarbonate resin composition and molded article

The present invention relates to a polycarbonate resin composition and a molded article.

Polycarbonate resins are excellent in impact resistance, heat resistance, transparency, and the like, and have been used for a long time, for example, in molded products such as light guide plates, various lenses, and nameplates.

For example, Patent Document 1 discloses an aromatic polycarbonate resin composition for a light guide plate, which is formulated and stabilized in an aromatic polycarbonate resin whose ratio of weight average molecular weight to number average molecular weight is specified in a specific range. Agent and release agent.

In Patent Document 2, as a resin composition for a light guide plate, a resin composition including a polycarbonate, a polymethyl methacrylate, a cyclic olefin copolymer, and the like is disclosed. The resin composition has a high light transmittance and a low light transmittance. Birefringent thermoplastic resin.

Patent Document 3 discloses a polycarbonate resin composition for an optical molded product, which is obtained by blending polystyrene and a phosphorus-based antioxidant in a polycarbonate resin.

Patent Document 4 discloses a polycarbonate resin composition for a light guide member, which is prepared by blending two types of phosphite stabilizers and fatty acid esters in an aromatic polycarbonate resin having a specific viscosity average molecular weight. Moreover, one type of phosphite-based stabilizer has a specific structure, and is smaller than the other type of phosphite-based stabilizer.

However, in recent years, not only the light transmittance of optical molded products is required, but also various properties such as thermal stability, mechanical strength, hue, brightness, extrusion moldability, weather resistance, and long-term reliability are required for their use. For the characteristics, the resin compositions disclosed in Patent Documents 1 to 4 cannot sufficiently satisfy the above requirements.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2007-204737

[Patent Document 2] Japanese Patent Laid-Open No. 2007-214001

[Patent Document 3] Japanese Patent Laid-Open No. 2011-133647

[Patent Document 4] Japanese Patent Laid-Open No. 2013-234233

The present invention provides a polycarbonate resin composition capable of imparting excellent characteristics depending on the use of a molded article. The present invention also provides a molded product obtained by molding the polycarbonate resin composition and suitable for various applications.

The polycarbonate resin composition in the present invention comprises a polycarbonate resin (A), a phosphorus-based antioxidant (B), a fatty acid ester (C), and an ultraviolet absorber (D). The phosphorus-based antioxidant ( The amount of B) is 0.04 to 0.1 parts by weight based on 100 parts by weight of the polycarbonate resin (A), and the amount of the fatty acid ester (C) is 0.03 based on 100 parts by weight of the polycarbonate resin (A). ~ 0.5 parts by weight, the amount of the ultraviolet absorber (D) is 0 to 1 part by weight based on 100 parts by weight of the polycarbonate resin (A), and the phosphorus-based antioxidant (B) is at least two kinds of compounds. One of the at least two compounds is a compound represented by the general formula (1),

(Wherein R ¹ represents an alkyl group having 1 to 20 carbon atoms, and a represents an integer of 0 to 3)

The other type of the phosphorus-based antioxidant (B) is a compound represented by any one of the general formulae (2) to (4),

(In the formula, R ² , R ³ , R ^5, and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an alkyl ring having 6 to 12 carbon atoms. Alkyl, aralkyl or phenyl having 7 to 12 carbons; R ⁴ represents a hydrogen atom or an alkyl having 1 to 8 carbons; X represents a single bond, a sulfur atom, or a formula: -CHR ^7- (here, R ⁷ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms); A represents an alkylene group having 1 to 8 carbon atoms or the formula: * -COR ^8- (this Where R ⁸ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a group represented by an oxygen-side bond); Y and Z are each a hydroxyl group and a carbon atom having 1 to 8 carbon atoms. Alkoxy or aralkoxy having 7 to 12 carbons, the other representing a hydrogen atom or alkyl having 1 to 8 carbons)

(In the formula, R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted by an alkyl group, and b and c each independently represent an integer of 0 to 3)

(Wherein R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted by an alkyl group)

The amount of the compound represented by the general formula (1) is 40 to 80% by weight based on the total amount of the phosphorus-based antioxidant (B).

The molded article in the present invention is obtained by molding the polycarbonate resin composition.

The molded product of the present invention obtained by molding the polycarbonate resin composition of the present invention has not only high light transmittance, but also excellent thermal stability, high mechanical strength, excellent color tone, and high In addition to brightness, excellent extrusion moldability, excellent weather resistance, etc., even when exposed to high-temperature and high-humidity conditions, the decrease in light transmittance is small, and it has excellent long-term reliability.

Hereinafter, embodiments will be described in detail. However, there is a case where unnecessary detailed explanation is omitted. For example, a detailed description of a well-known item may be omitted or a duplicate description of substantially the same configuration may be omitted. The reason is to prevent the following description from becoming unnecessarily lengthy so as to facilitate the understanding of those skilled in the art.

In addition, the inventors and others provide the following explanations in order for those skilled in the art to fully understand the present invention, and are not intended to limit the subject matter described in the scope of patent applications.

(Embodiment 1: Polycarbonate resin composition)

The polycarbonate resin composition of Embodiment 1 is a polycarbonate resin (A), a phosphorus-based antioxidant (B), a fatty acid ester (C), and an ultraviolet absorber (D). The polycarbonate resin composition of the present invention may contain other components as necessary.

Polycarbonate resin (A) is an ester obtained by reacting various dihydroxy diaryl compounds with carbochlorine or by reacting dihydroxy diaryl compounds with carbonates such as diphenyl carbonate. Aggregate obtained by exchange method. As a representative example, a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is mentioned.

Examples of the dihydroxydiaryl compound other than bisphenol A include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis ( 4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3- (Methylphenyl) propane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2- Bis (hydroxyaryl) alkanes such as bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane; 1,1 -Bis (hydroxyaryl) cycloalkanes such as bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane; 4,4'-dihydroxydiphenyl ether, Dihydroxydiaryl ethers such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether; Dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide; 4 2,4'-dihydroxydiphenylsulfene, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfene and other dihydroxydiarylfluorenes; 4,4'-dihydroxy Diphenyl difluorene, 4,4'-dihydroxy-3,3'-dimethyldiphenyl fluorene, and other dihydroxy diaryl hydrazones are used alone or in combination of two or more. In addition to these, you can also use pipe , Dipiperidinyl hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl and the like.

Furthermore, you may mix and use the said dihydroxy diaryl compound and the trivalent or more phenol compound shown below, for example.

Examples of the trivalent or higher phenol compounds include resorcinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6 -Dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4,4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

The viscosity average molecular weight of the polycarbonate resin (A) is preferably 10,000 to 100,000, and more preferably 12,000 to 30,000. When producing such a polycarbonate resin (A), a molecular weight regulator, a catalyst, and the like may be used as necessary.

The phosphorus-based antioxidant (B) is a component that improves the thermal stability and color tone of the obtained polycarbonate resin composition.

The polycarbonate resin composition in the present invention contains at least two compounds as the phosphorus-based antioxidant (B). One of the at least two compounds is a compound represented by the general formula (1): [Chem 5]

(In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, and a represents an integer of 0 to 3).

In the general formula (1), R ¹ is an alkyl group having 1 to 20 carbon atoms, but is more preferably an alkyl group having 1 to 10 carbon atoms.

Examples of the compound represented by the general formula (1) include: phenyl phosphite, tolyl phosphite, (2,4-di-tert-butylphenyl) phosphite, and ginsenophosphite Phenyl esters, etc. Among these, particularly preferred is ginseng (2,4-di-tert-butylphenyl) phosphite, such as commercially available Irgafos 168 ("Irgafos" is a registered trademark of BASF Societas Europaea manufactured by BASF Corporation). ).

Examples of the phosphorus-based antioxidant (B) other than the compound represented by the general formula (1) include compounds represented by the general formula (2):

(In the formula, R ² , R ³ , R ^5, and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an alkyl ring having 6 to 12 carbon atoms. Alkyl, aralkyl or phenyl having 7 to 12 carbons; R ⁴ represents a hydrogen atom or an alkyl having 1 to 8 carbons; X represents a single bond, a sulfur atom, or a formula: -CHR ^7- (here, R ⁷ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms); A represents an alkylene group having 1 to 8 carbon atoms or the formula: * -COR ^8- (this Where R ⁸ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a group represented by an oxygen-side bond); Y and Z are each a hydroxyl group and a carbon atom having 1 to 8 carbon atoms. An alkoxy group or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms).

In the general formula (2), R ² , R ³ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and 6 to 12 carbon atoms. Alkylcycloalkyl, aralkyl or phenyl with 7 to 12 carbon atoms.

Here, examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, and Tripentyl, isooctyl, third octyl, 2-ethylhexyl, and the like. Examples of the cycloalkyl group having 5 to 8 carbon atoms include cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the alkylcycloalkyl group having 6 to 12 carbon atoms include 1-methylcyclopentyl, 1-methylcyclohexyl, and 1-methyl-4-isopropylcyclohexyl. Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, and the like.

The aforementioned R ² , R ³ and R ⁵ are each preferably an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms or an alkyl cycloalkyl group having 6 to 12 carbon atoms. It is particularly preferred that R ² and R ⁵ are each independently a third alkyl group such as a third butyl group, a third pentyl group, a third octyl group, a cyclohexyl group, or a 1-methylcyclohexyl group. In particular, R ^{3 is} preferably a carbon number of 1 to 5 such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, and third pentyl. The alkyl group is more preferably a methyl group, a third butyl group, or a third pentyl group.

The aforementioned R ^{6 is} preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, and further preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, or n- Alkyl groups having 1 to 5 carbon atoms such as butyl, isobutyl, second butyl, third butyl, and third pentyl.

In the general formula (2), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include the alkyl groups exemplified in the description of R ² , R ³ , R ^5, and R ⁶ described above. In particular, R ^{4 is} preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group.

In the general formula (2), X represents a single bond, a sulfur atom, or a group represented by the formula: -CHR ^7- . Here, R ⁷ in the formula: —CHR ⁷ — represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms and the cycloalkyl group having 5 to 8 carbon atoms include the alkyl groups and cycloalkyl groups exemplified in the description of R ² , R ³ , R ^5, and R ⁶ . In particular, X is preferably a methylene group substituted with a single bond, methylene, or methylol, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl group. Preferably a single key.

In the general formula (2), A represents an alkylene group having 1 to 8 carbon atoms or a formula: * -COR ^8- . Examples of the alkylene group having 1 to 8 carbon atoms include methylene, ethylidene, propylidene, butylidene, pentamethylene, hexamethylene, octamethylene, and 2,2- Dimethyl-1,3-propene and the like are preferred. In addition, R ⁸ in the formula: * -COR ⁸ -represents a single bond or an alkylene group having 1 to 8 carbon atoms. Examples of the alkylene group having 1 to 8 carbon atoms representing R ^{8 include} the alkylene groups exemplified in the description of A above. R ^{8 is} preferably a single bond or ethylene. In addition, in the formula: * -COR ^8- , * is an oxygen-side bond, and represents a case where a carbonyl group is bonded to an oxygen atom of a phosphite group.

In the general formula (2), one of Y and Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkoxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or carbon number 1 ~ 8 alkyl. Examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a third butoxy group, and a pentoxy group. Examples of the aralkoxy group having 7 to 12 carbon atoms include benzyloxy, α-methylbenzyloxy, α, α-dimethylbenzyloxy, and the like. Examples of the alkyl group having 1 to 8 carbon atoms include the alkyl groups exemplified in the description of R ² , R ³ , R ^5, and R ⁶ described above.

Examples of the compound represented by the general formula (2) include: 2,4,8,10-tetra-third-butyl-6- [3- (3-methyl-4-hydroxy-5-third-butyl) Phenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphacycloheptene, 6- [3- (3,5-di-third-butyl-4 -Hydroxyphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphoheptene, 6- [3- (3,5-Di-third-butyl-4-hydroxyphenyl) propoxy] -4,8-di-third-butyl-2,10-dimethyl-12H-dibenzo [d, g] [1,3,2] Dioxaphosphatacyclo, 6- [3- (3,5-di-third-butyl-4-hydroxyphenyl) propanyloxy] -4 , 8-di-tert-butyl-2,10-dimethyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphataoctacyclic and the like. Among these, especially in a field requiring optical characteristics, when the obtained polycarbonate resin composition is used, it is preferably 2,4,8,10-tetra-third-butyl-6- [ 3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphacycloheptene, for example , Commercially available Sumilizer GPC "Sumilizer" (registered trademark) manufactured by Sumitomo Chemical Co., Ltd.).

Furthermore, examples of the phosphorus-based antioxidant (B) other than the compound represented by the general formula (1) include compounds represented by the general formula (3):

(In the formula, R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted by an alkyl group, and b and c each independently represent an integer of 0 to 3).

In the general formula (3), R ⁹ and R ¹⁰ are an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted by an alkyl group, but an alkyl group having 1 to 10 carbon atoms or an alkane group may be further preferred. Substituted aryl.

Examples of the compound represented by the general formula (3) include 3,9-bis (2,6-di-third-butyl-4-methylphenoxy) -2,4,8,10-tetra Oxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-di Phosphospiro [5,5] undecane and the like are commercially available as Adekastab PEP-36A, Adekastab PEP-8 ("Adekastab" is a registered trademark) manufactured by ADEKA Corporation. Among these, 3,9-bis (2,6-di-third-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9- Diphosphospiro [5,5] undecane.

Furthermore, as a phosphorus-based antioxidant (B) other than the compound represented by general formula (1), the compound represented by general formula (4) is mentioned, for example:

(In the formula, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted by an alkyl group).

Examples of the compound represented by the general formula (4) include [1,1'-biphenyl] -4,4'-diylbis [bis (2,4-di-tert-butylphenoxy) phosphine ], Etc. For example, Sandostab P-EPQ (trade name) manufactured by Clariant Japan Co., Ltd. is commercially available.

The amount of the phosphorus-based antioxidant (B) is 0.04 to 0.1 parts by weight, and preferably 0.05 to 0.09 parts by weight based on 100 parts by weight of the polycarbonate resin (A). Phosphorus resistance When the amount of the oxidizing agent (B) is less than 0.04 parts by weight, the effects of improving the thermal stability and color tone are insufficient. Conversely, when the amount of the phosphorus-based antioxidant (B) exceeds 0.1 parts by weight, the effect of improving the thermal stability and color tone becomes insufficient.

As the phosphorus-based antioxidant (B) other than the compound represented by the general formula (1), at least one kind may be appropriately selected from the compounds represented by the general formulae (2) to (4) and used.

The polycarbonate resin composition of the present invention contains a compound represented by the general formula (1) and compounds other than the compound represented by the general formula (1) as a phosphorus-based antioxidant (B) and a compound represented by the general formula (1). The amount is 40 to 80% by weight, preferably 42 to 70% by weight, based on the total amount of the phosphorus-based antioxidant (B). In the case where the amount of the compound represented by the general formula (1) is less than 40% by weight of the total amount of the phosphorus-based antioxidant (B), especially the improvement effect of thermal stability is not sufficient. , Yellowing is not suppressed and the hue is reduced. Conversely, when the amount of the compound represented by the general formula (1) exceeds 80% by weight of the total amount of the phosphorus-based antioxidant (B), especially the improvement effect of thermal stability is not sufficient, and due to molding at high temperature, In processing, yellowing was not suppressed and the hue was reduced.

The fatty acid ester (C) is a component that functions together with the above-mentioned phosphorus-based antioxidant (B) to suppress yellowing of the obtained polycarbonate resin composition and improve color tone. Furthermore, the fatty acid ester (C) is a component that imparts extrusion moldability to a polycarbonate resin composition when a molded article is produced by extrusion molding.

As the fatty acid ester (C), a general condensation compound of an aliphatic carboxylic acid and an alcohol can be used.

Examples of the aliphatic carboxylic acid include a saturated or unsaturated monocarboxylic acid, a dicarboxylic acid, and a tricarboxylic acid. The aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Among these, monocarboxylic acids and dicarboxylic acids having 6 to 36 carbon atoms are preferred, and saturated monocarboxylic acids having 6 to 36 carbon atoms are more preferred.

Specific examples of the aliphatic carboxylic acid include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, behenic acid, wax acid, and beeswax. Acids, triconic acid, montanic acid, glutaric acid, adipic acid, azelaic acid, etc.

Examples of the alcohol include saturated or unsaturated monohydric alcohols and polyhydric alcohols, and these alcohols may have substituents such as a fluorine atom, a chlorine atom, a bromine atom, and an aryl group. Among these, a saturated alcohol having a carbon number of 30 or less is preferred, and an aliphatic saturated monohydric alcohol and an aliphatic saturated polyol having a carbon number of 30 or less are more preferred. Furthermore, the aliphatic alcohol also includes an alicyclic alcohol.

Specific examples of the alcohol include octanol, decanol, dodecanol, tetradecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerol, pentaerythritol, 2, 2-dihydroxyperfluoropropanol, neopentyl glycol, di-trimethylolpropane, dipentaerythritol and the like.

Specific examples of the fatty acid ester (C) include behenyl behenate, octyldodecyl behenate, stearyl stearate, glyceryl monopalmitate, and glyceryl monostearate. Ester, glyceryl monooleate, glyceryl distearate, glyceryl tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol Tetrastearate and the like can be used alone or in combination of two or more kinds. Among these, stearates such as glycerol monostearate and pentaerythritol distearate are preferred. For example, Rikemal S-100A (trade name) manufactured by Riken Vitamin Co., Ltd. or Japan is commercially available. Unistar H476DP ("Unistar" is a registered trademark) manufactured by Oil Corporation.

The amount of the fatty acid ester (C) is based on 100 of the polycarbonate resin (A). The weight part is 0.03 to 0.5 weight part, and preferably 0.05 to 0.2 weight part. When the amount of the fatty acid ester (C) is less than 0.03 parts by weight, the effect of suppressing yellowing and improving hue, or the effect of imparting extrusion moldability are insufficient. Conversely, when the amount of the fatty acid ester (C) exceeds 0.5 parts by weight, the effect of improving the color tone or the effect of imparting extrusion moldability becomes insufficient.

The ultraviolet absorber (D) is a component that further improves the weather resistance of the obtained polycarbonate resin composition, and can be appropriately used according to the use of a molded article obtained by molding the polycarbonate resin composition. As described below, for example, when a molded article is used as an optical lens, by using a polycarbonate resin composition prepared by blending the ultraviolet absorber (D), it is possible to use even a sunlight or a light emitting diode (LED). (Light Emitting Diode) illumination can also be maintained in a state where the light transmittance of the molded product is high.

Examples of the ultraviolet absorber (D) include benzotriazole-based compounds, The ultraviolet absorber which is usually compounded into a polycarbonate resin, such as a system compound, a stilbene aniline compound, etc., is used individually or in combination of 2 or more types.

Examples of the benzotriazole-based compound include a compound represented by the general formula (5):

(In the formula, R ¹⁵ and R ¹⁶ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted by an alkyl group, and d and e each independently represent an integer of 0 to 3).

Examples of the compound represented by the general formula (5) include 2- (2-hydroxy-5-third octylphenyl) benzotriazole. For example, TINUVIN 329 (TINUVIN manufactured by BASF Corporation) is commercially available. (Registered trademark), Seesorb 709 manufactured by Shipro Kasei Co., Ltd., Kemisorb 79 manufactured by Chemipro Kasei Co., Ltd., and the like.

As three Compounds, for example, 2,4-diphenyl-6- (2-hydroxyphenyl-4-hexyloxyphenyl) 1,3,5-tris For example, TINUVIN 1577 manufactured by BASF is commercially available.

As an anilide compound, for example, formula (6): The indicated compounds and the like are commercially available, for example, Sanduvor VSU manufactured by Clariant Japan.

The amount of the ultraviolet absorber (D) is 0 to 1 part by weight, and preferably 0.05 to 0.5 part by weight based on 100 parts by weight of the polycarbonate resin (A). When the amount of the ultraviolet absorbent (D) exceeds 1 part by weight, the initial color tone of the obtained polycarbonate resin composition may be reduced. When the amount of the ultraviolet absorber (D) is 0.1 parts by weight or more, the effect of further improving the weather resistance of the polycarbonate resin composition is particularly exerted sufficiently.

Furthermore, in the polycarbonate resin composition of the first embodiment, As long as the effects in the present invention are not impaired, for example, various additives such as antioxidants, colorants, release agents, softeners, antistatic agents, impact modifiers, and polymers other than polycarbonate resin (A) are appropriately blended. .

The method for producing the polycarbonate resin composition is not particularly limited, and examples thereof include polycarbonate resin (A), phosphorus-based antioxidant (B), fatty acid ester (C), ultraviolet absorber (D), and The above-mentioned various additives or polymers other than the polycarbonate resin (A), etc., a method of appropriately adjusting the type and amount of each component, and mixing them with a known mixer such as a drum or a belt mixer; or A method of melt-kneading by an extruder. By these methods, particles of a polycarbonate resin composition can be easily obtained.

The shape and size of the particles of the polycarbonate resin composition obtained as described above are not particularly limited, as long as it is the shape and size of ordinary resin particles. Examples of the shape of the particles include an elliptical columnar shape and a cylindrical shape. As the size of the particles, the length is preferably about 2 to 8 mm. In the case of an elliptical column, the long diameter of the cross-section ellipse is about 2 to 8 mm, the short diameter is about 1 to 4 mm, and the shape is cylindrical. In this case, the diameter of the section circle is preferably about 1 to 6 mm. Furthermore, each particle that can be obtained is of such a size, and all particles that can form a particle aggregate are of such a size, and the average value of the particle aggregates is of such a size, and is not particularly limited.

As described above, the first embodiment is described as an example of the technology disclosed in this application. However, the technology in the present invention is not limited to this, and can also be applied to embodiments in which changes, substitutions, additions, omissions, and the like are appropriately performed.

(Embodiment 2: Molded Product)

The molded product of the second embodiment is obtained by molding the polycarbonate resin composition of the first embodiment obtained as described above.

The manufacturing method of the said molded article is not specifically limited, For example, the method of shape | molding a polycarbonate resin composition by a well-known injection molding method, a compression molding method, etc. are mentioned.

As a molded article in the present invention, an optical lens, a light guide for a vehicle lamp, a light guide film, a surface light emitting material, a name plate, and the like are preferably exemplified.

In particular, when a molded article is used as an optical lens, a polycarbonate resin composition prepared by blending the above-mentioned ultraviolet absorber (D) and having better weather resistance is used, so that even if it is irradiated by sunlight or LED lighting, etc. After that, it can be maintained in a state where the light transmittance of the molded product is high.

Especially when the molded product is a light guide for a vehicle lamp, the light guide for a vehicle lamp has excellent thermal stability, and has a high light transmittance even when the molding process is performed at a high temperature, which is sufficiently suppressed. Those who turn yellow and have excellent hue are used as lighting tools that use a light source such as an LED in the vicinity to light up and give high visibility. Therefore, even if the light guide for a vehicle lamp is a thin type having a thickness of about 0.4 mm, there are few cases where the color tone is changed and the appearance is reduced, or the resin itself is deteriorated by high temperature molding, and the industrial use value is extremely high.

In addition, the light guide for daylight (daytime light guide) in the present invention refers to the daytime available near various vehicle lamps such as headlights, auxiliary headlights such as fog lights, and daytime running lights. Light guide for lighting.

Especially when the molded product is a light-guiding film, the light-guiding film is excellent in thermal stability, and has high light transmittance even in the case of molding processing at a high temperature, which sufficiently suppresses yellowing and is excellent in color tone. . Therefore, even if the light guide film is 600 For thicknesses of less than about μm, there are fewer cases where the color tone changes and the appearance decreases, or the resin itself deteriorates through high-temperature molding. The balance of brightness, light transmittance, and color tone stability is good, and the extrusion moldability is also good. Excellent, so the industrial use value is extremely high.

In addition, the light guide film in the present invention refers to a film used in various display parts such as a liquid crystal display device of a portable computer such as a smart phone, preferably having a thickness of 600 μm or less, and more preferably 400 μm or less.

The light-guiding film in the present invention is obtained by extruding the particles of the polycarbonate resin composition or the like. The manufacturing method of a light guide film is not specifically limited, For example, a well-known shaping | molding method, such as a well-known T-die extrusion molding method and a calender molding method, can be used. In addition, a sheet-shaped molded article of a polycarbonate resin composition can be obtained by a known injection molding method, compression molding method, and the like, and if necessary, processed from the sheet-shaped molded product to a desired thickness by cutting or the like. The film.

As described above, the second embodiment is described as an example of the technology disclosed in this application. However, the technology in the present invention is not limited to this, and can be applied to embodiments in which changes, substitutions, additions, and omissions are appropriately performed.

[Example]

Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited to these examples. In addition, "part" and "%" are based on weight unless otherwise specified in advance.

Use the following as raw materials.

1. Polycarbonate resin (A)

Polycarbonate resin synthesized from bisphenol A and carbochloride

Calibre 200-30

(Brand name, manufactured by Sumika Styron Polycarbonate Co., Ltd., "Calibre" is a registered trademark of Styron Europe GmbH, viscosity average molecular weight: 18000, hereinafter referred to as "PC")

2. Phosphorus antioxidant (B) 2-1. Ginseng (2,4-di-tert-butylphenyl) phosphite represented by the following formula

Irgafos 168

(Trade name, manufactured by BASF, hereinafter referred to as "B1")

2-2. 3,9-bis (2,6-di-third-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3, represented by the following formula, 9-Diphosphaspiro [5,5] undecane

Adekastab PEP-36

(Product name, manufactured by ADEKA Corporation, hereinafter referred to as "R2")

3. Fatty acid ester (C)

Glycerol monostearate

Rikemal S-100A

(Product name, manufactured by Riken Vitamin Co., Ltd., hereinafter referred to as "GM")

4. Ultraviolet absorbent (D)

2- (2-hydroxy-5-third octylphenyl) benzotriazole

TINUVIN 329

(Trade name, manufactured by BASF, hereinafter referred to as "UV")

(1) First embodiment [Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-2]

Each of the above raw materials was put into a drum at a ratio shown in Table 1 at one time, and after dry-mixing for 10 minutes, a biaxial extruder (manufactured by Japan Steel Manufacturing Co., Ltd., TEX30α) was used at a melting temperature of 240 ° C Melt-knead to obtain pellets of a polycarbonate resin composition.

In addition, the particles obtained in Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-2 are all approximately elliptic columns, and the size (average (mm)) of the aggregate containing 100 particles They are described below.

Using the obtained granules, each evaluation was performed by the following method. will The results are shown in Table 1.

(a) Initial hue

After the obtained granules were dried at 120 ° C for 4 hours or more, using an injection molding machine (manufactured by Fanuc Co., Ltd., ROBOSHOT S2000i100A), the molding temperature was 280 ° C and the mold temperature was 80 ° C. JIS K 7139 "Plastic -Test piece "type A multifunctional test piece (length 168mm x thickness 4mm). The end surface of the 168mm long optical path test piece was cut, and the cut end surface was mirror-finished using a resin plate end surface mirror machine (manufactured by Megaro Technica Co., Ltd., Pla-Beauty PB-500).

A spectrophotometer (manufactured by Hitachi, Ltd., UH4150) was equipped with a long-path measurement accessory device, using a 50W halogen lamp as a light source, and covering the front of the light source with 5.6mm × 2.8mm and the sample before covering 6.0mm × 2.8 In a state of mm, in a region of a wavelength of 380 to 780 nm, a standard light source D65 is used for the entire length direction, and the spectral transmittance of each 1 nm test piece is measured with a 10-degree field of view. Based on the measured spectral transmittance, the respective yellowness was determined and used as the initial hue YI with a length of 168 mm. In addition, a YI of 13 or less is regarded as good (in the table, indicated by ○), and a YI of more than 13 is regarded as defective (in the table, indicated by ×).

(b) Yellowing suppression effect

After the molten particles were allowed to stand at 280 ° C. for 15 minutes in the cylinder of the injection molding machine used in the above-mentioned (a) initial color tone, a 168 mm long optical path test piece was produced in the same manner as in (a) above.

For this test piece, the length 168 was obtained in the same manner as in (a) above. YI in mm is calculated by subtracting the value obtained in (a) from the obtained value to calculate ΔYI. In addition, ΔYI is 11 or less is considered good (indicated by ○ in the table), and more than 11 is considered poor (indicated by × in the table).

(c) Long-term reliability

A 168 mm long optical path test piece was produced in the same manner as in (a) above. A spectrophotometer (manufactured by Hitachi, Ltd., UH4150) was equipped with a long-path measurement accessory device, using a 50W halogen lamp as a light source, and covering the front of the light source with 5.6mm × 2.8mm and the sample before covering 6.0mm × 2.8 In the state of mm, the spectral transmittance of each 1 nm test piece is measured in the region of the wavelength of 380 to 780 nm in the entire length direction. The measured spectral transmittances are accumulated and the ten digits are rounded to obtain the cumulative transmittance before the test.

Next, the test piece was placed in a constant temperature and humidity tank (manufactured by ADVANTEC, constant temperature and humidity device AG-327), and the hydrolysis test was performed at a temperature of 90 ° C. and a relative humidity of 90% for 500 hours. After the test, calculate the cumulative transmittance of the test piece after the test in the same way as above, and calculate the Δ cumulative transmittance (the difference between the cumulative transmittance = the cumulative transmittance before the test-the cumulative transmittance after the test) . Δ Cumulative transmittance indicates the degree of change in the cumulative transmittance before and after the test, and indicates the situation that the smaller the Δ cumulative transmittance, the lower the transmittance even after being exposed to high temperature and humidity conditions. The smaller the better the long-term reliability. In addition, the Δ cumulative transmittance is less than 5000 (good in the table, indicated by ○), and 5000 or more is regarded as poor (in the table, indicated by x).

The polycarbonate resin compositions of Examples 1-1 to 1-3 not only formulated two compounds as phosphorus-based antioxidants (B), but also phosphorous acid ginseng (2,4) which belongs to the compound represented by the general formula (1). The amount of the di-third butyl phenyl) ester is adjusted within a range of 40 to 80% by weight based on the total amount of the phosphorus-based antioxidant (B). Therefore, the 168mm long optical path test pieces formed from these polycarbonate resin compositions are not only less yellow, but also excellent in initial hue, but also 168mm long light formed after being left at 280 ° C for 15 minutes. Cheng test piece, also fully inhibited yellowing, excellent thermal stability. In addition, even if the 168mm long optical path test piece formed from these polycarbonate resin compositions is subjected to a hydrolysis test for 500 hours at a temperature of 90 ° C and a relative humidity of 90%, the decrease in light transmittance is very small. , Long-term reliability is also excellent.

In contrast, regarding the polycarbonate resin composition of Comparative Example 1-1, the amount of the phosphorus-based antioxidant (B) based on 100 parts by weight of the polycarbonate resin (A) exceeded 0.1 part by weight, and the phosphorous acid ginseng ( The amount of 2,4-di-tert-butylphenyl) ester is less than 40% by weight of the total amount of the phosphorus-based antioxidant (B). Therefore, not only the 168mm long optical path test piece formed from the polycarbonate resin composition has a large yellowness, but the initial hue is poor, but also the 168mm long optical path test piece formed after being left at 280 ° C for 15 minutes. Insufficient suppression of yellow Change, the thermal stability is poor. In addition, after a 168 mm long optical path test piece formed from the polycarbonate resin composition was subjected to a hydrolysis test under high temperature and high humidity conditions for a long time, the transmittance was significantly reduced, and the long-term reliability was also poor.

Regarding the polycarbonate resin composition of Comparative Example 1-2, the amount of ginseng (2,4-di-tert-butylphenyl) phosphite exceeded 80% by weight of the total amount of the phosphorus-based antioxidant (B). Therefore, not only the 168mm long optical path test piece formed from the polycarbonate resin composition has a large yellowness, but the initial hue is poor, but also the 168mm long optical path test piece formed after being left at 280 ° C for 15 minutes. The yellowing was not sufficiently suppressed, and the thermal stability was poor.

(2) Second embodiment [Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-2]

Each of the above raw materials was put into a drum at a ratio shown in Table 2 at one time, and pellets of a polycarbonate resin composition were obtained by the same method as in the first embodiment. In addition, the particles obtained in Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-2 were all approximately elliptic columns, and the size (average (mm)) of the aggregate containing 100 particles They are described below.

Using the obtained pellets, each evaluation was performed in the same manner as in the first embodiment. The results are shown in Table 2.

In the evaluation of (a) initial hue, a YI of 16 or less was regarded as good (indicated by ○ in the table), and a value of more than 16 was regarded as defective (indicated by × in the table). In the evaluation of the (b) yellowing suppression effect, the residence time in the cylinder of the injection molding machine was changed to 10 minutes, and ΔYI was 18 or less to be good (in the table, it is indicated by ○). It is set as bad (in the table, it is represented by x).

The polycarbonate resin compositions of Examples 2-1 to 2-4 were blended with not only two compounds as phosphorus-based antioxidants (B), but also phosphorous acid ginseng (2, The amount of 4-di-tert-butylphenyl) ester is adjusted within a range of 40 to 80% by weight based on the total amount of the phosphorus-based antioxidant (B). Therefore, not only the 168mm long optical path test piece formed from the polycarbonate resin composition has a small yellowness and excellent initial hue, but also the 168mm long optical path test formed after being left at 280 ° C for 10 minutes. The sheet also sufficiently suppressed yellowing and was excellent in thermal stability. In addition, even if the 168mm long optical path test piece formed from these polycarbonate resin compositions is subjected to a hydrolysis test for 500 hours at a temperature of 90 ° C and a relative humidity of 90%, the decrease in light transmittance is very small. , Long-term reliability is also excellent.

On the other hand, regarding the polycarbonate resin composition of Comparative Example 2-1, the amount of the ultraviolet absorber (D) relative to 100 parts by weight of the polycarbonate resin (A) exceeds 1 Parts by weight. Therefore, the 168 mm long optical path test piece formed from the polycarbonate resin composition has a large yellowness and a poor initial hue.

Regarding the polycarbonate resin composition of Comparative Example 2-2, the amount of the phosphorus-based antioxidant (B) based on 100 parts by weight of the polycarbonate resin (A) exceeded 0.1 part by weight, and the phosphorous acid ginseng (2,4- The amount of the di-third butylphenyl) ester is less than 40% by weight of the total amount of the phosphorus-based antioxidant (B). Therefore, not only the 168mm long pathlength test piece formed from the polycarbonate resin composition has a large yellowness and poor initial hue, but also the 168mm long pathlength test piece formed after being left at 280 ° C for 10 minutes. The yellowing was not sufficiently suppressed, and the thermal stability was poor. In addition, after a 168 mm long optical path test piece formed from the polycarbonate resin composition was subjected to a hydrolysis test under high temperature and high humidity conditions for a long time, the transmittance was significantly reduced, and the long-term reliability was also poor.

(3) Third embodiment [Examples 3-1 to 3-4 and Comparative Examples 3-1 to 3-4]

Each of the above raw materials was put into a drum at a ratio shown in Table 3 at one time, and pellets of a polycarbonate resin composition were obtained by the same method as in the first embodiment. In addition, the particles obtained in Examples 3-1 to 3-4 and Comparative Examples 3-1 to 3-4 are all approximately elliptic columns, and the size (average (mm)) of the aggregate containing 100 particles They are described below.

Using the obtained granules, each evaluation was performed by the following method. The results are shown in Table 3.

(a) Initial hue

After the obtained granules were dried at 120 ° C for 4 hours or more, using an injection molding machine (manufactured by Fanuc Co., Ltd., ROBOSHOT S2000i100A), the molding temperature was 280 ° C and the mold temperature was 80 ° C. JIS K 7139 "Plastic -Test piece "type A multifunctional test piece (length 168mm x thickness 4mm). The end surface of the 168mm long optical path test piece was cut, and the cut end surface was mirror-finished using a resin plate end surface mirror machine (manufactured by Megaro Technica Co., Ltd., Pla-Beauty PB-500).

A spectrophotometer (manufactured by Hitachi, Ltd., UH4150) was equipped with a long-path measurement accessory device, using a 50W halogen lamp as a light source, and covering the front of the light source with 5.6mm × 2.8mm and the sample before covering 6.0mm × 2.8 In a state of mm, in a region of a wavelength of 380 to 780 nm, using a standard light source D65 for the entire length direction, the spectral transmittance of each 1 nm test piece was measured with a 10-degree field of view. Based on the measured spectral transmittance, each yellowness was determined and used as the initial hue YI with a length of 168 mm. In addition, a YI of 13 or less is regarded as good (in the table, indicated by ○), and a YI of more than 13 is regarded as defective (in the table, indicated by ×).

(b) Yellowing suppression effect

After the molten particles were allowed to stand at 280 ° C. for 15 minutes in the cylinder of the injection molding machine used in the above-mentioned (a) initial color tone, a 168 mm long optical path test piece was produced in the same manner as in (a) above.

For this test piece, YI having a length of 168 mm was obtained in the same manner as in (a) above, and ΔYI was calculated by subtracting the value obtained in (a) from the obtained value. In addition, ΔYI is 11 or less is considered good (indicated by ○ in the table), and more than 11 is considered poor (indicated by × in the table).

(c) Extrusion formability

Using an extrusion sheet forming machine (manufactured by Tanabe Plastics Machinery Co., Ltd., a single-axis 40mm sheet extruder), under the conditions of a screw revolution of 90 rpm and a melting temperature of 260 ° C, the obtained pellets were formed into a width of 250 mm and a thickness of 0.5mm sheet. The appearance of the obtained sheet and the contamination of the roll surface caused by volatile components during molding were visually observed, and evaluated based on the following evaluation criteria. In addition, if the evaluation is excellent or good, it is a level where there is no practical problem.

(Evaluation criteria)

Excellent (indicated by ◎ in the table): The surface of the sheet was completely free of streak marks, and there was no contamination of the roller surface.

Good (indicated by ○ in the table): There are almost no stripe marks on the surface of the sheet, and there is almost no contamination on the surface of the roller.

Normal (in the table, indicated by △): The surface of the sheet is marked with stripes, and the surface of the roller is also contaminated.

Defective (indicated by x in the table): There are more stripes on the surface of the sheet, and the contamination on the surface of the roller is also obvious.

(d) Long-term reliability

Evaluation of long-term reliability was performed by the same method as in the first embodiment.

The polycarbonate resin compositions of Examples 3-1 to 3-4 not only blended two compounds as phosphorus-based antioxidants (B), but also used phosphite (2,4) as a compound represented by the general formula (1). The amount of the di-third-butylphenyl) ester is adjusted within a range of 40 to 80% by weight based on the total amount of the phosphorus-based antioxidant (B). Therefore, not only the 168mm long optical path test pieces formed from these polycarbonate resin compositions are small in yellowness and excellent in initial hue, but also 168mm long formed after being left at 280 ° C for 15 minutes. The optical path test piece also sufficiently suppresses yellowing and is excellent in thermal stability. Furthermore, these polycarbonate resin compositions are excellent in extrusion moldability when molded into a sheet. In addition, even if a 168 mm long optical path test piece formed from these polycarbonate resin compositions is subjected to a hydrolysis test for 500 hours at a temperature of 90 ° C and a relative humidity of 90%, the decrease in light transmittance is very small. Long-term reliability is also excellent.

In contrast, regarding the polycarbonate resin composition of Comparative Example 3-1, the amount of the phosphorus-based antioxidant (B) based on 100 parts by weight of the polycarbonate resin (A) exceeded 0.1 part by weight, and the phosphorous acid ginseng ( The amount of 2,4-di-tert-butylphenyl) ester is lower than that of phosphorus-based antioxidants 40% by weight of the total amount of the agent (B). Therefore, not only the 168mm long optical path test piece formed from the polycarbonate resin composition has a large yellowness, but the initial hue is poor, but also the 168mm long optical path test piece formed after being left at 280 ° C for 15 minutes. The yellowing was not sufficiently suppressed, and the thermal stability was poor. In addition, after a 168 mm long optical path test piece formed from the polycarbonate resin composition was subjected to a hydrolysis test under high temperature and high humidity conditions for a long time, the transmittance decreased significantly, and the long-term reliability was also poor.

Regarding the polycarbonate resin composition of Comparative Example 3-2, the amount of ginseng (2,4-di-tert-butylphenyl) phosphite exceeded 80% by weight of the total amount of the phosphorus-based antioxidant (B). Therefore, not only the 168mm long optical path test piece formed from the polycarbonate resin composition has a large yellowness, but the initial hue is poor, but also the 168mm long optical path test piece formed after being left at 280 ° C for 15 minutes. The yellowing was not sufficiently suppressed, and the thermal stability was poor.

Regarding the polycarbonate resin composition of Comparative Example 3-3, the amount of the fatty acid ester (C) relative to 100 parts by weight of the polycarbonate resin (A) was less than 0.03 parts by weight. Therefore, a 168 mm long optical path test piece formed by allowing the polycarbonate resin composition to stand at 280 ° C. for 15 minutes did not sufficiently suppress yellowing and was inferior in thermal stability. Furthermore, the polycarbonate resin composition had poor extrusion moldability when it was formed into a sheet.

Regarding the polycarbonate resin composition of Comparative Example 3-4, the amount of the fatty acid ester (C) relative to 100 parts by weight of the polycarbonate resin (A) exceeded 0.5 parts by weight. Therefore, the 168 mm long optical path test piece formed from the polycarbonate resin composition has a large yellowness and a poor initial hue. Furthermore, the polycarbonate resin composition had poor extrusion moldability when it was formed into a sheet.

As mentioned above, the embodiment which is an example of the technique in this invention was demonstrated. A detailed description is provided for this purpose.

Therefore, among the components described in the detailed description, not only Constituent elements necessary to solve the problem are included, and in order to illustrate the above-mentioned technology, constituent elements not necessary to solve the problem may be included. Therefore, it is not necessary to directly consider these non-essential components as necessary because they are described in the detailed description.

In addition, since the above-mentioned embodiment is exemplified by those skilled in the present invention, various changes, substitutions, additions, omissions, etc. can be made within the scope of the patent application or its equivalent scope.

(Industrial availability)

The present invention can be preferably used, for example, as a molded product such as an optical lens, a light guide for a vehicle lamp, a light guide film, a surface light emitting material, or a name plate.

Claims (7)

A polycarbonate resin composition comprising a polycarbonate resin (A), a phosphorus antioxidant (B), a fatty acid ester (C), and an ultraviolet absorber (D). The phosphorus antioxidant (B ) Is 0.04 to 0.1 parts by weight relative to 100 parts by weight of the polycarbonate resin (A), and the amount of the fatty acid ester (C) is 0.03 to 100 parts by weight of the polycarbonate resin (A) 0.5 parts by weight, the amount of the ultraviolet absorber (D) is 0 to 1 part by weight with respect to 100 parts by weight of the polycarbonate resin (A), and the phosphorus-based antioxidant (B) is two kinds of compounds, the two kinds One of the compounds is a compound represented by the general formula (1),

(In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, and a represents an integer of 0 to 3) The other phosphorus-based antioxidant (B) is another compound represented by the general formula (3),

(In the formula, R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted with an alkyl group, and b and c each independently represent an integer of 0 to 3) The above general formula (1) The amount of the compound represented is 40 to 67% by weight of the total amount of the phosphorus-based antioxidant (B), and the fatty acid ester (C) is glycerol monostearate. The polycarbonate resin composition according to claim 1, wherein the compound represented by the general formula (1) is ginseng (2,4-di-t-butylphenyl) phosphite. The polycarbonate resin composition according to claim 1, wherein the 168mm long optical path test piece formed by the molding has a △cumulative penetration rate calculated based on the following formula less than 5000: △cumulative penetration rate=test Cumulative penetration rate before the test-Cumulative penetration rate after the test here, Cumulative penetration rate before the test: For the test piece for 500 hours of hydrolysis test under the conditions of temperature 90 ℃ and relative humidity 90%, the test piece will be 380~780nm area, the value obtained by accumulating the spectral transmittance in the full length direction measured every 1nm; and the cumulative transmittance after the test: for the test piece after the above hydrolysis test, the wavelength will be 380~ A value obtained by accumulating the spectral transmittance in the full-length direction obtained by measuring every 1 nm in the 780 nm region. The polycarbonate resin composition according to claim 1, in which the 168mm long optical path test piece formed by the molding has a spectral transmittance in the full-length direction measured from every wavelength of 380-780nm in the region of 380-780nm. The initial color tone YI is 13 or less. A molded product formed by molding the polycarbonate resin composition of claim 1. If the shaped product of claim 5, it is a light guide for car lights. If the shaped product of claim 5, it is a light guide film.