KR102058330B1 - Polycarbonate resin composition and optical molded article - Google Patents

Abstract

It is a polycarbonate resin composition which mix | blends 0.005-3.0 weight part of melt viscosity modifiers (B) and 0.005-1.0 weight part of a phosphite ester type compound (C) with respect to 100 weight part of polycarbonate resin (A), and it measures When the melt viscosity at the temperature of 220 ° C. and the shear rate of 10 sec ⁻¹ is η, the ratio η ^{1 /} η 2 of the melt viscosity η ¹ of the polycarbonate resin composition to the melt viscosity η 2 of the polycarbonate resin (A) is 0.45. ? 1 /? 2? 0.95 is satisfied, The polycarbonate resin composition.

Description

Polycarbonate resin composition and optical molded article {POLYCARBONATE RESIN COMPOSITION AND OPTICAL MOLDED ARTICLE}

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

Polycarbonate resins have been used for molded articles such as light guide plates, various lenses, name plates, and the like in view of excellent impact resistance, heat resistance, transparency, and the like.

For example, Patent Document 1 discloses an aromatic polycarbonate resin composition for light guide plates in which a stabilizer and a release agent are blended with an aromatic polycarbonate resin in which the ratio of the weight average molecular weight and the number average molecular weight is defined in a specific range. .

Patent document 2 discloses the polycarbonate resin composition for optical molded articles in which polystyrene and 1 type of phosphorus antioxidant were mix | blended with polycarbonate resin.

In addition, as disclosed in, for example, Patent Documents 3 to 6, in order to obtain excellent light transmittance and to improve the brightness of the optical member, various resin compositions in which polycarbonate resin and other materials are used in combination are proposed. have.

However, the polycarbonate resin compositions disclosed in Patent Literatures 3 to 6 have no deterioration in the light transmittance even in the case of molding as a material of a recent light guide plate (in particular, even when molded at high temperature in order to perform thin molding). It is not possible to sufficiently satisfy the demands of the

Japanese Patent Laid-Open No. 2007-204737 Japanese Patent Publication No. 09-020860 Japanese Patent Laid-Open No. 2011-133647 Japanese Patent Publication No. 11-158364 Japanese Patent Laid-Open No. 2001-215336 Japanese Patent Laid-Open No. 2004-051700

The present invention is a polycarbonate excellent in thermal stability, excellent in light transmittance, and excellent in light transmittance even when molded at high temperature without impairing the properties such as heat resistance and mechanical strength of the polycarbonate resin. It provides a resin composition.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to solve such a subject, and, as a result, to a polycarbonate resin composition which mix | blends a melt viscosity modifier (B) and a phosphite ester compound (C) with a polycarbonate resin (A) In this case, the ratio of the melt viscosity of the polycarbonate resin composition and the melt viscosity of the polycarbonate resin (A) contained therein is satisfied so as to satisfy a value in a specific range, so that even when molded at a high temperature, there is no decrease in light transmittance. It was found that a polycarbonate resin composition having good color and brightness was obtained, and completed the present invention.

That is, this invention is a polycarbonate which mix | blends 0.005-3.0 weight part of melt viscosity modifiers (B) and 0.005-1.0 weight part of phosphorous acid ester compound (C) with respect to 100 weight part of polycarbonate resins (A). It is a resin composition and the ratio of melt viscosity (eta) ¹ of polycarbonate resin composition and melt viscosity (eta) 2 of polycarbonate resin (A), when melt viscosity in measurement temperature 220 degreeC and shear rate 10sec- ¹ is set to (eta) It is providing the polycarbonate resin composition and the optical molded article which shape | molds it, (eta) 1 / (eta) 2 satisfy | fills 0.45 <= (eta) 1 / (eta) 2 <= 0.95.

The polycarbonate resin composition of the present invention is excellent in thermal stability and weather resistance without impairing the properties such as heat resistance, mechanical strength, and the like originally possessed by the polycarbonate resin, and also has a light transmittance even when molded at a high temperature. Would be excellent. Therefore, even if it is a thin light-guide plate about 0.3 mm in thickness, for example, when a color changes, an external appearance falls, and resin itself deteriorates through high temperature shaping | molding, there is little industrial utilization value.

EMBODIMENT OF THE INVENTION Below, embodiment is described in detail. However, the detailed description may be omitted more than necessary. For example, detailed descriptions of well-known matters or redundant descriptions of substantially the same configuration may be omitted. This is for avoiding unnecessary description below and facilitating the understanding by those skilled in the art.

In addition, the inventors provide the following description 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 claims by these.

The polycarbonate resin composition used by this invention mix | blends a polycarbonate resin (A), a melt viscosity modifier (B), and a phosphite ester type compound (C). Moreover, you may mix | blend another component with the polycarbonate resin composition used by this invention as needed.

The polycarbonate resin (A) used in the present invention is a phosgene method for reacting various dihydroxydiaryl compounds and phosgene or a carbonate ester such as a dihydroxydiaryl compound and diphenyl carbonate. It is a polymer obtained by the transesterification method. As a representative example, the polycarbonate resin manufactured from 2, 2-bis (4-hydroxyphenyl) propane (bisphenol A) is mentioned.

As said dihydroxy diaryl compound, in addition to bisphenol A, it is bis (4-hydroxyphenyl) methane, 1, 1-bis (4-hydroxyphenyl) ethane, 2, 2-bis (4-hydroxy), for example. Phenyl) 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 (4-hydroxy-3,5 Bis (hydroxyaryl) alkanes such as dibromo phenyl) propane and 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane; Bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclopentane and 1,1-bis (4-hydroxyphenyl) cyclohexane; Dihydroxy diaryl ethers such as 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether; Dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide; Dihydroxy diaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; Dihydroxy diaryl sulfones, such as 4,4'- dihydroxy diphenyl sulfone and 4,4'- dihydroxy-3,3'- dimethyl diphenyl sulfone, are mentioned, These are single or two or more types. It is used to mix. In addition to these, piperazine, dipiperidylhydroquinone, resorcin, 4,4'-dihydroxydiphenyl, etc. may be mixed and used.

You may use the said dihydroxy diaryl compound and the trihydric or more phenol compound shown below further, for example.

As said trivalent or more phenolic compound, for example, phloroglucine, 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) -benzol, 1,1,1-tri- (4-hydroxyphenyl)- Ethane, 2,2-bis- [4,4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane, and the like.

It is preferable that it is 10000-100000, and, as for the viscosity average molecular weight of polycarbonate resin (A), it is more preferable that it is 12000-30000. In addition, when manufacturing such polycarbonate resin (A), a molecular weight modifier, a catalyst, etc. can be used as needed.

The melt viscosity modifier (B) used in the present invention is sheared by lowering the shear viscosity of the polycarbonate resin by behaving like any kind of lubricant when molding the polycarbonate resin composition. It means that the heat generation is suppressed from occurring more than necessary, and furthermore, it has the effect of reducing or suppressing the heat generation in the polycarbonate resin.

As the melt viscosity modifier (B), when the melt viscosity at the measurement temperature of 220 ° C. and the shear rate of 10 sec ⁻¹ is η, melting of the melt viscosity η ¹ of the polycarbonate resin composition and the polycarbonate resin (A) If the ratio (eta) 1 / (eta) 2 of viscosity (eta) 2 can be adjusted so that it may satisfy 0.45 <= (eta) 1 / (eta) 2 <0.95, it will not specifically limit, The polyether derivative represented by following General formula (1) etc. is typically mentioned. . In addition, a silicone type compound, a glycerin type compound, a pentaerythritol type compound, etc. are mentioned.

General formula (1):

Wherein R and R 'each independently represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, X is an alkylene group having 2 to 4 carbon atoms, Y is a branched alkylene group having 3 to 5 carbon atoms, and m and n are Each independently represents an integer of 3 to 60, and m + n represents an integer of 8 to 90)

Examples of the polyether derivatives of the formula (1), glycol-modified polytetramethylene glycol unit and containing the 1-ethyl-ethylene glycol units _{(e.g., HO- (CH 2 CH 2 CH} 2 CH 2 O) 24 (CH ₂ CH (C ₂ H ₅ ) O) ₁₃ -H and the like), for example, DCD-2000 (weight average molecular weight 2000) manufactured by Nichi Oil Co., Ltd., and the like. It is preferable that the weight average molecular weights of the polyether derivative represented by General formula (1) are 1000-4000.

Moreover, as a polyether derivative, the polyether derivative represented by following General formula (2), General formula (3), or General formula (4) among the polyether derivative represented by General formula (1) is suitable.

General formula (2):

(Wherein m and n each independently represent an integer of 3 to 60, and m + n represents an integer of 8 to 90)

Examples of the polyether derivatives of the formula (2), comprising a glycol-modified polytetramethylene glycol unit and 2-methyl-tetramethylene glycol units (e. G., HO- (CH ₂ CH ₂ CH ₂ CH ₂ O) ₂₂ ( _{CH 2 CH 2 CH (CH 3} ) CH 2 O) 5 -H , etc.) may be mentioned, for example, the Hodogaya Kagaku Kogyo (Co., Ltd.) of PTG-L1000 (weight average molecular weight 1000), PTG-L2000 ( Weight average molecular weight 2000), or PTG-L3000 (weight average molecular weight 3000) or the like. It is preferable that the weight average molecular weights of the polyether derivative represented by General formula (2) are 1000-4000.

General formula (3):

(Wherein m and n each independently represent an integer of 3 to 60, and m + n represents an integer of 8 to 90)

As the polyether derivative represented by the general formula (3), a modified glycol comprising ethylene glycol units and propylene glycol units _{(e.g., C 4 H 9 O- (CH} 2 CH 2 O) 21 (CH 2 CH (CH ₃ ) O) ₁₄ -H or C ₄ H ₉ O- (CH ₂ CH ₂ O) ₃₀ (CH ₂ CH (CH ₃ ) O) ₃₀ -H, etc.) is suitable, for example, uni-lube 60MB-26I ( Weight average molecular weight 1700), Unilube 50MB-72 (weight average molecular weight 3000), etc. are commercially available. It is preferable that the weight average molecular weights of the polyether derivative represented by General formula (3) are 1000-4000.

General formula (4):

(Wherein m and n each independently represent an integer of 3 to 60, and m + n represents an integer of 8 to 90)

Examples of the polyether derivatives of the formula (4), a modified glycol comprising ethylene glycol units and propylene glycol units (e. _{G., HO- (CH 2 CH 2 O} ) 17 (CH 2 CH (CH 3) O) _17- H is suitable and commercially available, for example, unilube 50DE-25 (weight average molecular weight 1750), etc. The weight average molecular weight of the polyether derivative represented by the general formula (4) is 1000 to 4000. desirable.

Until now, attempts have been made to improve the light transmittance of polycarbonate resins by adding linear polyoxyalkylene glycols, but since the polyoxyalkylene glycols have insufficient heat resistance, the polyoxyalkylene glycols are blended. When one polycarbonate resin composition is molded at a high temperature, the luminance and light transmittance of the molded article are lowered. In contrast, a melt viscosity modifier such as a polyether derivative represented by the general formula (1) is a bifunctional random copolymer, has high heat resistance, and is blended with a specific polyether derivative represented by the general formula (1). The molded article which shape | molded the polycarbonate resin composition at high temperature has high brightness and light transmittance.

Moreover, since the melt viscosity modifier (B) used by this invention is excellent also in compatibility with polycarbonate resin (A) from the point which has moderate lipophilic, the polycarbonate which mix | blended this melt viscosity modifier (B) Transparency of the molded article obtained from the nate resin composition also improves. It is preferable that the weight average molecular weights of the polyether derivative used for such a melt viscosity modifier (B) are 1000-4000, Furthermore, it is 2000-3000. When the weight average molecular weight of a polyether derivative is 1000-4000, while sufficient improvement effect of a light transmittance can be expected, a light transmittance does not rise and there is no possibility that a light transmittance may fall.

The amount of the polyether derivative is 0.005 to 3.0 parts by weight, preferably 0.1 to 1.5 parts by weight, and preferably 0.3 to 1.2 parts by weight based on 100 parts by weight of the polycarbonate resin (A). When the amount of the polyether derivative is less than 0.005 parts by weight, the effect of improving light transmittance and color is insufficient. On the contrary, when the amount of the polyether derivative exceeds 3.0 parts by weight, the dissolution rate increases and the light transmittance decreases.

A phosphite ester type compound (C) is mix | blended with the polycarbonate resin composition in this invention with melt viscosity modifiers (B), such as a specific polyether derivative. Thus, by simultaneously mixing a melt viscosity modifier (B) and a phosphite ester type compound (C), it can prevent generation of the shear heat of a polycarbonate resin composition to the maximum, and a polycarbonate resin (A) The polycarbonate resin composition with improved light transmittance can be obtained even when properties such as heat resistance and mechanical strength, which are inherently possessed, are not impaired, and even at high temperatures.

As a phosphite ester compound (C) used by this invention, the compound represented, for example by following General formula (5) is especially suitable.

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

In said general formula (5), although R <^1> is a C1-C20 alkyl group, it is preferable that it is a C1-C10 alkyl group further.

As a compound represented by General formula (5), a triphenyl phosphite, a tricresyl phosphite, a tris (2, 4-di-t- butylphenyl) phosphite, a trisnonyl phenyl phosphite, etc. are mentioned, for example. Can be. Among these, tris (2,4-di-t-butylphenyl) phosphite is particularly suitable, for example, Irgafos 168 ("Irgarfoss" manufactured by BASF Corporation) is a registered trademark of BASF Societas Europa. Commercially available).

As said phosphite ester type compound, the compound represented, for example by following General formula (6) besides the compound represented by the said General formula (5) is mentioned.

(Wherein R ² , R ³ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, and a 7 to 12 carbon atoms) An aralkyl group or a phenyl group, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, X represents a single bond, a sulfur atom or a formula: -CHR ^7- (wherein R ⁷ represents a hydrogen atom, An alkyl group or a cycloalkyl group having 5 to 8 carbon atoms, wherein A is an alkylene group having 1 to 8 carbon atoms or a formula: * -COR ^8- (wherein R ⁸ is a single bond or an alkyl having 1 to 8 carbon atoms); A rene group, and * denotes a bond on the oxygen side) Y and Z each represent a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, Hydrogen source on the other side Or an alkyl group having 1 to 8 carbon atoms)

In general formula (6), R <^2> , R <^3> , R <^5> and R <^6> are respectively independently a hydrogen atom, a C1-C8 alkyl group, a C5-C8 cycloalkyl group, a C6-C12 alkylcycloalkyl group, C7-C12 aralkyl group or a phenyl group is shown.

Here, as the alkyl group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, t-pen A methyl group, i-octyl group, t-octyl group, 2-ethylhexyl group, etc. are mentioned. As a C5-C8 cycloalkyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group etc. are mentioned, for example. As a C6-C12 alkylcycloalkyl group, a 1-methylcyclopentyl group, 1-methylcyclohexyl group, 1-methyl-4-i-propylcyclohexyl group etc. are mentioned, for example. As a C7-12 aralkyl group, a benzyl group, the (alpha)-methyl benzyl group, the (alpha), (alpha)-dimethylbenzyl group etc. are mentioned, for example.

R ² , R ³ and R ⁵ are each independently an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkylcycloalkyl group having 6 to 12 carbon atoms. In particular, R ² and R ⁵ are each independently a t-alkyl group such as a t-butyl group, a t-pentyl group, a t-octyl group, a cyclohexyl group, or a 1-methylcyclohexyl group. In particular, R ³ has 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group and t-pentyl group It is preferable that it is an alkyl group, and it is more preferable that it is a methyl group, t-butyl group, or t-pentyl group.

It is preferable that said R <^6> is a hydrogen atom, a C1-C8 alkyl group, or a C5-C8 cycloalkyl group, and a hydrogen atom, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i- It is more preferable that it is an alkyl group of 1 to 5 carbon atoms, such as a butyl group, sec-butyl group, t-butyl group, and t-pentyl group.

In General formula (6), R <^4> represents a hydrogen atom or a C1-C8 alkyl group. As a C1-C8 alkyl group, the alkyl group illustrated by description of said R <^2> , R <^3> , R <^5> and R <^6> is mentioned, for example. 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 formula (6), X represents a single bond, a sulfur atom or a group represented by the formula: -CHR ⁷ - group represented by. Here, the formula: -CHR ⁷ - R ⁷ represents a cycloalkyl group of a hydrogen atom, an alkyl group having 5 to 8 or 1 to 8 carbon atoms in the. As a C1-C8 alkyl group and a C5-C8 cycloalkyl group, the alkyl group and cycloalkyl group which were illustrated in the description of said R <^2> , R <^3> , R <^5> and R <^6> , respectively are mentioned, for example. In particular, X is preferably a single bond, a methylene group, or a methylene group substituted with a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, and the like. More preferably, it is a bond.

In the formula (6), A is an alkylene group having 1 to 8 carbon atoms or a group represented by the formula of: * -COR ⁸ - represents a group represented by the. Examples of the alkylene group having 1 to 8 carbon atoms include methylene group, ethylene group, propylene group, butylene group, pentamethylene group, hexamethylene group, octamethylene group, 2,2-dimethyl-1,3-propylene group and the like. These are mentioned, Preferably it is a propylene group. In addition, R <^8> in a formula: * -COR < ⁸ >-represents a single bond or a C1-C8 alkylene group. As a C1-C8 alkylene group which shows R <^8> , the alkylene group illustrated by description of said A is mentioned, for example. R ⁸ is preferably a single bond or an ethylene group. In addition, * in formula: * -COR < ⁸ >-is a bond on the oxygen side, and shows that the carbonyl group couple | bonds with the oxygen atom of a phosphite group.

In General formula (6), Y and Z represent either a hydroxyl group, a C1-C8 alkoxy group, or a C7-C12 aralkyloxy group, and the other is a hydrogen atom or a C1-C8 alkyl group. Indicates. As a C1-C8 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, t-butoxy group, a pentyloxy group, etc. are mentioned, for example. As a C7-12 aralkyloxy group, a benzyloxy group, the (alpha)-methyl benzyloxy group, the (alpha), (alpha)-dimethyl benzyloxy group etc. are mentioned, for example. As a C1-C8 alkyl group, the alkyl group illustrated by description of said R <^2> , R <^3> , R <^5> and R <^6> is mentioned, for example.

As a compound represented by General formula (6), for example, 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-t-butylphenyl) Propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine, 6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -2, 4,8,10-tetra-t-butyldibenzo [d, f] [1,3,2] dioxaphosphine, 6- [3- (3,5-di-t-butyl-4-hydroxy Phenyl) propoxy] -4,8-di-t-butyl-2,10-dimethyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphosine, 6- [3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -4,8-di-t-butyl-2,10-dimethyl-12H-dibenzo [d, g] [1,3, 2] dioxaphosphosine etc. are mentioned. Among these, 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4, when using the obtained polycarbonate resin composition especially in the field | area where an optical characteristic is calculated | required. -Hydroxy-5-t-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine are suitable, for example, the smistizer GP by Sumitomo Chemical Co., Ltd. ("Smallizer" is a registered trademark) available commercially.

As the phosphite ester compound (C), in addition to the compound represented by the general formula (5) and the compound represented by the general formula (6), for example, the compound represented by the general formula (7) can be suitably used. have.

(In formula, R <^9> and R <^10> respectively independently represents the C1-C20 alkyl group or the aryl group which may be substituted by the alkyl group, and b and c respectively independently represent the integer of 0-3.)

As the compound represented by the general formula (7), for example, Adeka's staff PEP-36 (&quot; Adeka's staff 'is a registered trademark) manufactured by Adeka Co., Ltd. is commercially available.

The amount of the phosphite ester compound (C) is 0.005 to 1.0 part by weight, preferably 0.01 to 0.5 part by weight, and more preferably 0.02 to 0.1 part by weight based on 100 parts by weight of the polycarbonate resin (A). When the amount of the phosphite ester compound (C) is less than 0.005 parts by weight, the effect of improving light transmittance and color is insufficient. In contrast, even when the amount of the phosphite ester compound (C) exceeds 1.0 part by weight, the effect of improving light transmittance and color is insufficient.

In addition to the above components, in the polycarbonate resin composition according to the embodiment, for example, the use of a molded article obtained by molding a polycarbonate resin composition with an ultraviolet absorber, which is a component that further improves weather resistance of the polycarbonate resin composition obtained. It can use suitably according to the.

As a ultraviolet absorber, the ultraviolet absorber normally mix | blended with polycarbonate resin, such as a benzotriazole type compound, a triazine type compound, a benzophenone type compound, and an oxalate anhydride type compound, is used individually or in combination of 2 or more types, for example. Can be used.

As the benzotriazole compound, for example, as the benzotriazole compound, 2- (2-hydroxy-5-t-octylphenyl) benzotriazole and 2- (3-tert-butyl-2-hydroxy-5- Methylphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di-tert-pentyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2H-benzotriazole-2- Yl) -4-methyl-6- (3,4,5,6-tetrahydrophthalimylmethyl) phenol, 2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole, 2- [2'-hydroxy-3,5-di (1,1-dimethylbenzyl) phenyl] -2H-benzotriazole And 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) 4- (1,1,3,3-tetramethylbutyl) phenol]. Especially, 2- (2-hydroxy-5-t-octylphenyl) benzotriazole etc. are suitable, For example, TINUVIN 329 (Tinuvin is a registered trademark) and cipro by BASF Corporation. Seesaw 709 manufactured by Kasei Co., Ltd. and Chemisob 79 manufactured by Kasei Co., Ltd. are commercially available.

As a triazine type compound, it is 2, 4- diphenyl-6- (2-hydroxyphenyl-4-hexyloxyphenyl) 1, 3, 5- triazine, 2- [4, 6-bis (2, 4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl ) -5-[(hexyl) oxy] phenol, and the like, for example, Tinuvin 1577 manufactured by BASF, Inc. is commercially available.

As an oxalate anhydride type compound, Sanduvor VSU etc. by Clariant Japan Co., Ltd. can be obtained commercially, for example.

As a benzophenone type compound, 2, 4- dihydroxy benzophenone, 2-hydroxy-4-n-octoxy benzophenone, etc. are mentioned, for example.

The quantity of a ultraviolet absorber is 0-1.0 weight part with respect to 100 weight part of polycarbonate resins (A), and it is preferable that it is 0-0.5 weight part. When the quantity of a ultraviolet absorber (D) exceeds 1.0 weight part, there exists a possibility that the initial stage color of the polycarbonate resin composition obtained may fall. Moreover, especially when the quantity of a ultraviolet absorber (D) is 0.1 weight part or more, the effect which improves the weather resistance of a polycarbonate resin composition further is exhibited large.

Moreover, in the polycarbonate resin composition which concerns on embodiment, in the range which does not impair the effect in this invention, For example, various additives, such as another antioxidant, a coloring agent, a mold release agent, a softener, an antistatic agent, an impact modifier, Polymers other than the polycarbonate resin (A) may be appropriately blended.

There is no restriction | limiting in particular in the manufacturing method of a polycarbonate resin composition, A polycarbonate resin (A), a melt viscosity modifier (B), and a phosphite ester type compound (C), said various additives and polycarbonate as needed With respect to polymers other than the resin (A), there may be mentioned a method of appropriately adjusting the type and amount of each component and mixing them with a known mixer such as a tumbler or a ribbon blender, or a method of melt kneading with an extruder. have. By these methods, pellets of the polycarbonate resin composition can be easily obtained.

There is no restriction | limiting in particular in the shape and size of the pellet of the polycarbonate resin composition obtained as mentioned above, What is necessary is just the shape and size which a general resin pellet has. For example, an elliptical columnar shape, a columnar shape, etc. are mentioned as a shape of a pellet. As the size of the pellet, one having a length of about 2 to 8 mm is suitable, and in the case of an elliptic columnar shape, one having a long diameter of a cross section ellipse of about 2 to 8 mm and a short diameter of about 1 to 4 mm is suitable. In this case, it is suitable that the diameter of a cross section circle is about 1-6 mm. In addition, each obtained pellet may be such a size, all the pellets which form a pellet aggregate may be such a magnitude | size, the average value of a pellet aggregate may be such a magnitude | size, and there is no limitation in particular.

The polycarbonate resin composition of the present invention is obtained by molding the polycarbonate resin composition obtained as described above.

There is no limitation in particular in the manufacturing method of the polycarbonate resin composition of this invention, For example, the method of shape | molding a polycarbonate resin composition by a well-known injection molding method, compression molding method, etc. is mentioned.

As mentioned above, embodiment was described as an illustration of this invention. However, the technique in the present invention is not limited to this, and can be applied to embodiments in which modifications, substitutions, additions, omissions, and the like are appropriately performed.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, "part" and "%" are each a basis of weight unless there is particular notice.

The following were used as a raw material.

1. Polycarbonate Resin (A):

Polycarbonate Resin Synthesized from Bisphenol A and Carbonyl Chloride

Caliber 200-80

(A brand name, product made by Smica styrene polycarbonate, Inc., a "caliber" are registered trademarks of styrene europe GmbH, the viscosity average molecular weight: 15000, hereinafter referred to as "PC")

2. Melt viscosity modifier (B) (polyether derivative of the following formula):

2-1. Modified glycols (polyether derivatives) comprising tetramethylene glycol units and 2-methyltetramethylene glycol units:

(Brand name, product made by Hodogaya Kagaku Kogyo Co., Ltd., weight average molecular weight: 2000, hereinafter referred to as "compound B1")

2-2. Modified glycol (polyether derivative) comprising tetramethylene glycol unit and 1-ethylethylene glycol unit:

(Brand name, Nichiyu Co., Ltd., weight average molecular weight: 2000, hereinafter referred to as "compound B2")

2-3. Modified glycols (polyether derivatives) comprising ethylene glycol units and propylene glycol units:

UniLube 50MB-72

(Brand name, Nichiyu Co., Ltd., weight average molecular weight: 3000, hereinafter referred to as "Compound B3")

2-4. Modified glycols (polyether derivatives) comprising ethylene glycol units and propylene glycol units:

UniLube 60MB-26I

(Brand name, Nichiyu Co., Ltd., weight average molecular weight: 1700, hereinafter referred to as "compound B4")

2-5. Modified glycols (polyether derivatives) comprising ethylene glycol units and propylene glycol units:

Uni-Lube 50DE-25

(Brand name, Nichiyu Co., Ltd., weight average molecular weight: 1750, hereinafter referred to as "Compound B5")

3. Phosphorous ester compound (C):

3-1. Tris (2, 4-di-t-butylphenyl) phosphite represented by the following formula

Irgafos 168

(Brand name, product made by BASF Corporation, `` compound C1 '' hereinafter)

3-2. 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-t-butylphenyl) propoxy] dibenzo [d represented by the following formula: , f] [1,3,2] dioxaphosphine

Smeizer GP

(Brand name, Sumitomo Chemical Co., Ltd. make, `` compound C2 '' hereinafter)

3-3. 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5] represented by the following formula: , 5] Undecan

Adecas Staff PEP-36

(Brand name, Adekaze, `` compound C3 '' hereinafter)

(Examples 1 to 17 and Comparative Examples 1 to 6)

Each said raw material is put into the tumbler collectively at the ratio shown in Table 1 and Table 2, and after dry-mixing for 10 minutes, using a twin screw extruder (TEX30alpha made from Nippon Sekosho Co., Ltd.) at the melting temperature of 220 degreeC. Melt kneading was carried out to obtain pellets of the polycarbonate resin composition. In addition, the pellets obtained by the Example and the comparative example are substantially elliptic columnar shape, and the aggregate containing 100 pellets has the average value of the length of about 5.1 mm-about 5.4 mm, respectively, and the average value of the long diameter of a cross section ellipse is about 4.1 mm. To about 4.3 mm and a short diameter averaged from about 2.2 mm to about 2.3 mm.

Using the obtained pellets, each test piece for evaluation was produced and used for evaluation according to the following method. The results are shown in Table 1 and Table 2.

(Measuring method of melt viscosity)

After drying the obtained pellet and the pellet of polycarbonate resin (A) at 120 degreeC or more for 4 hours, measurement temperature 220 using a capillary rheometer (the Shimadzu Corporation make, flow tester CFT-500) Melt viscosity was measured in the range of ¹ degreeC ^-1 to 100sec <^-1> of shear rate. ¹ and the melt viscosity of the polycarbonate resin (A) were made into (eta) 2 for the melt viscosity of the polycarbonate resin composition in shear rate 10sec <^-1> .

(Production method of test piece)

After drying the obtained pellets at 120 degreeC for 4 hours or more, it prescribed | regulated by JISK7139 "plastic test piece" at the molding temperature of 360 degreeC and the mold temperature of 80 degreeC using the injection molding machine (RoboSHOT S2000i100A made from FANAK Co., Ltd.). The multipurpose test piece A type (length 168 mm x thickness 4 mm) was produced. The end surface of this test piece was cut and mirror-processed with respect to the cutting end surface using the resin plate end surface mirror machine (made by Megarotechnica Co., Ltd., Flabeauty PB-500).

(Evaluation method of integrated transmittance)

A long light path measurement accessory was installed in a spectrophotometer (Hitachi Seisakusho Co., Ltd., UH4150), and a 5.6 mm x 2.8 mm mask before the light source and a 6.0 mm x 2.8 mm mask before the sample were installed using a 50 W halogen lamp as the light source. In the state used, the spectral transmittance of each test piece for every 1 nm was measured with respect to the full length direction of a test piece in the area | region of the wavelength 380-780 nm. Each integrated transmittance was calculated | required by integrating the measured spectral transmittances and rounding off the ten digits. Moreover, integrated transmittance | permeability was made into good (shown in (circle) in table), and less than 30000 was bad (indicated by x in table).

(Evaluation method of yellowness)

Based on the spectral transmittance measured in said evaluation method of integrated transmittance | permeability, each yellowness was calculated | required in 10 degree | time field of view using the standard light source D65. Moreover, when yellowness was 20 or less (it shows with ○ in a table), and it exceeds 20, it was set as defect (it shows with x in a table).

In the polycarbonate resin compositions of Examples 1 to 18, a melt viscosity modifier (B) such as a specific polyether derivative and a phosphite ester compound (C) are each specified in the polycarbonate resin (A). It is compounded with. Therefore, the test piece molded from the polycarbonate resin composition has a high integrated transmittance and a small yellowness.

Thus, when the polycarbonate resin composition of Examples 1-18 does not impair the heat resistance which the polycarbonate resin (A) has inherently, is high in the light transmittance in a visible region, and is molded at high temperature Edo is excellent in light transmittance. And the molded article which shape | molded such polycarbonate resin composition is excellent in color, since yellowness is small, and also in the case of carrying out molding process at high temperature, it is excellent in color.

On the other hand, since the amount of melt viscosity modifiers (compound B1), such as a specific polyether derivative, is small in the polycarbonate resin composition of the comparative example 1, the integrated transmittance is low and yellowness is also large. Thus, the molded article which shape | molded the polycarbonate resin composition of the comparative example 1 is inferior in brightness | luminance and a hue.

Since the polycarbonate resin composition of the comparative example 2 has many quantities of the specific melt viscosity modifier (compound B1), while the integrated transmittance | permeability is low and yellowness is also large. Thus, the molded article which shape | molded the polycarbonate resin composition of the comparative example 2 is inferior in brightness | luminance and a hue.

Since the polycarbonate resin composition of the comparative example 3 has little quantity of a phosphite ester type compound (C), a test piece has a big yellowness. Thus, the molded article which shape | molded the polycarbonate resin composition of the comparative example 3 is inferior in color.

Since the polycarbonate resin composition of Comparative Example 4 has a large amount of phosphorous acid ester compound (C), the integrated transmittance is low and the yellowness is large. Thus, the molded article which shape | molded the polycarbonate resin composition of the comparative example 4 is inferior in brightness | luminance and a hue.

Since the polycarbonate resin composition of the comparative example 5 has little quantity of a specific melt viscosity modifier (compound B5), while the integrated transmittance | permeability is low and yellowness is also large. Thus, the molded article which shape | molded the polycarbonate resin composition of the comparative example 5 is inferior in brightness | luminance and a hue.

Since the polycarbonate resin composition of the comparative example 6 has many quantities of the specific melt viscosity modifier (compound B5), while the integrated transmittance | permeability is low and yellowness is also large. Thus, the molded article which shape | molded the polycarbonate resin composition of the comparative example 5 is inferior in brightness | luminance and a hue.

As mentioned above, embodiment was described as an example of the technique in this invention. Therefore, detailed description was provided.

Accordingly, the components described in the detailed description may include not only components essential for solving the problem but also components that are not essential for solving the problem in order to illustrate the above technology. Therefore, having such non-essential components described in the detailed description, it should not be recognized that such non-essential components are essential.

In addition, since embodiment mentioned above is for illustration of the technique in this invention, various changes, substitution, addition, omission, etc. can be made in a claim or its equivalent range.

The polycarbonate resin composition of the present invention is excellent in thermal stability and weather resistance without impairing the properties such as heat resistance, mechanical strength, and the like originally possessed by the polycarbonate resin, and also has a light transmittance even when molded at a high temperature. Would be excellent. Therefore, even if it is a thin light-guide plate about 0.3 mm in thickness, for example, when a color changes, an external appearance falls, and resin itself deteriorates through high temperature shaping | molding, there is little industrial utilization value.

Claims (11)

0.005 to 3.0 parts by weight of the melt viscosity modifier (B) and 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2 based on 100 parts by weight of the polycarbonate resin (A) -2 A polycarbonate resin composition comprising 0.005 to 1.0 parts by weight of a phosphite ester compound (C) excluding 4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane,
When the melt viscosity at the measurement temperature of 220 ° C. and the shear rate of 10 sec ⁻¹ is η, the ratio η ^{1 /} η 2 of the melt viscosity η ¹ of the polycarbonate resin composition and the melt viscosity η 2 of the polycarbonate resin (A) is 0.45≤η1 / η2≤0.95,
Said melt viscosity modifier (B) is a polyether derivative represented by following General formula (1), The polycarbonate resin composition whose weight average molecular weights of this polyether derivative are 1000-4000.
General formula (1):

Wherein R and R 'each independently represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, X is an alkylene group having 2 or 3 carbon atoms, Y is a branched alkylene group having 3 to 5 carbon atoms, and m and n are Each independently represents an integer of 3 to 60, and m + n represents an integer of 8 to 90) The polycarbonate according to claim 1, wherein the ratio η1 / η2 of the melt viscosity η1 of the polycarbonate resin composition and the melt viscosity η2 of the polycarbonate resin (A) satisfies 0.45 ≦ η1 / η2 ≦ 0.80. Bonate resin composition. The polycarbonate resin composition of Claim 1 whose compounding quantity of the said melt viscosity modifier (B) is 0.3-1.2 weight part with respect to 100 weight part of said polycarbonate resin (A). The polycarbonate according to claim 1, wherein an integrated transmittance in a region of wavelength 380 to 780 nm of the test piece (168 mm in total length x 4 mm in thickness) injection molded from the polycarbonate resin composition at a molding temperature of 360 ° C is 30000 or more. Bonate resin composition. The polyether derivative according to claim 1, wherein the polyether derivative represented by the general formula (1) is a polyether derivative represented by the following general formula (3) and the weight average molecular weight of the polyether derivative is 1000 to 4000. Bonate resin composition.
General formula (3):

(Wherein m and n each independently represent an integer of 3 to 60, and m + n represents an integer of 8 to 90) The polyether derivative according to claim 1, wherein the polyether derivative represented by the general formula (1) is a polyether derivative represented by the following general formula (4), wherein the weight average molecular weight of the polyether derivative is 1000 to 4000. Bonate resin composition.
General formula (4):

(Wherein m and n each independently represent an integer of 3 to 60, and m + n represents an integer of 8 to 90) The polycarbonate resin composition according to claim 1, wherein the phosphite ester compound (C) is at least one compound selected from compounds represented by the following general formulas (5), (6) and (7).
Formula (5):

(In formula, R <^1> represents the aryl group which may be substituted by the C1-C20 alkyl group or alkyl group, and a shows the integer of 0-3.)
Formula (6):

(Wherein R ² , R ³ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, and a 7 to 12 carbon atoms) An aralkyl group or a phenyl group, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, X represents a single bond, a sulfur atom or a formula: -CHR ^7- (wherein R ⁷ represents a hydrogen atom, An alkyl group or a cycloalkyl group having 5 to 8 carbon atoms, wherein A is an alkylene group having 1 to 8 carbon atoms or a formula: * -COR ^8- (wherein R ⁸ is a single bond or an alkyl having 1 to 8 carbon atoms); A rene group, and * denotes a bond on the oxygen side) Y and Z each represent a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, Hydrogen source on the other side Or an alkyl group having 1 to 8 carbon atoms)
Formula (7):

(In formula, R <^9> , R <^10> is the aryl group which may be substituted by the C1-C20 alkyl group or alkyl group, b, c shows the integer of 0-3.) The polycarbonate resin composition according to claim 7, wherein the compound represented by the general formula (5) is tris (2,4-di-t-butylphenyl) phosphite. The compound represented by the above general formula (6) is 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-t -Butylphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine, Polycarbonate resin composition. The molded article for optics containing the polycarbonate resin composition in any one of Claims 1-9. The optical molded article according to claim 10, wherein the molded article is a light guide plate.