KR101908877B1 - Polycarbonate resin composition and molded article - Google Patents

Abstract

(B), the fatty acid ester (C) and the ultraviolet absorber (D), and the phosphorus antioxidant (B), the phosphoric acid ester (C) and the ultraviolet absorber Is 0.04 to 0.1 parts by weight, 0.03 to 0.5 parts by weight and 0 to 1 part by weight, and the phosphorus-based antioxidant (B) is at least two kinds of compounds, based on 100 parts by weight of the polycarbonate resin (A) Wherein one of them is a phosphite compound and the amount of the phosphite compound is 40 to 80% by weight of the total amount of the phosphorus antioxidant (B), and a molded article comprising the polycarbonate resin composition.

Description

POLYCARBONATE RESIN COMPOSITION AND MOLDED ARTICLE [0002]

This disclosure relates to polycarbonate resin compositions and molded articles.

BACKGROUND ART Polycarbonate resins are conventionally used in molded articles such as light guide plates, various lenses and nameplates in that they have excellent impact resistance, heat resistance and transparency.

For example, Patent Document 1 discloses an aromatic polycarbonate resin composition for a light guide plate 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 to the number average molecular weight is specified within a specific range.

Patent Document 2 discloses a resin composition comprising a thermoplastic resin having high light transmittance and low birefringence such as polycarbonate, polymethyl methacrylate, and cyclic olefin copolymer as a resin composition for a light guide plate .

Patent Document 3 discloses a polycarbonate resin composition for optical molded articles in which a polycarbonate resin is blended with polystyrene and one kind of phosphorus-based antioxidant.

Patent Document 4 discloses that an aromatic polycarbonate resin having a specific viscosity-average molecular weight is blended with two phosphite stabilizers and fatty acid esters, one phosphite stabilizer has a specific structure, Discloses a polycarbonate resin composition for a light-guiding member which is smaller in content than a filler-based stabilizer.

However, in recent years, optical molded articles have been required to have not only light transmittance but also various properties depending on their use among various properties such as heat stability, mechanical strength, color, brightness, extrusion moldability, weather resistance and long-term reliability And the resin compositions disclosed in Patent Documents 1 to 4 do not satisfy these requirements sufficiently.

Japanese Patent Application Laid-Open No. 2007-204737 Japanese Patent Application Laid-Open No. 2007-214001 Japanese Patent Laid-Open No. 11-133647 Japanese Patent Application Laid-Open No. 2013-234233

The present disclosure provides a polycarbonate resin composition capable of imparting excellent properties to the use of a molded article. The present disclosure also provides a molded article which is formed by molding the polycarbonate resin composition and is suitable for various uses.

The polycarbonate resin composition in the present disclosure is a polycarbonate resin composition,

(A), a phosphorus-based antioxidant (B), a fatty acid ester (C) and an ultraviolet absorber (D)

The amount of the phosphorus antioxidant (B) is 0.04 to 0.1 part by weight based on 100 parts by weight of the polycarbonate resin (A)

The amount of the fatty acid ester (C) is 0.03 to 0.5 part by weight based on 100 parts by weight of the polycarbonate resin (A)

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)

Wherein the phosphorus antioxidant (B) is at least two kinds of compounds, and 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)

, ≪ / RTI >

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

In the molded article of the present disclosure,

(A), a phosphorus-based antioxidant (B), a fatty acid ester (C) and an ultraviolet absorber (D)

The amount of the phosphorus antioxidant (B) is 0.04 to 0.1 part by weight based on 100 parts by weight of the polycarbonate resin (A)

The amount of the fatty acid ester (C) is 0.03 to 0.5 part by weight based on 100 parts by weight of the polycarbonate resin (A)

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)

Wherein the phosphorus antioxidant (B) is at least two kinds of compounds, and 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)

, ≪ / RTI >

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

.

The molded article of the present disclosure obtained by molding the polycarbonate resin composition of the present disclosure has not only high light transmittance but also excellent heat stability, high mechanical strength, excellent color, high luminance, excellent extrusion moldability, Etc., there is little deterioration in light transmittance even after being provided under high temperature and high humidity conditions, and excellent long term reliability is also obtained.

Hereinafter, embodiments will be described in detail. However, the detailed description may be omitted more than necessary. For example, there is a case where a detailed description of a well-known item or a duplicate description of a substantially same configuration is omitted. This is for the purpose of facilitating understanding by those skilled in the art, avoiding unnecessary redundancy in the following description.

Furthermore, the inventors shall provide the following description to enable those skilled in the art to fully understand the present disclosure, and are not intended to limit the subject matter recited in the claims.

(Embodiment 1: polycarbonate resin composition)

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

The polycarbonate resin (A) can be produced by a phosgene method in which various dihydroxy diaryl compounds are reacted with phosgene, or by an ester exchange method in which a dihydroxy diaryl compound is reacted with a carbonic ester such as diphenyl carbonate . Representative examples include polycarbonate resins prepared from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

Examples of the dihydroxy diaryl compound include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2- Phenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2- -Bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy- (Dibromophenyl) 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; Dihydroxydialyl ethers such as 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethyl diphenyl ether; Dihydroxydialylsulfides such as 4,4'-dihydroxydiphenyl sulfide; Dihydroxydialylsulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfoxide; Dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfone, and 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfone. These may be used singly or in combination of two or more . In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, and the like may be mixed and used.

The dihydroxy diaryl compound may be used in combination with, for example, a trivalent or higher phenol compound shown below.

Examples of the trivalent or higher phenol compound include fluoroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6- Tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) Ethane and 2,2-bis- [4,4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane.

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

The phosphorus antioxidant (B) is a component for improving the thermal stability and color of the obtained polycarbonate resin composition.

The polycarbonate resin composition of the present disclosure 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):

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

≪ / RTI >

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 triphenyl phosphite, tricresyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, trisnonylphenyl phosphite, . Of these, tris (2,4-di-t-butylphenyl) phosphite is particularly suitable, and for example, commercially available as Irgafos 168 (BASF SE, registered trademark of BASF SE) It is possible.

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):

(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, 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 group represented by the formula: -CHR ⁷ - (wherein R ⁷ represents a hydrogen atom, A represents an alkylene group having 1 to 8 carbon atoms or a group represented by the formula: -COR ⁸ - (wherein R ⁸ represents a single bond or a carbon number of 1 to 8, And Y represents an alkyl group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and Y and Z each represent a hydrogen atom, And the other is a hydrogen atom or a carbon May represent an alkyl group of 1 to 8)

And the like.

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, an alkylcycloalkyl group having 6 to 12 carbon atoms , An aralkyl group having 7 to 12 carbon atoms, or a phenyl group.

Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i- Butyl group, i-octyl group, t-octyl group, 2-ethylhexyl group and the like. Examples of the cycloalkyl group having 5 to 8 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the alkylcycloalkyl group having 6 to 12 carbon atoms include a 1-methylcyclopentyl group, a 1-methylcyclohexyl group and a 1-methyl-4-i-propylcyclohexyl group. Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group,? -Methylbenzyl group,?,? - dimethylbenzyl group and the like.

It is preferable that each of R ² , R ³ and R ⁵ is 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, it is preferable that R ² and R ⁵ are each independently a t-alkyl group such as a t-butyl group, a t-pentyl group or a t-octyl group, a cyclohexyl group or a 1-methylcyclohexyl group. Particularly, R ³ is a group having 1 to 5 carbon atoms such as a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec- Alkyl group, more preferably a methyl group, a t-butyl group or a t-pentyl group.

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 is preferably a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, More preferably an alkyl group having 1 to 5 carbon atoms such as methyl, ethyl, propyl, butyl, sec-butyl, t-butyl or t-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 above. In particular, R ⁴ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, 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 and cycloalkyl groups exemplified in the description of R ² , R ³ , R ⁵ and R ⁶ , respectively. Particularly, X is preferably a single bond, a methylene group, or a methylene group substituted with a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group or a t- Bond.

In the general formula (2), A represents an alkylene group having 1 to 8 carbon atoms or a group represented by the formula: --COR ⁸ -. Examples of the alkylene group having 1 to 8 carbon atoms include methylene, ethylene, propylene, butylene, pentamethylene, hexamethylene, octamethylene, 2,2-dimethyl- And preferably a propylene group. 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 which represents R ⁸ include the alkylene groups exemplified in the description of A above. R ⁸ is preferably a single bond or an ethylene group. In the formula: * -COR ⁸ -, * represents the bond on the oxygen side, indicating that the carbonyl group is bonded to the oxygen atom of the phosphite group.

In the general formula (2), Y and Z represent a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms Alkyl group. Examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a t-butoxy group, and a pentyloxy group. Examples of the aralkyloxy group having 7 to 12 carbon atoms include benzyloxy group,? -Methylbenzyloxy group,?,? - dimethylbenzyloxy group 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 above.

Examples of the compound represented by the general formula (2) include 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy- Propoxy] dibenzo [d, f] [1,3,2] dioxaphosphepine, 6- [3- (3,5- 4,8,10-tetra-t-butyldibenzo [d, f] [1,3,2] dioxaphosphepin, 6- [3- (3,5- Dibenzo [d, g] [l, 3,2] dioxaphosphosine, 6- [3- (3-methylphenyl) propoxy] -4,8-di- , 5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -4,8-di-t- butyl-2,10- 2] dioxaphosphosine, and the like. Among them, in the case where the polycarbonate resin composition to be obtained is used in an area where optical characteristics are particularly required, 2,4,8,10-tetra-t-butyl-6- [3- (3- -Hydroxy-5-t-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphepine are suitable, for example, Sumilitogam (GP) (&Quot; Smilizer " is a registered trademark).

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):

(Wherein R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group optionally substituted with an alkyl group, and b and c each independently represent an integer of 0 to 3)

And the like.

In the general formula (3), R ⁹ and R ¹⁰ are each an alkyl group having 1 to 20 carbon atoms or an aryl group optionally substituted with an alkyl group, but more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group optionally substituted with an alkyl group Do.

Examples of the compound represented by the general formula (3) include 3,9-bis (2,6-di-t-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa- Diphosphaspiro [5,5] undecane, 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9- For example, ADEKA STEP PEP-36A and ADEKA STEP PEP-8 (registered trademark of Adeka Staff) available from ADEKA are commercially available. Among these, 3,9-bis (2,6-di-t-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane Is suitable.

Examples of the phosphorus-base antioxidant (B) other than the compound represented by the general formula (1) include compounds represented by the general formula (4):

(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 optionally substituted with an alkyl group)

And the like.

Examples of the compound represented by the general formula (4) include [1,1'-biphenyl] -4,4'-diyl bis [bis (2,4-di-t-butylphenoxy) For example, Sandoset P-EPQ (trade name) available from Clariant Japan Co., Ltd. is commercially available.

The amount of the phosphorus antioxidant (B) is preferably 0.04 to 0.1 part by weight, more preferably 0.05 to 0.09 part by weight, per 100 parts by weight of the polycarbonate resin (A). When the amount of the phosphorus-based antioxidant (B) is less than 0.04 parts by weight, the effect of improving the thermal stability and color is insufficient. On the contrary, when the amount of the phosphorus antioxidant (B) exceeds 0.1 part by weight, the effect of improving the thermal stability and color is insufficient.

As the phosphorus antioxidant (B) other than the compound represented by the general formula (1), for example, at least one of the compounds represented by the general formulas (2) to (4) may be suitably selected and used.

In the polycarbonate resin composition of the present disclosure, the phosphorus-based antioxidant (B) contains at least two compounds together with the compound represented by the general formula (1) ) Is 40 to 80% by weight, preferably 42 to 70% by weight, of the total amount of the phosphorus-based antioxidant (B). When the amount of the compound represented by the general formula (1) is less than 40% by weight of the total amount of the phosphorus antioxidant (B), the effect of improving the thermal stability is inadequate and the yellowing is not suppressed The color is deteriorated. Conversely, even when the amount of the compound represented by the general formula (1) exceeds 80% by weight of the total amount of the phosphorus antioxidant (B), the effect of improving the thermal stability is insufficient, The color is not suppressed and the color is lowered.

The fatty acid ester (C) acts together with the phosphorus-based antioxidant (B) to inhibit the yellowing of the obtained polycarbonate resin composition and improve the color. The fatty acid ester (C) is a component imparting extrusion moldability to a polycarbonate resin composition when a molded article is produced by extrusion molding.

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

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

Specific examples of the aliphatic carboxylic acid include aliphatic carboxylic acids such as palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, , Tetra triacontanoic acid, montanic acid, glutaric acid, adipic acid, and azelaic acid.

Examples of the alcohol include saturated or unsaturated monohydric alcohols and polyhydric alcohols, and these alcohols may have a substituent such as a fluorine atom, a chlorine atom, a bromine atom, or an aryl group. Of these, saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols and aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable. Aliphatic alcohols also include alicyclic alcohols.

Specific examples of the alcohols include alcohols such as octanol, decanol, dodecanol, tetradecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2- Perfluoropropanol, neopentylene glycol, ditrimethylol propane, dipentaerythritol, and the like.

Specific examples of the fatty acid ester (C) include, for example, behenyl behenate, octyldodecyl behenate, stearyl stearate, glycerin monopalmitate, glycerin monostearate, glycerin monooleate, glycerin distearate, Pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, etc. These may be used alone or in combination of two or more kinds Can be used in combination. Of these, stearic acid esters such as glycerin monostearate and pentaerythritol distearate are suitable. For example, stearic acid esters such as Rikemal S-100A (trade name) manufactured by Riken Vitamin Co., Ltd. and UniStar H476DP (" Unistar " is a registered trademark) is commercially available.

The amount of the fatty acid ester (C) is preferably 0.03 to 0.5 parts by weight, and more preferably 0.05 to 0.2 parts by weight based on 100 parts by weight of the polycarbonate resin (A). When the amount of the fatty acid ester (C) is less than 0.03 parts by weight, the effect of suppressing yellowing and improving color and the effect of imparting extrusion moldability is insufficient. On the other hand, even when the amount of the fatty acid ester (C) exceeds 0.5 parts by weight, the effect of improving color and the effect of imparting extrusion moldability become insufficient.

The ultraviolet absorber (D) is a component for further improving the weather resistance of the obtained polycarbonate resin composition, and can be suitably used depending on the use of the molded article obtained by molding the polycarbonate resin composition. As described later, when a molded article is used as an optical lens, the polycarbonate resin composition containing the ultraviolet absorber (D) is used, so that even after irradiation with sunlight or LED illumination, the light transmittance Can be kept high.

As the ultraviolet absorber (D), there can be used, for example, ultraviolet absorbers which are usually incorporated in polycarbonate resins, such as benzotriazole-based compounds, triazine-based compounds and anilyl oxalate-based compounds, have.

As the benzotriazole-based compound, for example, a compound represented by the general formula (5):

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

And the like.

Examples of the compound represented by the general formula (5) include 2- (2-hydroxy-5-t-octylphenyl) benzotriazole and the like. For example, TINUVIN 329 Sisob 709 manufactured by Sipro Kasei Co., Ltd. and Kemisub 79 manufactured by Chemiprocess Chemical Co., Ltd. are commercially available.

As the triazine compound, for example, 2,4-diphenyl-6- (2-hydroxyphenyl-4-hexyloxyphenyl) 1,3,5-triazine and the like can be given. TINUVIN 1577 and the like are commercially available.

As the oxalanilide-based compound, for example, a compound represented by the formula (6):

For example, Sanduvor VSU manufactured by Clariant Japan Co., Ltd. are commercially available.

The amount of the ultraviolet absorber (D) is preferably 0 to 1 part by weight, more preferably 0.05 to 0.5 part by weight based on 100 parts by weight of the polycarbonate resin (A). If the amount of the ultraviolet absorber (D) is more than 1 part by weight, the initial color of the obtained polycarbonate resin composition may be lowered. 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 exhibited.

The polycarbonate resin composition according to Embodiment 1 may contain various additives such as an antioxidant, a colorant, a releasing agent, a softener, an antistatic agent, an impact modifier, and the like in a range that does not impair the effect of the present disclosure, A polymer other than the polycarbonate resin (A) may be suitably blended.

The method for producing the polycarbonate resin composition is not particularly limited and the polycarbonate resin (A), phosphorus antioxidant (B), fatty acid ester (C) and ultraviolet absorber (D) Or a polymer other than the polycarbonate resin (A) by appropriately adjusting the kind and amount of each component and mixing them with a known mixer such as a tumbler or a ribbon blender, or a method of mixing them by a melt- . By these methods, pellets of the polycarbonate resin composition can be easily obtained.

The shape and size of the pellets of the polycarbonate resin composition obtained as described above are not particularly limited and may be the shape and the size of a general resin pellet. Examples of the shape of the pellet include an elliptical columnar shape, a cylindrical shape, and the like. The pellet preferably has a length of about 2 to 8 mm. In the case of an elliptical pillar, it is preferable that the long diameter of the cross section ellipse is about 2 to 8 mm and the short diameter is about 1 to 4 mm, Is preferably about 1 to 6 mm in diameter. The size of each pellet obtained may be such a size, or the size of all the pellets forming the pellet aggregate may be such a size, and the average value of the aggregates of pellets may be such a size, and there is no particular limitation.

As described above, the first embodiment has been described as an example of the technique disclosed in the present application. However, the technology of the present disclosure is not limited to this, but may be applied to embodiments in which modification, replacement, addition, omission, etc. are appropriately performed.

(Embodiment 2: molded article)

The molded article according to Embodiment 2 is obtained by molding the polycarbonate resin composition according to Embodiment 1 obtained as described above.

The method for producing the molded article is not particularly limited, and for example, a method of molding a polycarbonate resin composition by a known injection molding method, compression molding method and the like can be given.

As the molded article in the present disclosure, 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 suitably exemplified.

Particularly, when the molded product is an optical lens, the ultraviolet absorber (D) is blended and the polycarbonate resin composition having superior weatherability is used, so that even after irradiation with sunlight or LED illumination, Can be maintained.

Particularly, when the molded article is a light guide for a vehicle lamp, the light guide for a vehicle lamp is excellent in thermal stability and has a high light transmittance even when molded at a high temperature, For example, a light source such as an LED, and is used as a lamp that exhibits high visibility. Therefore, even when the light guide for a vehicle lamp is thin, even if it is thin, the appearance of the lamp changes due to its hue, and the resin itself is hardly deteriorated through high-temperature molding, resulting in extremely high industrial value.

The light guide for a vehicle lamp (daylight light guide) in the present disclosure refers to a light guide for a vehicle lamp, which is provided near various lamps for a vehicle such as a vehicle head lamp such as a head lamp, an auxiliary head lamp such as a fog lamp, Light guide means light.

Particularly, when the molded product is a light guide film, the light guide film has excellent thermal stability and has a high light transmittance even when molded at high temperature, and the yellowing is sufficiently suppressed and the color is excellent. Therefore, even when the light guide film has a thickness of about 600 탆 or less, it is less likely that the appearance changes due to a change in hue, the resin itself is deteriorated through high temperature molding, and the balance between brightness, light transmittance and color stability is good In addition, because of excellent extrusion moldability, industrial value is extremely high.

The light guide film in the present disclosure is preferably a film having a thickness of 600 占 퐉 or less, more preferably a thickness of 400 占 퐉 or less, which is used for various display portions such as a liquid crystal display of a portable computer such as a smart phone, .

The light guide film in the present disclosure is obtained by extrusion molding the pellets of the polycarbonate resin composition. There is no particular limitation on the production method of the light guide film, and conventional molding methods such as a known T-die extrusion molding method, calender molding method and the like can be employed. Further, a sheet-shaped molded article of a polycarbonate resin composition may be obtained by a known injection molding method, compression molding method or the like, and processed into a film having a desired thickness by cutting or the like from the sheet-like molded article, if necessary.

As described above, the second embodiment has been described as an example of the technique disclosed in the present application. However, the technology of the present disclosure is not limited to this, but may be applied to embodiments in which modification, replacement, addition, omission, etc. are appropriately performed.

<Examples>

Hereinafter, the present disclosure will be described in detail by way of examples, but the present disclosure is not limited to these examples. Unless otherwise stated, &quot; part &quot; and &quot;% &quot; are by weight.

The following materials were used as raw materials.

1. Polycarbonate resin (A)

Polycarbonate resin synthesized from bisphenol A and carbonyl chloride

Caliber 200-30

(Trade name, manufactured by Sumikastar Theory Polycarbonate Co., Ltd., "Caliber" is a registered trademark of Star Theory Europe GmbH, viscosity average molecular weight: 18000, hereinafter referred to as "PC"

2. Phosphorus antioxidant (B)

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

Irga Force 168

(Trade name, manufactured by BASF, hereinafter referred to as &quot; B1 &

2-2. (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5, 5] Undecan

Adeka Staff PEP-36

(Trade name, manufactured by ADEKA Corporation, hereinafter referred to as "B2"),

3. Fatty acid ester (C)

Glycerin monostearate

Rikemal S-100A

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

4. Ultraviolet absorber (D)

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

TINUVIN 329

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

(1) First Embodiment

Examples 1-1 to 1-2, Reference Example 1-3 and Comparative Examples 1-1 to 1-2

The respective raw materials were put into a tumbler in a batch as shown in Table 1, dry mixed for 10 minutes, and melt-kneaded at a melting temperature of 240 占 폚 using a twin-screw extruder (TEX30? To obtain pellets of a polycarbonate resin composition.

In addition, the pellets obtained in Examples 1-1 to 1-2, Reference Example 1-3 and Comparative Examples 1-1 to 1-2 were all in an almost elliptical columnar shape, and the size of the aggregate including 100 pellets (mm)) are respectively as follows.

Using the obtained pellets, each evaluation was carried out according to the following method. The results are shown in Table 1.

(A) Initial color

The obtained pellets were dried at 120 캜 for 4 hours or more and then molded at a molding temperature of 280 캜 and a mold temperature of 80 캜 using an injection molding machine (ROBOSHOT S2000i100A, manufactured by PANAC CO., LTD.) According to JIS K 7139 A multi-purpose test piece A (total length 168 mm x thickness 4 mm) was produced. The section of the 168 mm long optical path length test piece was cut and subjected to mirror-surface processing with respect to the cutting end face using a resin plate cross-section mirror machine (Flavin PB-500 manufactured by Megaro Technica Co., Ltd.).

A light source attachment device was installed in a spectrophotometer (UH4150, manufactured by Hitachi Seisakusho Co., Ltd.), and a 50 W halogen lamp was used as a light source, and a mask of 5.6 mm x 2.8 mm before the light source and 6.0 mm x 2.8 mm In the used state, the spectral transmittance of the test piece per 1 nm in the region of the wavelength of 380 to 780 nm was measured with respect to the entire longitudinal direction, using a standard light source D65 at a 10-degree field of view. Based on the measured spectral transmittance, the respective yellowness degrees were determined to be the initial color YI having a length of 168 mm. Also, the YI was 13 or less (good) (good), and if the YI was more than 13 (poor) (indicated by X in the table).

(B) Yellowing effect

The melt pellets were allowed to stand at 280 DEG C for 15 minutes in a cylinder of an injection molding machine used in (A) initial color, and 168 mm long light test pieces were produced in the same manner as in (A) above.

For this test piece, a YI value of 168 mm in length was obtained in the same manner as in the above (A), and the value obtained in (A) was subtracted from the obtained value to calculate YI. Also, the value of DELTA YI was 11 or less (indicated by o in the table), and the value of 11 or more was judged as defective (indicated by x in the table).

(C) long-term reliability

A 168 mm long-beam test piece was produced in the same manner as in the above (a). A light source attachment device was installed in a spectrophotometer (UH4150, manufactured by Hitachi Seisakusho Co., Ltd.), and a 50 W halogen lamp was used as a light source, and a mask of 5.6 mm x 2.8 mm before the light source and 6.0 mm x 2.8 mm In the used state, the spectral transmittance of the test piece per 1 nm in the region of the wavelength of 380 to 780 nm was measured with respect to the entire longitudinal direction. The measured spectral transmittance was integrated and rounded to 10, to obtain the accumulated transmittance before the test.

Subsequently, the test piece was placed in a constant temperature and humidity bath (ADVANTEC Co., Ltd., constant temperature and humidity chamber AG-327) and subjected to a hydrolysis test for 500 hours under the conditions of a temperature of 90 DEG C and a relative humidity of 90%. After completion of the test, the cumulative transmittance after the test of the test piece was obtained in the same manner as above, and the? Cumulative transmittance (difference in cumulative transmittance = cumulative transmittance before test - cumulative transmittance after test) was calculated. The? Cumulative transmittance represents the degree of change of the cumulative transmittance before and after the test. The smaller the? Cumulative transmittance, the less the decrease of the light transmittance even after the high temperature and high humidity conditions are provided, and the long term reliability is excellent. Also, the? Cumulative transmittance was less than 5,000 (indicated by? In the table) and 5,000 or more were found in the table (indicated by x in the table).

The polycarbonate resin compositions of Examples 1-1 to 1-2 and Reference Example 1-3 were prepared by mixing not only two compounds as the phosphorus-based antioxidant (B) but also the compounds represented by the general formula (1) (2,4-di-t-butylphenyl) phosphite is adjusted within a range of 40 to 80% by weight of the total amount of the phosphorus-based antioxidant (B). Therefore, the 168 mm long-light test specimens molded from these polycarbonate resin compositions are not only excellent in initial hue but also excellent in initial hue. Even in the test specimens having a length of 168 mm formed after staying at 280 캜 for 15 minutes, Sufficiently suppressed, and excellent in thermal stability. Further, the 168 mm long-light-transmitting test piece molded from these polycarbonate resin compositions exhibited very little deterioration in the light transmittance even after the hydrolysis test was conducted for 500 hours under the conditions of a temperature of 90 캜 and a relative humidity of 90% It is also excellent.

On the other hand, in the polycarbonate resin composition of Comparative Example 1-1, the amount of the phosphorus-based antioxidant (B) in excess of 0.1 part by weight per 100 parts by weight of the polycarbonate resin (A) Di-t-butylphenyl) phosphite is less than 40% by weight of the total amount of the phosphorus antioxidant (B). Therefore, the 168 mm long-light test piece molded from the polycarbonate resin composition had a large yellow color and a low initial color, and the 168 mm long-wavelength test piece molded after standing at 280 캜 for 15 minutes had a yellow color sufficiently inhibited And the thermal stability is poor. Further, after the hydrolysis test was performed for a long time under a high temperature and high humidity condition, the 168 mm long light test piece molded from the polycarbonate resin composition remarkably decreased in the light transmittance and the long-term reliability deteriorated.

In the polycarbonate resin composition of Comparative Example 1-2, the amount of tris (2,4-di-t-butylphenyl) phosphite exceeds 80% by weight of the total amount of the phosphorus antioxidant (B). Therefore, the 168 mm long-light test piece molded from the polycarbonate resin composition had a large yellow color and a low initial color, and the 168 mm long-wavelength test piece molded after standing at 280 캜 for 15 minutes had a yellow color sufficiently inhibited And the thermal stability is poor.

(2) Second Embodiment

Examples 2-1 to 2-3, Reference Example 2-4, and Comparative Examples 2-1 to 2-2

The respective raw materials were put into a tumbler collectively at the ratios shown in Table 2, and pellets of the polycarbonate resin composition were obtained in the same manner as in the first embodiment. In addition, the pellets obtained in Examples 2-1 to 2-3, Reference Example 2-4 and Comparative Examples 2-1 to 2-2 were all in an almost elliptical columnar shape, and the size of the aggregate including 100 pellets (mm)) are respectively as follows.

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

(A) In the evaluation of the initial color, YI was 16 or less in good condition (indicated by o in the table), and in case of exceeding 16, YI was judged in poor condition (indicated by X in the table). Further, in the evaluation of the yellowing suppression effect, (B) the residence time in the cylinder of the injection molding machine was changed to 10 minutes, and the value of? YI was 18 or less (indicated by? In the table) Quot; in the table).

The polycarbonate resin compositions of Examples 2-1 to 2-3 and Reference Example 2-4 were prepared by mixing not only two kinds of compounds as the phosphorus-based antioxidant (B) but also the two kinds of compounds represented by the general formula (1) (2,4-di-t-butylphenyl) phosphite is adjusted within a range of 40 to 80% by weight of the total amount of the phosphorus-based antioxidant (B). Therefore, the 168 mm long-light-transmitting test piece molded from the polycarbonate resin composition has a small yellow color and excellent initial color, and even if the 168 mm long-wavelength test piece molded after staying at 280 캜 for 10 minutes has sufficient yellowing And is excellent in thermal stability. Further, the 168 mm long-light-transmitting test piece molded from these polycarbonate resin compositions exhibited very little deterioration in the light transmittance even after the hydrolysis test was conducted for 500 hours under the conditions of a temperature of 90 캜 and a relative humidity of 90% Respectively.

In contrast, in 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) exceeded 1 part by weight. Therefore, the 168 mm long-wavelength test specimen molded from the polycarbonate resin composition has a high yellowness and a poor initial color.

The polycarbonate resin composition of Comparative Example 2-2 was obtained in such a manner that the amount of the phosphorus-based antioxidant (B) relative to 100 parts by weight of the polycarbonate resin (A) was more than 0.1 part by weight, -t-butylphenyl) phosphite is less than 40% by weight of the total amount of the phosphorus antioxidant (B). Therefore, the 168 mm long-light test piece molded from the polycarbonate resin composition had a large yellow color and a low initial color, and the 168 mm long-wavelength test piece molded after standing at 280 캜 for 10 minutes exhibited sufficient yellowing And the thermal stability is poor. Further, after the hydrolysis test was performed for a long time under a high temperature and high humidity condition, the 168 mm long light test piece molded from the polycarbonate resin composition remarkably decreased in the light transmittance and the long-term reliability deteriorated.

(3) Third Embodiment

Examples 3-1 to 3-3, Reference Example 3-4, and Comparative Examples 3-1 to 3-4

The respective raw materials were put into a tumbler collectively at the ratios shown in Table 3, and pellets of a polycarbonate resin composition were obtained in the same manner as in the first embodiment. The pellets obtained in Examples 3-1 to 3-3, Reference Example 3-4, and Comparative Examples 3-1 to 3-4 were all in an almost elliptical columnar shape, and the size of the aggregate including 100 pellets (mm)) are respectively as follows.

Using the obtained pellets, each evaluation was carried out according to the following method. The results are shown in Table 3.

(A) Initial color

The obtained pellets were dried at 120 캜 for 4 hours or more and then molded at a molding temperature of 280 캜 and a mold temperature of 80 캜 using an injection molding machine (ROBOSHOT S2000i100A, manufactured by PANAC CO., LTD.) According to JIS K 7139 A multi-purpose test piece A (total length 168 mm x thickness 4 mm) was produced. The section of the test piece was cut with the 168 mm long light, and the cut surface was subjected to mirror-surface processing using a resin plate cross-section light-curing machine (Flavin PB-500, Megaro Technica Co., Ltd.).

A light source attachment device was installed in a spectrophotometer (UH4150, manufactured by Hitachi Seisakusho Co., Ltd.), and a 50 W halogen lamp was used as a light source, and a mask of 5.6 mm x 2.8 mm before the light source and 6.0 mm x 2.8 mm In the used state, the spectral transmittance of the test piece per 1 nm in the region of the wavelength of 380 to 780 nm was measured with respect to the entire longitudinal direction, using a standard light source D65 at a 10-degree field of view. Based on the measured spectral transmittance, the respective yellowness degrees were determined to be the initial color YI having a length of 168 mm. Also, the YI was 13 or less (good) (good), and if the YI was more than 13 (poor) (indicated by X in the table).

(B) Yellowing effect

The melt pellets were allowed to stand at 280 DEG C for 15 minutes in a cylinder of an injection molding machine used in (A) initial color, and 168 mm long light test pieces were produced in the same manner as in (A) above.

For this test piece, a YI value of 168 mm in length was obtained in the same manner as in the above (A), and the value obtained in (A) was subtracted from the obtained value to calculate YI. Also, the value of DELTA YI was 11 or less (indicated by o in the table), and the value of 11 or more was judged as defective (indicated by x in the table).

(C) Extrusion molding property

A sheet having a width of 250 mm and a thickness of 0.5 mm was formed from the obtained pellets under the conditions of a screw rotation number of 90 rpm and a melting temperature of 260 캜 by using an extrusion sheet molding machine (manufactured by Tanabe Plastics Co., Ltd., 40 mm sheet extruder) . The outer appearance of the obtained sheet and the contamination of the roll surface due to volatile components at the time of molding were visually observed and evaluated based on the following evaluation criteria. When the evaluation is good or good, there is no problem in practical use.

(Evaluation standard)

Good (in the table, indicated by ⊚):

There is no striped mark on the sheet surface and there is no contamination of the roll surface.

Good (indicated by o in the table):

There is almost no striped mark on the sheet surface, and there is little contamination of the roll surface.

Normal (indicated by, in the table):

There are stripe marks on the sheet surface and there is contamination of the roll surface.

Bad (in the table, indicated by x):

There are many stripe marks on the sheet surface, and the contamination of the roll surface is remarkable.

(D) Long-term reliability

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

In the polycarbonate resin compositions of Examples 3-1 to 3-3 and Reference Example 3-4, two kinds of compounds as the phosphorus-based antioxidant (B) were blended, (2,4-di-t-butylphenyl) phosphite is adjusted within a range of 40 to 80% by weight of the total amount of the phosphorus-based antioxidant (B). Therefore, the 168 mm long-light test specimens molded from these polycarbonate resin compositions are not only excellent in initial hue but also excellent in initial hue. Even in the test specimens having a length of 168 mm formed after staying at 280 캜 for 15 minutes, Sufficiently suppressed, and excellent in thermal stability. In addition, these polycarbonate resin compositions are excellent in extrusion moldability when formed into a sheet. Further, the 168 mm long-light-transmitting test piece molded from these polycarbonate resin compositions exhibited very little deterioration in the light transmittance even after the hydrolysis test was conducted for 500 hours under the conditions of a temperature of 90 캜 and a relative humidity of 90% It is also excellent.

On the other hand, in the polycarbonate resin composition of Comparative Example 3-1, the amount of the phosphorus-based antioxidant (B) in excess of 0.1 part by weight per 100 parts by weight of the polycarbonate resin (A) Di-t-butylphenyl) phosphite is less than 40% by weight of the total amount of the phosphorus antioxidant (B). Therefore, the 168 mm long-light test piece molded from the polycarbonate resin composition had a large yellow color and a low initial color, and the 168 mm long-wavelength test piece molded after standing at 280 캜 for 15 minutes had a yellow color sufficiently inhibited And the thermal stability is poor. Further, after the hydrolysis test was performed for a long time under a high temperature and high humidity condition, the 168 mm long light test piece molded from the polycarbonate resin composition remarkably decreased in the light transmittance and the long-term reliability deteriorated.

In the polycarbonate resin composition of Comparative Example 3-2, the amount of tris (2,4-di-t-butylphenyl) phosphite exceeds 80% by weight of the total amount of the phosphorus antioxidant (B). Therefore, the 168 mm long-light test piece molded from the polycarbonate resin composition had a large yellow color and a low initial color, and the 168 mm long-wavelength test piece molded after standing at 280 캜 for 15 minutes had a yellow color sufficiently inhibited And the thermal stability is poor.

In 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) is less than 0.03 part by weight. Therefore, the 168 mm long-wavelength test specimen formed after the polycarbonate resin composition was allowed to stand at 280 占 폚 for 15 minutes was not sufficiently inhibited from yellowing, resulting in poor thermal stability. In addition, the polycarbonate resin composition also has poor extrusion-forming properties when formed into a sheet.

The polycarbonate resin composition of Comparative Example 3-4 contained 0.5 parts by weight or more of the fatty acid ester (C) per 100 parts by weight of the polycarbonate resin (A). Therefore, the 168 mm long-wavelength test specimen molded from the polycarbonate resin composition has a high yellowness and a poor initial color. In addition, the polycarbonate resin composition also has poor extrusion-forming properties when formed into a sheet.

As described above, the embodiment has been described as an example of the technique in the present disclosure. Therefore, a detailed explanation has been provided.

Therefore, among the constituent elements described in the detailed description, not only essential constituent elements for solving the problems but also constituent elements which are not essential for solving the problems in order to exemplify the above-described technology can be included. Therefore, it is not necessary to admit that components that are not essential are described in the detailed description, and that components that are not essential to them are essential.

In addition, the above-described embodiments are intended to exemplify the technique of the present disclosure, and various modifications, substitutions, additions, omissions, and the like can be made in the claims or the equivalents thereof.

The present disclosure can be suitably used as a molded article such as, for example, an optical lens, a light guide for a vehicle lamp, a light guide film, a surface light emitting material, and a name plate.

Claims (7)

(A), a phosphorus-based antioxidant (B), a fatty acid ester (C) and an ultraviolet absorber (D)
The amount of the phosphorus antioxidant (B) is 0.04 to 0.1 part by weight based on 100 parts by weight of the polycarbonate resin (A)
The amount of the fatty acid ester (C) is 0.05 to 0.2 parts by weight based on 100 parts by weight of the polycarbonate resin (A)
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)
Wherein the phosphorus antioxidant (B) is at least two kinds of compounds, and 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)
, &Lt; / RTI &gt;
Wherein the amount of the compound represented by the general formula (1) is 40 to 67% by weight of the total amount of the phosphorus-based antioxidant (B)
Wherein the fatty acid ester (C) is glycerin monostearate. The polycarbonate resin composition according to claim 1, wherein the compound represented by the general formula (1) is tris (2,4-di-t-butylphenyl) phosphite. The polycarbonate resin composition according to claim 1, wherein the 168 mm long optical path test piece formed by molding the polycarbonate resin composition has an? Cumulative transmittance of less than 5000, calculated on the basis of the following formula:
? Cumulative transmittance = cumulative transmittance before test - cumulative transmittance after test
(here,
Total transmittance before test: The spectral transmittance in the entire longitudinal direction measured for every 1 nm in the region of the wavelength of 380 to 780 nm was integrated with respect to the test piece before the 500 hours of hydrolysis test under the conditions of the temperature of 90 캜 and the relative humidity of 90% , And
Total transmittance after test: The value obtained by integrating the spectral transmittance in the entire longitudinal direction measured for each 1 nm in a wavelength region of 380 to 780 nm with respect to the test piece provided in the hydrolysis test. The polycarbonate resin composition according to any one of claims 1 to 6, wherein the initial color YI obtained from the spectral transmittance in the entire longitudinal direction measured in every 1 nm in the region of the wavelength of 380 to 780 nm of the 168 mm long- Borate resin composition. A molded article obtained by molding the polycarbonate resin composition according to claim 1. The molded article according to claim 5, which is a light guide for a vehicle lamp. The molded article according to claim 5, which is a light guide film.