JP6014788B1 - Polycarbonate resin composition and molded product - Google Patents

Abstract

A polycarbonate resin (A1) having a structural unit derived from a fluorene dihydroxy compound and a phosphorus antioxidant (B) are contained, and the amount of the phosphorus antioxidant (B) is 100 parts by weight of the polycarbonate resin (A1). Polycarbonate resin composition of 0.02 to 1.5 parts by weight, polycarbonate resin (A2) having a structural unit derived from a fluorene-based dihydroxy compound and a structural unit derived from a dinaphthothiophene compound, and a phosphorus-based antioxidant (B) A polycarbonate resin composition containing 0.02 to 1.5 parts by weight of the phosphorus-based antioxidant (B) with respect to 100 parts by weight of the polycarbonate resin (A2), and a molded article comprising them.

Description

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

  Optical glasses are used as optical members in optical systems such as web cameras and portable information terminal cameras used in the security field, and optical systems such as sensors, because of their excellent heat resistance and dimensional stability. However, in recent years, further downsizing of optical members has been required, and optical glass is not practical because it is difficult to mold and inferior in productivity.

  Therefore, by adopting a thermoplastic resin as an alternative material for optical glass, mass production of optical members by injection molding becomes possible, and productivity is improved.

  Among thermoplastic resins, polycarbonate resin is widely used as an optical member by taking advantage of its impact resistance, heat resistance and transparency. In particular, a polycarbonate resin containing a structural unit derived from 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene is optically derived from its structure and has a high refractive index and a small orientation birefringence. From the viewpoint of performance, it has been proposed to use the polycarbonate resin as an optical member such as various lenses, prisms, and disks (for example, Patent Documents 1 to 4).

  However, the polycarbonate resin containing the structural unit may turn yellow due to poor thermal stability during polymerization, and there is a risk of limitations when the resulting optical member is used for exterior parts or the like. is there.

International Publication No. 2007/142149 JP-A-10-101787 Japanese Patent No. 5440500 Japanese Patent Laying-Open No. 2015-007246

  Since the present disclosure maintains excellent optical performance such as high light transmittance and high refractive index, it has excellent thermal stability and good fluidity. Provided is a polycarbonate resin composition which can be processed. Moreover, this indication provides the molded article which shape | molded this polycarbonate resin composition.

（式中、Ｇ^１及びＧ^２は、それぞれ独立して、水素原子、炭素数１〜４のアルキル基又は炭素数１〜３のアルコキシル基を示す。Ｌは、炭素数２〜４のアルキレン基を示す。ｍは、０〜２の整数を示す）
で表されるジヒドロキシ化合物由来の構成単位と、一般式（２）：

（式中、Ｍは、炭素数２〜４のアルキレン基を示す。ｎは、０〜２の整数を示す）
で表されるジナフトチオフェン化合物由来の構成単位とを有するポリカーボネート樹脂（Ａ２）と、
リン系酸化防止剤（Ｂ）と
を含有してなり、
前記リン系酸化防止剤（Ｂ）の量が、前記ポリカーボネート樹脂（Ａ２）１００重量部に対して０．０２〜１．５重量部であるものである。 The polycarbonate resin composition in the present disclosure is :
General formula (1):

(In the formula, G ¹ and G ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyl group having 1 to 3 carbon atoms. L represents an alkylene group having 2 to 4 carbon atoms. M represents an integer of 0 to 2)
A structural unit derived from a dihydroxy compound represented by the general formula (2):

(In the formula, M represents an alkylene group having 2 to 4 carbon atoms, and n represents an integer of 0 to 2).
A polycarbonate resin (A2) having a structural unit derived from a dinaphthothiophene compound represented by:
Containing a phosphorus-based antioxidant (B),
The amount of the phosphorus antioxidant (B) is 0.02 to 1.5 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A2).

（式中、Ｇ^１及びＧ^２は、それぞれ独立して、水素原子、炭素数１〜４のアルキル基又は炭素数１〜３のアルコキシル基を示す。Ｌは、炭素数２〜４のアルキレン基を示す。ｍは、０〜２の整数を示す）
で表されるジヒドロキシ化合物由来の構成単位と、一般式（２）：

（式中、Ｍは、炭素数２〜４のアルキレン基を示す。ｎは、０〜２の整数を示す）
で表されるジナフトチオフェン化合物由来の構成単位とを有するポリカーボネート樹脂（Ａ２）と、
リン系酸化防止剤（Ｂ）と
を含有してなり、
前記リン系酸化防止剤（Ｂ）の量が、前記ポリカーボネート樹脂（Ａ２）１００重量部に対して０．０２〜１．５重量部であるポリカーボネート樹脂組成物
からなるものである。 The molded article in the present disclosure is
General formula (1):

(In the formula, G ¹ and G ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyl group having 1 to 3 carbon atoms. L represents an alkylene group having 2 to 4 carbon atoms. M represents an integer of 0 to 2)
A structural unit derived from a dihydroxy compound represented by the general formula (2):

(In the formula, M represents an alkylene group having 2 to 4 carbon atoms, and n represents an integer of 0 to 2).
A polycarbonate resin (A2) having a structural unit derived from a dinaphthothiophene compound represented by:
Containing a phosphorus-based antioxidant (B),
An amount of the phosphorous antioxidant (B) is a polycarbonate resin composition in which the amount is 0.02 to 1.5 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A2).

  The polycarbonate resin composition in the present disclosure maintains excellent optical performance such as high light transmittance, high refractive index and the like, and has excellent thermal stability and good fluidity. Molding at low temperatures is also possible.

  Hereinafter, embodiments will be described in detail. However, more detailed explanation than necessary may be omitted. For example, detailed descriptions of already well-known matters and repeated descriptions for substantially the same configuration may be omitted. This is to avoid the following description from becoming unnecessarily redundant and to facilitate understanding by those skilled in the art.

  The inventor provides the following explanation for those skilled in the art to fully understand the present disclosure, and is not intended to limit the subject matter described in the claims.

(Embodiment 1-1-Polycarbonate resin composition I)
The polycarbonate resin composition I according to Embodiment 1-1 includes a polycarbonate resin (A1) and a phosphorus-based antioxidant (B). In addition, the polycarbonate resin composition I in this indication may contain the other component as needed.

（式中、Ｇ^１及びＧ^２は、それぞれ独立して、水素原子、炭素数１〜４のアルキル基又は炭素数１〜３のアルコキシル基を示す。Ｌは、炭素数２〜４のアルキレン基を示す。ｍは、０〜２の整数を示す）
で表されるジヒドロキシ化合物由来の構成単位を有する重合体である。 The polycarbonate resin (A1) has the general formula (1):

(In the formula, G ¹ and G ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyl group having 1 to 3 carbon atoms. L represents an alkylene group having 2 to 4 carbon atoms. M represents an integer of 0 to 2)
It is a polymer which has a structural unit derived from the dihydroxy compound represented by these.

In the general formula (1) representing the dihydroxy compound, G ¹ and G ² are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and L is an alkyl group having 2 to 4 carbon atoms. It is preferably an alkylene group, and m is preferably 0 or 1.

で表される９，９−ビス（４−（２−ヒドロキシエトキシ）フェニル）フルオレン、
式（１−２）：

で表される９，９−ビス（４−ヒドロキシフェニル）フルオレン、
式（１−３）：

で表される９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン
等が挙げられ、これらの中でも、９，９−ビス（４−（２−ヒドロキシエトキシ）フェニル）フルオレンが特に好ましい。 As the dihydroxy compound represented by the general formula (1), for example,
Formula (1-1):

9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene represented by
Formula (1-2):

9,9-bis (4-hydroxyphenyl) fluorene represented by
Formula (1-3):

9,9-bis (4-hydroxy-3-methylphenyl) fluorene represented by the formula, among which 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene is particularly preferable.

  The polycarbonate resin (A1) is, for example, a transesterification method in which a dihydroxy compound represented by the general formula (1) and a carbonic acid diester are reacted in the presence of a basic compound catalyst and / or a transesterification catalyst as necessary. Can be manufactured by.

  Examples of the carbonic acid diester include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate. Among these, diphenyl carbonate is particularly preferable.

  Examples of the basic compound catalyst include alkali metal compounds, alkaline earth metal compounds, ammonium compounds, and amine compounds.

  Examples of the alkali metal compound include organic acid salts such as sodium, potassium, cesium, and lithium, inorganic salts, oxides, hydroxides, hydrides, and alkoxides. Specifically, for example, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate Sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium borohydride and the like.

  Examples of the alkaline earth metal compound include organic acid salts such as magnesium, calcium, strontium, and barium, inorganic salts, oxides, hydroxides, hydrides, and alkoxides. Specifically, for example, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate , Magnesium acetate, calcium acetate, strontium acetate, barium acetate and the like.

  Examples of the ammonium compounds and amine compounds include quaternary ammonium hydroxides and salts thereof, and tertiary amines. Specific examples include quaternary ammonium hydroxides having an alkyl group, an aryl group, etc., such as tetramethylammonium hydroxide, and tertiary amines such as triethylamine, dimethylbenzylamine, triphenylamine, and the like.

  The transesterification catalyst is preferably a salt of zinc, tin, zirconium, lead or the like, and these can be used alone or in combination of two or more. Specific examples include zinc acetate, tin acetate, dibutyltin dilaurate, and lead acetate.

  The transesterification method in which the dihydroxy compound and the carbonic acid diester are reacted is a method in which melt polycondensation is carried out while removing by-products under normal pressure or reduced pressure, and the reaction is carried out in one step or two steps. It is carried out in a multi-stage process of stages or more. The conditions for the transesterification method are not particularly limited as long as the desired polymer (polycarbonate resin (A1)) can be obtained. For example, the following conditions can be employed.

  Specifically, first, the raw material dihydroxy compound and carbonic acid diester are melted, and then at a normal pressure (760 Torr), 120 to 260 ° C., preferably 180 to 240 ° C., 0.5 to 5 hours, preferably Is reacted for 0.7 to 4 hours. Next, the polycondensation reaction between the dihydroxy compound and the carbonic acid diester can be promoted by raising the degree of pressure reduction of the reaction system (˜several Torr) and further raising the temperature (˜280 ° C.) in consideration of the degree of polymerization of the polymer. it can. The reaction may be carried out batchwise or continuously. The reactor is a vertical stirring tank equipped with a helical ribbon stirring blade, an anchor blade for high viscosity liquid stirring, a large blend stirring blade that can be applied in a wide viscosity range, a full zone stirring blade, etc. Alternatively, it may be a horizontal stirring tank equipped with paddle blades, lattice blades, glasses blades and the like. Furthermore, an extruder type equipped with a screw may be used, and the reactor can be used in appropriate combination in consideration of the viscosity of the polymer.

  In addition, for the purpose of removing low molecular weight substances such as unreacted substances and by-products remaining in the polymer as a post-process, (i) a polymer obtained by dissolving the polymer in an organic solvent (good solvent) such as dichloromethane After preparing the solution, a method of fractionating the precipitate using an organic solvent (poor solvent) such as methanol or ethanol as a precipitant, (ii) putting the polymer into an extruder having a high theoretical surface renewal frequency and pelletizing A method (for example, see JP-A-01-149827), (iii) a method in which water is added to a polymer and kneaded and extruded while degassing under conditions that do not cause hydrolysis (for example, Japanese Patent Publication No. 05-027647). Or the like can be used.

  The amount of the carbonic acid diester added to the dihydroxy compound is adjusted to be about 0.9 to 1.1 mol with respect to 1 mol of the dihydroxy compound, so that a high molecular weight polymer is obtained. Preferably, it is about equimolar with the dihydroxy compound.

Further, when the basic compound catalyst and / or the transesterification catalyst is added, it is adjusted to be about 1.0 × 10 ^{−8 to} 1.0 × 10 ⁻⁴ mol with respect to 1 mol of the dihydroxy compound. It is preferable to do.

  The refractive index (hereinafter also referred to as nd) of the polycarbonate resin (A1) with respect to the d-line (wavelength 587.6 nm) is preferably 1.637 or more, more preferably 1.639 or more. Thus, when the nd is 1.637 or more, the obtained polycarbonate resin composition I is an optical member such as various lenses, prisms, and disks, in particular, lenses for exterior parts that require designability, It is suitable for an optical member such as a lens provided in a camera of an information terminal.

  The polystyrene-reduced weight average molecular weight (hereinafter also referred to as Mw) of the polycarbonate resin (A1) is preferably 15000 to 40000, more preferably 17000 to 35000. Thus, the fluidity | liquidity of the polycarbonate resin composition I obtained is favorably maintained because Mw is the range of 15000-40000.

  The glass transition temperature (hereinafter also referred to as Tg) of the polycarbonate resin (A1) is preferably 130 ° C. or higher, and more preferably 140 ° C. or higher. Thus, when the Tg is 130 ° C. or higher, the heat resistance of the obtained polycarbonate resin composition I is favorably maintained.

  The phosphorus-based antioxidant (B) in the present Embodiment 1-1 is a component that works together with the polycarbonate resin (A1) to improve the thermal stability of the obtained polycarbonate resin composition I.

（式中、Ｒ^１、Ｒ^２、Ｒ^４及びＲ^５は、それぞれ独立して、水素原子、炭素数１〜８のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基又はフェニル基を示す。Ｒ^３は、水素原子又は炭素数１〜８のアルキル基を示す。Ｘは、単結合、硫黄原子又は式：−ＣＨＲ^６−（ここで、Ｒ^６は、水素原子、炭素数１〜８のアルキル基又は炭素数５〜８のシクロアルキル基を示す）で表される基を示す。Ａは、炭素数１〜８のアルキレン基又は式：＊−ＣＯＲ^７−（ここで、Ｒ^７は、単結合又は炭素数１〜８のアルキレン基を示し、＊は、酸素側の結合手であることを示す）で表される基を示す。Ｙ及びＺは、いずれか一方がヒドロキシル基、炭素数１〜８のアルコキシ基又は炭素数７〜１２のアラルキルオキシ基を示し、もう一方が水素原子又は炭素数１〜８のアルキル基を示す）
で表される化合物が挙げられる。 Examples of the phosphorus antioxidant (B) include the general formula (3):

^{(Wherein, R 1, R 2, R} 4 and ^{R 5} are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, cycloalkyl group having 5 to 8 carbon atoms, 6 to 12 carbon atoms alkylcycloalkyl group, .R ³ showing an aralkyl group or a phenyl group having 7 to 12 carbon atoms, .X represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, a single bond, a sulfur atom or the formula: -CHR ^6- (wherein R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms) A represents a group having 1 to 8 carbon atoms. Or an alkylene group of the formula: * —COR ⁷ — (wherein R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a bond on the oxygen side) Y and Z are either a hydroxyl group or an alcohol having 1 to 8 carbon atoms. A xyl group or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms)
The compound represented by these is mentioned.

In General Formula (3), R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 6 carbon atoms. -12 alkylcycloalkyl group, a C7-12 aralkyl group, or a phenyl group is shown.

  Here, examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, and t-butyl. Group, t-pentyl 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 1-methylcyclopentyl group, 1-methylcyclohexyl group, 1-methyl-4-i-propylcyclohexyl group and the like. Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group, α-methylbenzyl group, α, α-dimethylbenzyl group and the like.

R ¹ , R ² and R ⁴ are preferably 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 ¹ and R ⁴ are preferably 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. In particular, R ² represents the number of 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 preferably an alkyl group of 1 to 5, more preferably a methyl group, a t-butyl group or a t-pentyl group.

R ⁵ is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an i-propyl group. , An n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, a t-pentyl group, or the like, more preferably an alkyl group having 1 to 5 carbon atoms.

In general formula (3), ^{R 3} 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, for example, the ^{R 1,} R 2, alkyl groups exemplified in the description of ^{R 4} and ^{R 5} are mentioned. In particular, R ³ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group.

In the general formula (3), X represents a single bond, a sulfur atom or a group represented by the formula: —CHR ⁶ —. Here, R ⁶ in the formula: —CHR ⁶ — represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms and the cycloalkyl group having 5 to 8 carbon atoms include the alkyl groups and cycloalkyl groups exemplified in the description of R ¹ , R ² , R ⁴ and R ⁵ , respectively. It is done. In particular, X is 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, a t-butyl group, or the like. It is preferably a single bond, and more preferably a single bond.

In the general formula (3), A represents an alkylene group having 1 to 8 carbon atoms or a group represented by the formula: * —COR ⁷ —. Examples of the alkylene group having 1 to 8 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and a 2,2-dimethyl-1,3-propylene group. And is preferably a propylene group. Further, the formula: * - COR ⁷ - in ^{R 7} 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 indicates the R ^7, for example, alkylene groups exemplified in the description of the A. R ⁷ is preferably a single bond or an ethylene group. Further, * in the formula: * —COR ⁷ — is a bond on the oxygen side and indicates that the carbonyl group is bonded to the oxygen atom of the phosphite group.

In General Formula (3), one of Y and Z represents 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 1 to 1 carbon atoms. 8 represents an alkyl group. 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. Examples of the aralkyloxy group having 7 to 12 carbon atoms include benzyloxy group, α-methylbenzyloxy group, α, α-dimethylbenzyloxy group and the like. Examples of the alkyl group having 1 to 8 carbon atoms, for example, the ^{R 1,} R 2, alkyl groups exemplified in the description of ^{R 4} and ^{R 5} are mentioned.

  Examples of the compound represented by the general formula (3) include 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-hydroxyphenyl) propoxy] -4,8-di-t-butyl-2,10-dimethyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 6- [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionyloxy] -4,8-di-t-butyl-2, 0-dimethyl -12H- dibenzo [d, g] [1,3,2] dioxaphosphocin, and the like. Among these, 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-) is particularly used when the obtained polycarbonate resin composition I is used in a field where optical properties are required. 4-Hydroxy-5-t-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine is suitable, for example, Sumitizer GP manufactured by Sumitomo Chemical Co., Ltd. Is commercially available as a registered trademark.

  The compound represented by the general formula (3) is produced by reacting phenols or bisphenols, phosphorus trihalide and an amine compound. This production usually employs a two-stage reaction method in which a phenol or bisphenol is first reacted with phosphorus trihalide to produce an intermediate, and then an amine compound is reacted. The reaction is usually performed in an organic solvent in an environment of 0 to 200 ° C.

（式中、Ｒ^８は、炭素数１〜２０のアルキル基を示し、ａは、０〜３の整数を示す）
で表される化合物が挙げられる。 In addition to the compound represented by the general formula (3) as the phosphorus-based antioxidant (B), for example, the general formula (4):

(Wherein R ⁸ represents an alkyl group having 1 to 20 carbon atoms, and a represents an integer of 0 to 3)
The compound represented by these is mentioned.

In the general formula (4), R ⁸ is an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms.

  Examples of the compound represented by the general formula (4) include triphenyl phosphite, tricresyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, and trisnonylphenyl phosphite. It is done. Among these, tris (2,4-di-t-butylphenyl) phosphite is particularly suitable. For example, Irgaphos 168 manufactured by BASF ("Irgaphos" is a registered trademark of BISF Societas Europea) is commercially available. Is available.

（式中、Ｒ^９及びＲ^１０は、それぞれ独立して、炭素数１〜２０のアルキル基又はアルキル基で置換されていてもよいアリール基を示し、ｂ及びｃは、それぞれ独立して、０〜３の整数を示す）
で表される化合物が挙げられる。 As the phosphorus-based antioxidant (B), for example, the general formula (5):

(Wherein R ⁹ and R ¹⁰ each independently represents 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 represents 0 Represents an integer of ~ 3)
The compound represented by these is mentioned.

In the general formula (5), R ⁹ and R ¹⁰ are an alkyl group having 1 to 20 carbon atoms or an aryl group optionally substituted with an alkyl group, and further an alkyl group having 1 to 10 carbon atoms. Or it is preferable that it is the aryl group which may be substituted by the alkyl group.

  Examples of the compound represented by the general formula (5) include 3,9-bis (2,6-di-t-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9. -Diphosphaspiro [5,5] undecane, 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, etc. For example, ADK STAB PEP-36A and ADK STAB PEP-8 (“ADEKA STAB” is a registered trademark) manufactured by ADEKA Corporation 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 Is preferred.

（式中、Ｒ^１１、Ｒ^１２、Ｒ^１３及びＲ^１４は、それぞれ独立して、炭素数１〜２０のアルキル基又はアルキル基で置換されていてもよいアリール基を示す）
で表される化合物が挙げられる。 As the phosphorus-based antioxidant (B), for example, the general formula (6):

(Wherein R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group optionally substituted with an alkyl group)
The compound represented by these is mentioned.

  Examples of the compound represented by the general formula (6) include [1,1′-biphenyl] -4,4′-diylbis [bis (2,4-di-t-butylphenoxy) phosphine]. For example, Irgaphos P-EPQ (trade name) manufactured by BASF and Sandstub P-EPQ (trade name) manufactured by Clariant Japan Co., Ltd. are commercially available.

  Among the compounds represented by the above general formulas (3) to (6) which are phosphorus antioxidants (B), compounds represented by the general formula (3) which are cyclic phosphite compounds, When the compound represented by the general formula (4) which is a phosphoric ester compound is combined with the polycarbonate resin (A1) having a structural unit derived from the dihydroxy compound represented by the general formula (1), A polycarbonate resin composition I with extremely improved thermal stability can be obtained while maintaining excellent optical performance.

  The amount of the phosphorus-based antioxidant (B) is 0.02 to 1.5 parts by weight, preferably 0.03 to 1 part by weight, and more preferably 0.8 to 100 parts by weight of the polycarbonate resin (A1). 04 to 0.5 parts by weight. When the amount of the phosphorus-based antioxidant (B) is less than 0.02 parts by weight, the effect of improving the thermal stability cannot be obtained. Conversely, when the amount of the phosphorus-based antioxidant (B) exceeds 1.5 parts by weight, the refractive index is greatly reduced.

  In the polycarbonate resin composition I according to Embodiment 1-1, other than known various additives, polycarbonate resin (A1), and polycarbonate resin (A2) to be described later, as long as the effects of the present disclosure are not impaired. These polymers and the like may be appropriately blended.

  Examples of the polymer other than the various additives and the polycarbonate resin (A1) and the polycarbonate resin (A2) include, for example, antioxidants; fluorescent brighteners; colorants such as titanium oxide, carbon black, and dyes; calcium carbonate, clay, Silica, glass fiber, glass sphere, glass flake, carbon fiber, talc, mica, various whiskers, etc .; fluidity improvers; flame retardants such as bromine compounds, phosphorus compounds, silicone compounds; Spreading agents such as bean oil, liquid paraffin, etc .; polyesters having structural units derived from dihydroxy compounds derived from bisphenol A, polyesters such as polyethylene terephthalate, polybutylene terephthalate, polystyrene, high impact polystyrene, polyarylate, ABS resin, AES resin Etc. Other thermoplastic resins such as polymers usually used after alloying with tyrene polymers, polypropylene and polycarbonate; rubbers such as polybutadiene, polyacrylates, ethylene / propylene rubbers, methacrylic esters, styrene, acrylonitrile, etc. Examples include various impact resistance improvers such as rubber-reinforced resins obtained by graft polymerization of compounds.

  The production method of the polycarbonate resin composition I is not particularly limited, and the polycarbonate resin (A1) and the phosphorus-based antioxidant (B), and the various additives, the polycarbonate resin (A1), and the polycarbonate resin (A2) as necessary. ) For polymers other than), adjust the type and amount of each component as appropriate, mix them together using a tumbler, ribbon blender, high-speed mixer, etc., and then melt the mixture using a normal single-screw extruder or twin-screw extruder A method of kneading and pelletizing, a method of appropriately adjusting the types of each component and separately weighing them, putting them into a extruder from a plurality of feeding devices, a method of melting and kneading them into pellets, and a method for adding phosphorus to polycarbonate resin (A1) The system antioxidant (B) is blended at a high concentration, once melt mixed, and pelletized to obtain a master batch, and then the master Batch and polycarbonate resin (A1) and was mixed at a desired mixing ratio, can be employed to melt-kneading method is pelletized and the like.

  Arbitrary conditions can be selected according to the situation for the position at which the components are introduced into the extruder, the extrusion temperature, the screw rotation speed, the supply amount, and the like when the components are melt-kneaded. Further, the master batch and the polycarbonate resin (A1) can be directly mixed into a molding machine after dry mixing at a desired blending ratio to form a molded product to be described later.

  The shape and size of the pellets of the polycarbonate resin composition I obtained as described above are not particularly limited, and may be any shape and size that general resin pellets have. For example, examples of the shape of the pellet include an elliptical columnar shape and a cylindrical shape. The size of the pellet is preferably about 2 to 8 mm in length, and in the case of an elliptical column, the major axis of the cross-sectional ellipse is about 2 to 8 mm and the minor axis is preferably about 1 to 4 mm. In the case of a columnar shape, the diameter of the cross-sectional circle is preferably about 1 to 6 mm. Each of the obtained pellets may be such a size, all the pellets forming the pellet aggregate may be such a size, and the average value of the pellet aggregate is this Such a size may be sufficient, and there is no limitation in particular.

(Embodiment 1-II: Polycarbonate resin composition II)
The polycarbonate resin composition II according to Embodiment 1-II contains a polycarbonate resin (A2) and a phosphorus-based antioxidant (B). Note that the polycarbonate resin composition II in the present disclosure may contain other components as necessary.

（式中、Ｇ^１及びＧ^２は、それぞれ独立して、水素原子、炭素数１〜４のアルキル基又は炭素数１〜３のアルコキシル基を示す。Ｌは、炭素数２〜４のアルキレン基を示す。ｍは、０〜２の整数を示す）
で表されるジヒドロキシ化合物由来の構成単位と、一般式（２）：

（式中、Ｍは、炭素数２〜４のアルキレン基を示す。ｎは、０〜２の整数を示す）
で表されるジナフトチオフェン化合物由来の構成単位とを有する共重合体である。 The polycarbonate resin (A2) has the general formula (1):

(In the formula, G ¹ and G ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyl group having 1 to 3 carbon atoms. L represents an alkylene group having 2 to 4 carbon atoms. M represents an integer of 0 to 2)
A structural unit derived from a dihydroxy compound represented by the general formula (2):

(In the formula, M represents an alkylene group having 2 to 4 carbon atoms, and n represents an integer of 0 to 2).
And a structural unit derived from a dinaphthothiophene compound.

In the general formula (1) representing the dihydroxy compound, G ¹ and G ² are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and L is an alkyl group having 2 to 4 carbon atoms. It is preferably an alkylene group, and m is preferably 0 or 1.

  Examples of the dihydroxy compound represented by the general formula (1) include 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene represented by the formula (1-1) and the formula (1- 9,9-bis (4-hydroxyphenyl) fluorene represented by 2), 9,9-bis (4-hydroxy-3-methylphenyl) fluorene represented by the formula (1-3), and the like. Among these, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene is particularly preferable because it is easily copolymerized with a dinaphthothiophene compound represented by the general formula (2) described later.

The dinaphthothiophene compound is a compound in which two benzene rings not condensed with a thiophene ring each have a substituent (functional group):-(OM) _n- OH. In the general formula (2) representing the dinaphthothiophene compound, M is preferably an alkylene group having 2 to 4 carbon atoms, n is preferably 1 or 2, particularly 1. It is preferable from the point that a high refractive index can be provided by the obtained polycarbonate resin (A2). In addition, the compound in which the substitution position in the two benzene rings not condensed with the thiophene ring is 3,11 is easily copolymerized with the dihydroxy compound represented by the general formula (1), and there are few unreacted monomers. Is preferable.

で表される３，１１−ジヒドロキシエトキシジナフトチオフェン、
式（２−２）：

で表される２，１２−ジヒドロキシエトキシジナフトチオフェン、
式（２−３）：

で表される３，１１−ビス（２−（２−ヒドロキシエトキシ）エトキシ）ジナフトチオフェン
等が挙げられ、これらの中でも、前記一般式（１）で表されるジヒドロキシ化合物と共重合し易いので未反応モノマーが少なく、得られるポリカーボネート樹脂（Ａ２）の黄色度を良好に維持することができ、より高い屈折率を付与することができるという点から、３，１１−ジヒドロキシエトキシジナフトチオフェンが特に好ましい。 As the dinaphthothiophene compound represented by the general formula (2), for example,
Formula (2-1):

3,11-dihydroxyethoxydinaphthothiophene represented by
Formula (2-2):

2,12-dihydroxyethoxydinaphthothiophene represented by
Formula (2-3):

3,11-bis (2- (2-hydroxyethoxy) ethoxy) dinaphthothiophene represented by the above, and among these, it is easy to copolymerize with the dihydroxy compound represented by the general formula (1). In particular, 3,11-dihydroxyethoxydinaphthothiophene is preferable in that it has few unreacted monomers, can maintain the yellowness of the obtained polycarbonate resin (A2) well, and can impart a higher refractive index. preferable.

  The polycarbonate resin (A2) can be produced, for example, by the following method using the dihydroxy compound represented by the general formula (1) and the dinaphthothiophene compound represented by the general formula (2).

  First, a carbonic acid diester is added to the dihydroxy compound represented by the general formula (1), a basic compound catalyst and / or a transesterification catalyst is added as necessary, and these are heated and melted with stirring.

  As said carbonic acid diester, the compound which can be used when manufacturing the said polycarbonate resin (A1) is illustrated, for example, Diphenyl carbonate is especially preferable.

  Examples of the basic compound catalyst include alkali metal compounds, alkaline earth metal compounds, ammonium compounds, and amine compounds. Examples of these alkali metal compounds, alkaline earth metal compounds, ammonium compounds, and amine compounds include the above-mentioned compounds. The compound which can be used when manufacturing polycarbonate resin (A1) is illustrated, respectively.

  Examples of the transesterification catalyst include compounds that can be used in producing the polycarbonate resin (A1).

  In order to melt the dihydroxy compound and the carbonic acid diester, for example, heating to 120 to 260 ° C., and further to 180 to 240 ° C. at normal pressure (760 Torr) in an inert gas atmosphere such as nitrogen gas or argon gas. And stirring for 0.5 to 2 hours is preferable.

  Next, the dinaphthothiophene compound represented by the general formula (2) is added to the heated melt of the dihydroxy compound and the carbonic acid diester, and a polymerization reaction is performed.

  For example, the polymerization reaction may be performed by stirring the heated melt and the dinaphthothiophene compound for 0.5 to 1.5 hours, and then taking 0.5 to 1 hour in consideration of the degree of polymerization of the polymer. It is preferable to carry out by raising the degree of decompression of (˜a few Torr) and stirring at 120 to 260 ° C., further 180 to 240 ° C., for further 0.3 to 0.5 hours.

  And after completion | finish of the said polymerization reaction, the reaction system is cooled and the polycarbonate resin (A2) which is the target copolymer can be obtained.

  Further, as a subsequent step, (i) the copolymer is dissolved in an organic solvent (good solvent) such as dichloromethane for the purpose of removing low molecular weight substances such as unreacted monomers and by-products remaining in the copolymer. After preparing the copolymer solution, a method of precipitating with an organic solvent (poor solvent) such as methanol or ethanol as a precipitant, (ii) introducing the copolymer into an extruder having a high theoretical surface renewal frequency A method of pelletizing (for example, see JP-A-01-149827), (iii) a method of adding water to the copolymer and kneading and extruding while degassing under conditions that do not cause hydrolysis (for example, special For example, Japanese Patent Publication No. 05-027647) can be used.

  In addition, there is no limitation in particular in the reaction apparatus used when manufacturing polycarbonate resin (A2), For example, the reaction apparatus which can be used when manufacturing the said polycarbonate resin (A1) is illustrated.

  When producing the polycarbonate resin (A2), the blending ratio of the dihydroxy compound represented by the general formula (1) and the dinaphthothiophene compound represented by the general formula (2), that is, the structural unit derived from the dihydroxy compound The ratio with the structural unit derived from the dinaphthothiophene compound (dihydroxy compound / dinaphthothiophene compound) is 10/90 to 99.8 / 0.2, more preferably 20/80 to 99.5 / 0. 5 is preferable. When the ratio exceeds 99.8 / 0.2, there is a risk that the effect of improving the refractive index may not be seen. When the ratio is less than 10/90, the melting point of the dinaphthothiophene compound is Due to the high value, the reaction system may become unmelted in the reaction apparatus.

  The amount of the carbonic acid diester added to the dihydroxy compound is adjusted to be about 0.9 to 1.1 mol with respect to 1 mol in total of the dihydroxy compound and the dinaphthothiophene compound. It is preferable from the viewpoint of obtaining a polymer, and more preferably about equimolar to the total.

Furthermore, when adding the said basic compound catalyst and / or the said transesterification catalyst, it is 1.0 * 10 < ^-8 > -1.0 * 10 < ^- > with respect to 1 mol in total of a dihydroxy compound and a dinaphtho thiophene compound. It is preferable to adjust so that it may become about ⁴ mol.

  The nd of the polycarbonate resin (A2) is preferably 1.640 or more, more preferably 1.650 or more. Since the polycarbonate resin (A2) has a higher refractive index than the polycarbonate resin (A1), it is particularly suitable for optical members such as various lenses, prisms, and disks, especially for exterior parts that require design. And an optical member such as a lens provided in a camera of a portable information terminal.

  The Mw of the polycarbonate resin (A2) is preferably 15000-40000, more preferably 17000-35000. Thus, fluidity | liquidity of the polycarbonate resin composition II obtained is favorably maintained because Mw is the range of 15000-40000.

  The Tg of the polycarbonate resin (A2) is preferably 130 ° C. or higher, more preferably 140 ° C. or higher. Thus, when Tg is 130 degreeC or more, the heat resistance of the polycarbonate resin composition II obtained is maintained favorable.

  The phosphorus antioxidant (B) in the present Embodiment 1-1 is a component that works with the polycarbonate resin (A2) to improve the thermal stability of the obtained polycarbonate resin composition II.

  As the phosphorus antioxidant (B), for example, the same phosphorus antioxidant as the phosphorus antioxidant (B) contained in the polycarbonate resin composition I according to Embodiment 1-1 is used. Examples thereof include compounds represented by the general formulas (3) to (6).

  Among the compounds represented by the general formulas (3) to (6), the compound represented by the general formula (3) which is a cyclic phosphite compound and the general formula (3) which is a phosphite compound 4) A polycarbonate resin (A2) having a structural unit derived from a dihydroxy compound represented by the general formula (1) and a structural unit derived from a dinaphthothiophene compound represented by the general formula (2). In particular, a polycarbonate resin composition II having a higher refractive index and extremely improved thermal stability can be obtained while maintaining excellent optical performance.

  The amount of the phosphorus-based antioxidant (B) is 0.02 to 1.5 parts by weight, preferably 0.03 to 1 part by weight, more preferably 0.03 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A2). 04 to 0.5 parts by weight. When the amount of the phosphorus-based antioxidant (B) is less than 0.02 parts by weight, the effect of improving the thermal stability cannot be obtained. Conversely, when the amount of the phosphorus-based antioxidant (B) exceeds 1.5 parts by weight, the refractive index is greatly reduced.

  In the polycarbonate resin composition II according to Embodiment 1-II, other than known various additives, polycarbonate resin (A2) and the polycarbonate resin (A1), as long as the effects of the present disclosure are not impaired. A polymer or the like may be appropriately blended.

  Examples of the polymer other than the various additives, polycarbonate resin (A2), and polycarbonate resin (A1) are the same as the additives and polymers contained in the polycarbonate resin composition I according to Embodiment 1-1. Is exemplified.

  The production method of the polycarbonate resin composition II is not particularly limited, and the polycarbonate resin (A2) and the phosphorus-based antioxidant (B), and the various additives, the polycarbonate resin (A2), and the polycarbonate resin (A1) as necessary. ) For polymers other than), adjust the type and amount of each component as appropriate, mix them together using a tumbler, ribbon blender, high-speed mixer, etc., and then melt the mixture using a normal single-screw extruder or twin-screw extruder A method of kneading and pelletizing, a method of appropriately adjusting the types of each component, weighing them separately, putting them into a extruder from a plurality of feeding devices, a method of melting and kneading them into a pellet, and a method for adding phosphorus to polycarbonate resin (A2) The system antioxidant (B) is blended at a high concentration, once melt mixed, and pelletized to obtain a master batch, and then the master Batch and polycarbonate resin (A2) and was mixed at a desired mixing ratio, can be employed to melt-kneading method is pelletized and the like.

  Arbitrary conditions can be selected according to the situation for the position at which the components are introduced into the extruder, the extrusion temperature, the screw rotation speed, the supply amount, and the like when the components are melt-kneaded. Also, the master batch and the polycarbonate resin (A2) can be dry-mixed at a desired blending ratio and then directly charged into a molding machine to obtain a molded product to be described later.

  The shape and size of the pellets of the polycarbonate resin composition II obtained as described above are not particularly limited, and as with the polycarbonate resin composition I, the shape and size of general resin pellets may be used. Examples of the shape and size of the pellets are the same as those of the polycarbonate resin composition I. Each of the obtained pellets may be the size illustrated above, and all the pellets forming the pellet aggregate are The exemplified size may be used, and the average value of the pellet aggregate may be the exemplified size, and there is no particular limitation.

  As described above, Embodiments 1-I and 1-II have been described as examples of the technology disclosed in the present application. However, the technology in the present disclosure is not limited to this, and can also be applied to an embodiment in which changes, replacements, additions, omissions, and the like are appropriately performed.

(Embodiment 2: Molded product)
The molded product according to the second embodiment is obtained by molding the polycarbonate resin composition I according to the first embodiment I obtained as described above or the polycarbonate resin composition II according to the first embodiment II. is there.

  There is no particular limitation on the method for producing the molded article, and examples thereof include a method of molding the polycarbonate resin composition I or the polycarbonate resin composition II by a known injection molding method, extrusion molding method, injection / compression molding method, or the like. .

  The molded product according to the second embodiment obtained as described above is suitable as an optical member such as various lenses, prisms, and disks. In particular, the molded article according to the second embodiment is excellent in thermal stability and can be molded at a high temperature. Therefore, the molded article is required for a lens for exterior parts and a camera for a portable information terminal that require design properties. It is suitable as an optical member such as a lens provided. Note that a molded product obtained by molding a polycarbonate resin composition II containing a polycarbonate resin (A2) having a higher refractive index is required to have more design than a molded product obtained by molding the polycarbonate resin composition I. It is further suitable for an optical member such as a lens for exterior parts to be used and a lens provided in a camera of a portable information terminal.

  As described above, the second embodiment has been described as an example of the technique disclosed in the present application. However, the technology in the present disclosure is not limited to this, and can also be applied to an embodiment in which changes, replacements, additions, omissions, and the like are appropriately performed.

  Hereinafter, the present disclosure will be specifically described by way of examples. However, the present disclosure is not limited to these examples.

で表される９，９−ビス（４−（２−ヒドロキシエトキシ）フェニル）フルオレン The following were used as raw materials for the polycarbonate resin (A1) and / or the polycarbonate resin (A2).
(1) Dihydroxy compounds and BPEF
Formula (1-1):

9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene represented by the formula

で表される３，１１−ジヒドロキシエトキシジナフトチオフェン (2) Dinaphthothiophene compound / DHEODNT
Formula (2-1):

3,11-dihydroxyethoxydinaphthothiophene represented by

Production Example I-1 (Production of BPEF polymer)
264.2 g (0.6025 mol) of BPEF, 135.8 g (0.6339 mol) of diphenyl carbonate (hereinafter referred to as DPC) and 0.0015 g (1.8 × 10 ⁻⁵ mol) of sodium hydrogen carbonate were added to a stirrer and a distillate. The reactor was placed in a reactor equipped with a taking-out apparatus, and heated to 215 ° C. at a normal pressure (760 Torr) in a nitrogen gas atmosphere while stirring to melt.

  After stirring the reaction system for 90 minutes, the pressure was reduced to 150 Torr over 40 minutes, and the mixture was stirred for 20 minutes at 215 ° C. and 150 Torr to cause a polymerization reaction.

  After completion of the reaction, the reaction system was cooled to room temperature, and the polymer was dissolved in dichloromethane to prepare a polymer solution, followed by precipitation fractionation with methanol to obtain a target BPEF polymer (hereinafter referred to as polycarbonate resin (A1)). And BPEF PC-1).

Production Example I-2 (Production of BPEF polymer)
Polycarbonate resin (A1) in the same manner as in Production Example I-1, except that the amount of BPEF was changed to 268.7 g (0.6127 mol) and the amount of DPC was changed to 131.3 g (0.6129 mol). A BPEF polymer (hereinafter referred to as BPEF PC-2) was obtained.

Production Example II (Production of BPEF-DHEODNT copolymer)
40.74 g (0.0929 mol) of BPEF, 24.88 g (0.1161 mol) of DPC and 0.00029 g (3.5 × 10 ⁻⁶ mol) of sodium hydrogen carbonate were placed in a reactor equipped with a stirrer and a distillation apparatus. While stirring, the mixture was heated to 215 ° C. at a normal pressure (760 Torr) in a nitrogen gas atmosphere and melted.

  After stirring the reaction system for 90 minutes, 9.39 g (0.0232 mol) of DHEODNT was put into the reactor, and further stirred for 60 minutes, and then the pressure was reduced to 150 Torr over 40 minutes, and 215 ° C. and 150 Torr for 20 minutes. The polymerization reaction was carried out by stirring.

  After completion of the reaction, the reaction system was cooled to room temperature, and the polymer was dissolved in dichloromethane to prepare a copolymer solution. Then, precipitation fractionation was performed with methanol, and the target polycarbonate resin (A2) BPEF-DHEODNT A coalescence (hereinafter referred to as BPEF-DHEODNT) was obtained.

Test example (physical property measurement)
About obtained BPEF PC-1, BPEF PC-2, and BPEF-DHEODNT, nd, Mw, and Tg were measured with the following method. The results are shown in Table 1.

(A) Refractive index (nd)
The obtained polymer or copolymer was dried at 120 ° C. for 4 hours with a hot air circulating dryer, and then subjected to a mold temperature of 250 ° C. using a press molding machine (manufactured by Kondo Metal Industry Co., Ltd.). And formed into a test piece having a thickness of 1.5 mm. About this test piece, the refractive index was measured based on the method prescribed | regulated by JISK7142 "How to obtain | require a refractive index" using the multiwavelength Abbe refractometer (made by Atago Co., Ltd.).

(B) Weight average molecular weight (Mw)
Using a gel permeation chromatography measuring apparatus (Waters, Alliance 2695 Separations Module), Mw in terms of standard polystyrene was determined under the following measurement conditions.
Column type: Agilent Technologies
Plgel 5μm MIXED-C
Eluent: Tetrahydrofuran Flow rate: 1 ml / min.
Detection: Absorption at 254 nm

(C) Glass transition temperature (Tg)
Using a differential scanning calorimeter (Seiko Instruments Co., Ltd., DSC6200), the temperature was raised to 250 ° C. in a nitrogen gas atmosphere, and after cooling to −100 ° C., the temperature raising rate was 10 ° C./min. The Tg observed when the temperature was raised was confirmed.

  The following were used as raw materials for the polycarbonate resin composition I and / or the polycarbonate resin composition II.

1-1. Polycarbonate resin (A1)
・ BPEF PC-1
・ BPEF PC-2

1-2. Polycarbonate resin (A2)
・ BPEF-DHEODNT

で表される２，４，８，１０−テトラ−ｔ−ブチル−６−〔３−（３−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）プロポキシ〕ジベンゾ〔ｄ，ｆ〕〔１，３，２〕ジオキサホスフェピン
スミライザーＧＰ
（商品名、住友化学（株）製、以下、化合物Ａという） 2. Phosphorous antioxidant (B)
2-1. Cyclic phosphite ester compound

2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-t-butylphenyl) propoxy] dibenzo [d, f] [1, 3,2] Dioxaphosphepine Sumilizer GP
(Trade name, manufactured by Sumitomo Chemical Co., Ltd., hereinafter referred to as Compound A)

で表される３，９−ビス（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノキシ）−２，４，８，１０−テトラオキサ−３，９−ジフォスファスピロ［５，５］ウンデカン
アデカスタブＰＥＰ−３６
（商品名、（株）ＡＤＥＫＡ製、以下、化合物Ｂという） 2-2. Phosphite compounds ・ The following formula:

3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane ADK STAB PEP-36
(Trade name, manufactured by ADEKA Corporation, hereinafter referred to as Compound B)

で表されるトリス（２，４−ジ−ｔ−ブチルフェニル）フォスファイト
イルガフォス１６８
（商品名、ＢＡＳＦ社製、以下、化合物Ｃという） 2-3. Phosphite compounds ・ The following formula:

Tris (2,4-di-t-butylphenyl) phosphite represented by the formula Irgaphos 168
(Trade name, manufactured by BASF, hereinafter referred to as Compound C)

で表される［１，１´−ビフェニル］−４，４´−ジイルビス［ビス（２，４−ジ−ｔ−ブチルフェノキシ）フォスフィン］
イルガフォスＰ−ＥＰＱ
（商品名、ＢＡＳＦ社製、以下、化合物Ｄという） 2-4. Phosphate ester compounds:

[1,1′-biphenyl] -4,4′-diylbis [bis (2,4-di-t-butylphenoxy) phosphine] represented by
Irgaphos P-EPQ
(Trade name, manufactured by BASF, hereinafter referred to as Compound D)

3. Hindered phenolic antioxidant, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ADK STAB AO-50
(Trade name, manufactured by ADEKA Corporation, hereinafter referred to as Compound E)

Examples I-1 to I-7 and Comparative Examples I-1 to I-3
The raw materials were collectively put into a tumbler at the ratios shown in Table 2, and after dry mixing for 10 minutes, a twin-screw extruder (manufactured by Nippon Steel Works, TEX30α, shaft diameter = 30 mmφ, L / D) = 41), the mixture was melt-kneaded at a melting temperature of 220 ° C. to obtain pellets of a polycarbonate resin composition. In addition, all the pellets obtained in Examples I-1 to I-7 and Comparative Examples I-1 to I-3 are substantially elliptical cylinders, and the aggregates consisting of 100 pellets are as follows. It was a size (average value (mm)).
Length Major Diameter of Section Ellipse Minor Diameter of Section Ellipse Example I-1 5.0 4.0 2.5
I-2 5.0 3.9 2.7
I-3 5.1 4.0 2.7
I-4 5.2 4.2 2.9
I-5 5.2 4.1 2.9
I-6 5.2 4.1 2.7
I-7 5.0 3.9 2.8
Comparative Example I-1 5.2 4.0 2.6
I-2 5.0 4.1 2.8
I-3 5.2 4.1 2.9

  Each evaluation was performed according to the following method using the obtained pellet. The results are shown in Table 2.

(A) Yellowness After the obtained pellets were dried at 120 ° C. for 4 hours with a hot-air circulating dryer, using a press molding machine (manufactured by Kondo Metal Industry Co., Ltd.), the mold temperature was adjusted to 250 ° C. And formed into a test piece having a thickness of 1.5 mm.

  About this test piece, Yellowness Index (yellowness) was measured on condition of a D65 light source and a viewing angle of 10 degrees using the spectrophotometer (Murakami Color Research Laboratory make, CMS35-SP). In addition, the yellowness was less than 7.0 as good (indicated by ◯ in the table), and 7.0 or higher was determined as poor (indicated by x in the table).

(I) Total light transmittance (a) About the test piece shape | molded similarly to evaluation of the said yellow degree, using spectrophotometer (Corporation | KK Murakami Color Research Laboratory make, HM-150), it is JIS K 7361-. The total light transmittance was measured in accordance with the method specified in 1 “Plastics—Test method for total light transmittance of transparent material—Part 1: Single beam method”. The total light transmittance was 86.0% or more as good (indicated by ◯ in the table) and less than 86.0% was defective (indicated by x in the table).

(C) Refractive index (nd)
(A) About the test piece shape | molded similarly to evaluation of the yellowness, using a multiwavelength Abbe refractometer (made by Atago Co., Ltd.), the method prescribed | regulated by JISK7142 "Plastic-Determination of refractive index" The refractive index was measured according to the above. A refractive index of 1.6370 or higher was evaluated as good (indicated by ◯ in the table), and less than 1.6370 was determined as defective (indicated by x in the table).

(D) Fluidity After the obtained pellets were dried at 120 ° C. for 4 hours with a hot-air circulating dryer, using a Koka type flow tester (manufactured by Shimadzu Corporation) at a cylinder temperature of 220 ° C. The apparent melt viscosity (Pa · s) at a shear rate of 1000 (sec-1) was determined. A melt viscosity of less than 1700 Pa · s was determined to be good (indicated by a circle in the table) and 1700 Pa · s or higher was determined to be defective (indicated in the table by x).

(E) Comprehensive judgment The evaluation of yellowness, total light transmittance, refractive index and fluidity is all acceptable (indicated in the table by a circle), and even one defective is rejected (table) Middle, indicated by x).

  In the polycarbonate resin compositions I of Examples I-1 to I-7, the phosphorus antioxidant (B) is used as an antioxidant, and the amount of the phosphorus antioxidant (B) is It is adjusted within the range of 0.02 to 1.5 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A1). Therefore, all the test pieces molded from these polycarbonate resin compositions I under the conditions of 250 ° C. not only have high total light transmittance and refractive index, but also have very low yellowness and excellent thermal stability. Moreover, the melt viscosity is low at 220 ° C. and the fluidity is good.

  In particular, as phosphorus antioxidant (B), polycarbonate resin composition I (Example I-2) using compound A which is a cyclic phosphite compound and compound C which is a phosphite compound are used. The used polycarbonate resin composition I (Example I-5) has higher total light transmittance and refractive index, lower yellowness, and further excellent thermal stability.

  On the other hand, in the polycarbonate resin composition of Comparative Example I-1, the amount of the phosphorus antioxidant (B) with respect to 100 parts by weight of the polycarbonate resin (A1) is less than 0.02 parts by weight. Therefore, the test piece molded from this polycarbonate resin composition has good total light transmittance and refractive index, but has high yellowness and poor thermal stability.

  In the polycarbonate resin composition of Comparative Example I-2, the amount of the phosphorus-based antioxidant (B) with respect to 100 parts by weight of the polycarbonate resin (A1) exceeds 1.5 parts by weight. Therefore, the test piece molded from this polycarbonate resin composition has good yellowness and total light transmittance, but has a low refractive index.

  In the polycarbonate resin composition of Comparative Example I-3, a hindered phenol-based antioxidant is used instead of the phosphorus-based antioxidant (B). Therefore, although the test piece molded from this polycarbonate resin composition has a good refractive index, it not only has a low total light transmittance, but also has a high yellowness and a poor thermal stability.

Examples II-1 to II-6 and Comparative Examples II-1 to II-3
Except that the respective raw materials were blended in the ratios shown in Table 3, pellets of a polycarbonate resin composition were obtained in the same manner as in Examples I-1 to I-7 and Comparative Examples I-1 to I-3. In addition, all the pellets obtained in Examples II-1 to II-6 and Comparative Examples II-1 to II-3 are substantially elliptical cylinders, and the aggregates consisting of 100 pellets are as follows. It was a size (average value (mm)).
Length Major Diameter of Section Ellipse Minor Diameter of Section Ellipse Example II-1 5.1 4.0 2.6
II-2 5.0 3.9 2.7
II-3 5.1 4.2 2.6
II-4 5.1 4.1 2.9
II-5 5.3 4.1 2.9
II-6 5.2 4.1 2.8
Comparative Example II-1 5.2 4.0 2.6
II-2 5.1 4.0 2.7
II-3 5.2 4.1 2.9

  Each evaluation was performed in the same manner as in Examples I-1 to I-7 and Comparative Examples I-1 to I-3 using the obtained pellets. The results are shown in Table 3.

  For the pellets obtained in Examples II-1 to II-6 and Comparative Examples II-1 to II-3, the yellowness is less than 28.0 (indicated by ○ in the table), 28.0. The above are poor (indicated by x in the table), the total light transmittance is good at 79.0% or more (indicated by ◯ in the table), the less than 79.0% is defective (indicated by x in the table), refraction The rate is good at 1.6500 or more (indicated by ◯ in the table), poor at less than 1.6500 (indicated by x in the table), and the melt viscosity is less than 1000 Pa · s (indicated by ◯ in the table), 1000 Pa · s or more was regarded as defective (indicated by x in the table).

  In the polycarbonate resin compositions II of Examples II-1 to II-6, the phosphorus antioxidant (B) is used as an antioxidant, and the amount of the phosphorus antioxidant (B) is It is adjusted within the range of 0.02 to 1.5 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A2). Therefore, all the test pieces molded from these polycarbonate resin compositions II under the conditions of 250 ° C. not only have high total light transmittance and refractive index, but also have low yellowness and excellent thermal stability. In addition, the melt viscosity at 220 ° C. is low and the fluidity is good.

  In particular, the polycarbonate resin composition II (Example II-2) using the compound A which is a cyclic phosphite compound as the phosphorus antioxidant (B) has higher total light transmittance and refractive index. The yellowness is smaller and the thermal stability is even better.

  On the other hand, in the polycarbonate resin composition of Comparative Example II-1, the amount of the phosphorus antioxidant (B) with respect to 100 parts by weight of the polycarbonate resin (A2) is less than 0.02 parts by weight. Therefore, the test piece molded from this polycarbonate resin composition has good total light transmittance and refractive index, but has high yellowness and poor thermal stability.

  In the polycarbonate resin composition of Comparative Example II-2, the amount of the phosphorus-based antioxidant (B) with respect to 100 parts by weight of the polycarbonate resin (A2) exceeds 1.5 parts by weight. Therefore, although the test piece molded from this polycarbonate resin composition has good yellowness, not only the total light transmittance is low but also the refractive index is low.

  In the polycarbonate resin composition of Comparative Example II-3, not the phosphorus-based antioxidant (B) but a hindered phenol-based antioxidant is used. Therefore, the test piece molded from this polycarbonate resin composition has good total light transmittance and refractive index, but has high yellowness and poor thermal stability.

  As described above, the embodiments have been described as examples of the technology in the present disclosure. To that end, a detailed explanation was provided.

  Accordingly, the components described in the detailed description include not only components essential for solving the problem but also components not essential for solving the problem in order to illustrate the above technique. obtain. Therefore, it should not be immediately recognized that these non-essential components are essential as the non-essential components are described in the detailed description.

  Moreover, since the above-mentioned embodiment is for demonstrating the technique in this indication, a various change, replacement, addition, abbreviation, etc. can be performed in a claim or its equivalent range.

  The present disclosure can be suitably used as optical members such as various lenses, prisms, disks, and the like, in particular, lenses for exterior parts that require designability, and lenses that are provided in cameras of portable information terminals.

Claims (6)

General formula (1):

(In the formula, G ¹ and G ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyl group having 1 to 3 carbon atoms. L represents an alkylene group having 2 to 4 carbon atoms. M represents an integer of 0 to 2)
A structural unit derived from a dihydroxy compound represented by:
General formula (2):

(In the formula, M represents an alkylene group having 2 to 4 carbon atoms, and n represents an integer of 0 to 2).
A polycarbonate resin (A2) having a structural unit derived from a dinaphthothiophene compound represented by:
Containing a phosphorus-based antioxidant (B),
The polycarbonate resin composition whose quantity of the said phosphorus antioxidant (B) is 0.02-1.5 weight part with respect to 100 weight part of said polycarbonate resin (A2). The dihydroxy compound represented by the general formula (1) is 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, and the dinaphthothiophene compound represented by the general formula (2) is 3, is a 11-dihydroxy ethoxy Gina shift thiophene, polycarbonate resin composition of claim 1. The phosphorus-based antioxidant (B) is represented by the general formula (3):

^{(Wherein, R 1, R 2, R} 4 and ^{R 5} are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, cycloalkyl group having 5 to 8 carbon atoms, 6 to 12 carbon atoms alkylcycloalkyl group, .R ³ showing an aralkyl group or a phenyl group having 7 to 12 carbon atoms, .X represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, a single bond, a sulfur atom or the formula: -CHR ^6- (wherein R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms) A represents a group having 1 to 8 carbon atoms. Or an alkylene group of the formula: * —COR ⁷ — (wherein R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a bond on the oxygen side) Y and Z are either a hydroxyl group or an alcohol having 1 to 8 carbon atoms. A xyl group or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms)
In a compound represented by a polycarbonate resin composition according to claim 1. The compound represented by the general formula (3) is 2,4,8,10-tetra-tert-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo. The polycarbonate resin composition according to claim 3 , which is [d, f] [1, 3 , 2] dioxaphosphine. A molded article comprising the polycarbonate resin composition according to claim 1 . The molded article according to claim 5 , which is a lens provided in a camera of a portable information terminal.