JP6895778B2 - Polycarbonate resin composition and molded article made of it - Google Patents

Description

The present invention relates to a phosphorescent polycarbonate resin composition. More specifically, the present invention relates to a polycarbonate resin composition in which a phosphorescent material is blended with polycarbonate and a decrease in phosphorescent property after weather resistance treatment is small, and a molded product comprising the polycarbonate resin composition.

The phosphorescent material utilizes the light emitted when the molecular energy is excited by the light irradiation from the outside and the energy rank is lowered to the original level over time. Since it emits light for a certain period of time that can be actually used, it is used for nighttime display applications such as car stops, road markings, and evacuation guidance signs. In particular, with regard to evacuation guidance signs, the problem of turning off the lights and losing sight of the evacuation route in the event of a disaster such as a fire or earthquake has become apparent in recent years, and the introduction of new functional equipment using phosphorescent materials is being promoted both in Japan and overseas. In such applications, it is expected to be installed for a long period of time, and there is a demand for a material with little discoloration and deterioration of phosphorescence with the passage of time.

On the other hand, aromatic polycarbonate resins are widely used as materials for various parts in the fields of electrical and electronic engineering, automobiles, construction, etc. because they are excellent in heat resistance, mechanical properties, dimensional stability, and the like. However, when the polycarbonate molded product is used for a long period of time, the mechanical properties deteriorate and discoloration occur with the passage of time. Therefore, a method of adding an ultraviolet absorber to the resin composition to prevent weather resistance deterioration is known.

In Patent Document 1, by blending Eu, Ln-activated silicate phosphor organic silane compound and / or silicone compound with polycarbonate, it is excellent in thermal stability during processing, hue of molded product, and long afterglow. The resin composition is disclosed. However, although there is an improvement effect on the ΔYI value after the heat aging test and the presence or absence of deformation after the moist heat resistance test, there is no description about the luminous property after the weather resistance test.

In Patent Documents 2 and 3, the phosphorescent polycarbonate resin is blended with an organic silane compound and / or a silicone compound to suppress thermal decomposition during processing, improve mechanical strength and heat resistance, and by heating. It is disclosed that the change in hue can be reduced. However, although there is an improvement effect on the light emission after the heat aging test and the presence or absence of deformation after the moisture heat resistance test, there is no description about the phosphorescence after the weather resistance test.

Patent Document 4 describes that by blending an ultraviolet absorber with a polycarbonate resin composed of a polycarbonate-polyorganosiloxane copolymer and polycarbonate, mechanical properties are maintained and molded products are yellowed during long-term outdoor use. It is disclosed that it is excellent in suppression. However, there is no description about the phosphorescent property when the phosphorescent material is included.

Japanese Unexamined Patent Publication No. 2009-215415 Japanese Unexamined Patent Publication No. 2010-159318 Japanese Unexamined Patent Publication No. 2010-159319 JP 2015-124304

An object of the present invention is to provide an aromatic polycarbonate resin composition having a small discoloration and an excellent retention rate of phosphorescence when used outdoors for a long period of time, and a molded product made of the same.

As a result of diligent research to achieve the above object, the present inventors have added a phosphorescent material, a light diffusing agent, and an ultraviolet absorber to polycarbonate and a polycarbonate-polydiorganosiloxane copolymer resin, so that they can be used outdoors. We have found that the discoloration and the retention rate of phosphorescent properties are improved during long-term use, and have reached the present invention. That is, according to the present invention, with respect to 100 parts by weight of the resin component composed of (A) polycarbonate resin (A component) and (B) polycarbonate-polydiorganosiloxane copolymer resin (B component), (C) phosphorescent material (C component). ) 1-35 parts by weight, (D) 0.05 to 10 parts by weight of the light diffusing agent (D component), and (E) 0.01 to 1 part by weight of the ultraviolet absorber (E component). Provided.

One of the more preferable aspects of the present invention is (2) a polycarbonate-polydi whose B component is composed of a polycarbonate block represented by the following general formula [1] and a polydiorganosiloxane block represented by the following general formula [3]. The polycarbonate resin composition according to the above configuration (1), which is an organosiloxane copolymer resin.

［上記一般式〔１〕において、Ｒ^１及びＲ^２は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１８のアルキル基、炭素原子数１〜１８のアルコキシ基、炭素原子数６〜２０のシクロアルキル基、炭素原子数６〜２０のシクロアルコキシ基、炭素原子数２〜１０のアルケニル基、炭素原子数６〜１４のアリール基、炭素原子数６〜１４のアリールオキシ基、炭素原子数７〜２０のアラルキル基、炭素原子数７〜２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、それぞれ複数ある場合はそれらは同一でも異なっていても良く、ａ及びｂは夫々１〜４の整数であり、Ｗは単結合もしくは下記一般式〔２〕で表される基からなる群より選ばれる少なくとも一つの基である。

[In the above general formula [1], R ¹ and R ² are independently hydrogen atom, halogen atom, alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, and 6 to 6 carbon atoms, respectively. 20 cycloalkyl groups, 6 to 20 carbon atoms cycloalkoxy groups, 2 to 10 carbon atoms alkenyl groups, 6 to 14 carbon atoms aryl groups, 6 to 14 carbon atoms aryloxy groups, carbon atoms Represents a group selected from the group consisting of an aralkyl group having a number of 7 to 20, an aralkyloxy group having a carbon atom number of 7 to 20, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. A and b are each an integer of 1 to 4, and W is at least one group selected from the group consisting of a single bond or a group represented by the following general formula [2].

（上記一般式〔２〕においてＲ^１１，Ｒ^１２，Ｒ^１３，Ｒ^１４，Ｒ^１５，Ｒ^１６，Ｒ^１７及びＲ^１８は夫々独立して水素原子、炭素原子数１〜１８のアルキル基、炭素原子数６〜１４のアリール基及び炭素原子数７〜２０のアラルキル基からなる群から選ばれる基を表し、Ｒ^１９及びＲ^２０は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１８のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数６〜２０のシクロアルキル基、炭素原子数６〜２０のシクロアルコキシ基、炭素原子数２〜１０のアルケニル基、炭素原子数６〜１４のアリール基、炭素原子数６〜１０のアリールオキシ基、炭素原子数７〜２０のアラルキル基、炭素原子数７〜２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、複数ある場合はそれらは同一でも異なっていても良く、ｃは１〜１０の整数、ｄは４〜７の整数である。）］

(In the above general formula [2], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are independently hydrogen atoms, alkyl groups having 1 to 18 carbon atoms, and carbon. Represents a group selected from the group consisting of an aryl group having 6 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ are independent hydrogen atoms, halogen atoms, and carbon atoms 1 to 18 respectively. Aryl group, alkoxy group with 1 to 10 carbon atoms, cycloalkyl group with 6 to 20 carbon atoms, cycloalkoxy group with 6 to 20 carbon atoms, alkenyl group with 2 to 10 carbon atoms, 6 carbon atoms From an aryl group of ~ 14, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group. Represents a group selected from the group, and if there are a plurality of groups, they may be the same or different, and c is an integer of 1 to 10 and d is an integer of 4 to 7.)]

（上記一般式〔３〕において、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、各々独立に水素原子、炭素数１〜１２のアルキル基又は炭素数６〜１２の置換若しくは無置換のアリール基であり、Ｒ^９及びＲ^１０は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基であり、ｅ及びｆは夫々１〜４の整数であり、ｐは自然数であり、ｑは０又は自然数であり、ｐ＋ｑは４以上１５０以下の自然数である。Ｘは炭素数２〜８の二価脂肪族基である。）

(In the above general formula [3], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently substituted with a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or 6 to 12 carbon atoms, respectively. Alternatively, they are unsubstituted aryl groups, and R ⁹ and R ¹⁰ are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 10 carbon atoms, and e and f. Is an integer of 1 to 4, p is a natural number, q is 0 or a natural number, p + q is a natural number of 4 or more and 150 or less. X is a divalent aliphatic group having 2 to 8 carbon atoms. .)

One of the more preferable aspects of the present invention is (3) a polydiorganosiloxane block represented by the following general formula [4] contained in the above general formula [3] based on the total weight of the polycarbonate resin composition. The polycarbonate resin composition according to the above configuration (1) or (2), wherein the content is 1.0% by weight or more.

（上記一般式〔４〕において、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、各々独立に水素原子、炭素数１〜１２のアルキル基又は炭素数６〜１２の置換若しくは無置換のアリール基であり、ｐは自然数であり、ｑは０又は自然数であり、ｐ＋ｑは４以上１５０以下の自然数である。）

(In the above general formula [4], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently substituted with a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or 6 to 12 carbon atoms, respectively. Alternatively, it is an unsubstituted aryl group, p is a natural number, q is 0 or a natural number, and p + q is a natural number of 4 or more and 150 or less.)

One of the more preferable embodiments of the present invention is characterized in that (4) the component E is an ultraviolet absorber containing a compound having a benzotriazole skeleton and a molecular weight of less than 500 as a main component. The polycarbonate resin composition according to any one of (1) to (3).

One of the more preferable embodiments of the present invention is (5) the polycarbonate resin composition according to any one of the above configurations (1) to (4), wherein the average particle size of the D component is 1 to 20 μm. Is.

One of the more preferable aspects of the present invention is (6) a molded product obtained by molding the polycarbonate resin composition according to any one of the above configurations (1) to (5).

Hereinafter, the present invention will be specifically described.

(Component A: Polycarbonate resin)
The polycarbonate resin used as the component A of the present invention is usually obtained by reacting a dihydroxy compound and a carbonate precursor by an interfacial polycondensation method or a molten ester exchange method, or a carbonate prepolymer by a solid phase ester exchange method. It is obtained by polymerizing with or by a ring-opening polymerization method of a cyclic carbonate compound. The dihydroxy component used here may be any as long as it is usually used as the dihydroxy component of aromatic polycarbonate, and may be bisphenols or aliphatic diols. Examples of bisphenols include 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4-hydroxyphenyl) -1-. Phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -3,3,5 -Trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3'-biphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-t-) Butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (3-bromo-4-hydroxyphenyl) Propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) Hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis ( 4-Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy- 3,3'-Dimethyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3, 3'-diphenyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenylsulfide, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis {2-( 4-Hydroxyphenyl) propyl} benzene, 1,4-bis (4-hydroxyphenyl) cyclohexane , 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4'-(1,3-adamantane) Diyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane and the like can be mentioned.

Examples of aliphatic diols include 2,2-bis- (4-hydroxycyclohexyl) -propane, 1,14-tetradecanediol, octaethylene glycol, 1,16-hexadecanediol, and 4,4'-bis (2-). Hydroxyethoxy) biphenyl, bis {(2-hydroxyethoxy) phenyl} methane, 1,1-bis {(2-hydroxyethoxy) phenyl} ethane, 1,1-bis {(2-hydroxyethoxy) phenyl} -1- Phenylethane, 2,2-bis {(2-hydroxyethoxy) phenyl} propane, 2,2-bis {(2-hydroxyethoxy) -3-methylphenyl} propane, 1,1-bis {(2-hydroxyethoxy) ) Phenyl} -3,3,5-trimethylcyclohexane, 2,2-bis {4- (2-hydroxyethoxy) -3,3'-biphenyl} propane, 2,2-bis {(2-hydroxyethoxy)- 3-Isopropyl} propane, 2,2-bis {3-t-butyl-4- (2-hydroxyethoxy) phenyl} propane, 2,2-bis {(2-hydroxyethoxy) phenyl} butane, 2,2 -Bis {(2-hydroxyethoxy) phenyl} -4-methylpentane, 2,2-bis {(2-hydroxyethoxy) phenyl} octane, 1,1-bis {(2-hydroxyethoxy) phenyl} decan, 2 , 2-bis {3-bromo-4- (2-hydroxyethoxy) phenyl} propane, 2,2-bis {3,5-dimethyl-4- (2-hydroxyethoxy) phenyl} propane, 2,2-bis {3-Cycloxyl-4- (2-hydroxyethoxy) phenyl} propane, 1,1-bis {3-cyclohexyl-4- (2-hydroxyethoxy) phenyl} cyclohexane, bis {(2-hydroxyethoxy) phenyl} diphenylmethane , 9,9-bis {(2-hydroxyethoxy) phenyl} fluorene, 9,9-bis {4- (2-hydroxyethoxy) -3-methylphenyl} fluorene, 1,1-bis {(2-hydroxyethoxy) ) Phenyl} cyclohexane, 1,1-bis {(2-hydroxyethoxy) phenyl} cyclopentane, 4,4'-bis (2-hydroxyethoxy) diphenyl ether, 4,4'-bis (2-hydroxyethoxy) ) -3,3'-Dimethyldiphenyl ether, 1,3-bis [2-{(2-hydroxyethoxy) phenyl} propyl] benzene, 1 , 4-bis [2-{(2-hydroxyethoxy) phenyl} propyl] benzene, 1,4-bis {(2-hydroxyethoxy) phenyl} cyclohexane, 1,3-bis {(2-hydroxyethoxy) phenyl} Cyclohexane, 4,8-bis {(2-hydroxyethoxy) phenyl} tricyclo [5.2.1.02,6] decane, 1,3-bis {(2-hydroxyethoxy) phenyl} -5,7-dimethyl Adamantane, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, 1,4: 3,6-dianhydro-D- Examples thereof include sorbitol (isosorbide), 1,4: 3,6-dianhydro-D-mannitol (isomannide), 1,4: 3,6-dianhydro-L-iditol (isoidide) and the like.

Of these, aromatic bisphenols are preferable, and among them, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4). -Hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-sulfonyl Diphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis {2- (4-hydroxyphenyl) Propyl} benzene and 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene are preferred, especially 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxy). Phenyl) cyclohexane, 4,4'-sulfonyldiphenol, and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene are preferred. Of these, 2,2-bis (4-hydroxyphenyl) propane, which has excellent strength and good durability, is most preferable. Moreover, these may be used individually or in combination of 2 or more types.

The polycarbonate resin used as the component A of the present invention may be a branched polycarbonate resin by using a branching agent in combination with the above dihydroxy compound. Examples of the trifunctional or higher polyfunctional aromatic compound used in such a branched polycarbonate resin include fluoroglusin, fluorogluside, or 4,6-dimethyl-2,4,6-tris (4-hydrokidiphenyl) hepten-2, 2. , 4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Etan, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4-[ 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, trisphenol such as α-dimethylbenzylphenol, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1, Examples thereof include 4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and their acid chlorides, among which 1,1,1-tris (4-hydroxy) Phenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable.

These polycarbonate resins are produced by a reaction means known per se for producing an ordinary aromatic polycarbonate resin, for example, a method of reacting an aromatic dihydroxy component with a carbonate precursor such as phosgene or carbonic acid diester. The basic means for the manufacturing method will be briefly described.

In a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually carried out in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. A catalyst such as a tertiary amine or a quaternary ammonium salt can also be used to promote the reaction. At that time, the reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 5 hours. The transesterification reaction using a carbonic acid diester as a carbonic acid precursor is carried out by a method of distilling the produced alcohol or phenol by stirring a predetermined ratio of aromatic dihydroxy components with the carbonic acid diester while heating in an inert gas atmosphere. .. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed by distilling off the produced alcohols or phenols under reduced pressure from the initial stage. It is also possible to use a catalyst usually used in a transesterification reaction to accelerate the reaction. Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferable.

In the present invention, a terminal terminator is used in the polymerization reaction. The terminal terminator is used for molecular weight regulation, and the obtained polycarbonate resin has excellent thermal stability as compared with the non-terminal-sealed polycarbonate resin. As such a terminal terminator, monofunctional phenols represented by the following general formulas [5] to [7] can be shown.

［式中、Ａは水素原子、炭素数１〜９のアルキル基、アルキルフェニル基（アルキル部分の炭素数は１〜９）、フェニル基、またはフェニルアルキル基（アルキル部分の炭素数１〜９）であり、ｒは１〜５、好ましくは１〜３の整数である］。

[In the formula, A is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkylphenyl group (the number of carbon atoms in the alkyl moiety is 1 to 9), a phenyl group, or a phenylalkyl group (the number of carbon atoms in the alkyl moiety is 1 to 9). And r is an integer of 1-5, preferably 1-3].

［式中、Ｘは−Ｒ−Ｏ−、−Ｒ−ＣＯ−Ｏ−または−Ｒ−Ｏ−ＣＯ−である、ここでＲは単結合または炭素数１〜１０、好ましくは１〜５の二価の脂肪族炭化水素基を示し、ｎは１０〜５０の整数を示す。］

[In the formula, X is -RO-, -R-CO-O- or -RO-CO-, where R is a single bond or 1 to 10 carbon atoms, preferably 1 to 5-2. It indicates a valent aliphatic hydrocarbon group, and n represents an integer of 10 to 50. ]

Specific examples of the monofunctional phenols represented by the general formula [5] include phenol, isopropylphenol, p-tert-butylphenol, p-cresol, p-cumylphenol, 2-phenylphenol, and 4-phenyl. Phenol, isooctylphenol and the like can be mentioned. Further, the monofunctional phenols represented by the above general formulas [6] to [7] are phenols having a long-chain alkyl group or an aliphatic ester group as a substituent, and these are used to end the polycarbonate resin. When sealed, these not only function as a terminal terminator or a molecular weight modifier, but also improve the melt fluidity of the resin, facilitate the molding process, and have the effect of lowering the water absorption rate of the resin, which is preferable. used. The substituted phenols of the above general formula [6] preferably have n of 10 to 30, particularly 10 to 26, and specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, and octadecylphenol. Examples thereof include eicosylphenol, docosylphenol, and triacylphenol. Further, as the substituted phenols of the above general formula [7], a compound in which X is -R-CO-O- and R is a single bond is suitable, and n is 10 to 30, particularly 10 to 26. Is preferable, and specific examples thereof include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eikosyl hydroxybenzoate, docosyl hydroxybenzoate, and triacontyl hydroxybenzoate. Among these monofunctional phenols, monofunctional phenols represented by the above general formula [5] are preferable, alkyl-substituted or phenylalkyl-substituted phenols are more preferable, and p-tert-butylphenol and p are particularly preferable. -Cumylphenol or 2-phenylphenol. It is desirable that the terminal terminator of these monofunctional phenols be introduced at the terminal at least 5 mol%, preferably at least 10 mol% with respect to the total terminal of the obtained polycarbonate resin, and the terminal terminator is used alone. Or a mixture of two or more types may be used.

The polycarbonate resin used as the component A of the present invention may be a polyester carbonate copolymerized with an aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or a derivative thereof, as long as the gist of the present invention is not impaired. Good.

The viscosity average molecular weight of the polycarbonate resin used as the component A of the present invention is preferably in the range of 13,000 to 25,000, more preferably 16,000 to 24,000, and preferably in the range of 18,000 to 23,000. Even more preferable, the range of 19,000 to 22,000 is most preferable. If the molecular weight exceeds 25,000, the melt viscosity may become too high and the moldability may be inferior, and if the molecular weight is less than 13,000, a problem may occur in mechanical strength. The viscosity average molecular weight referred to in the present invention was obtained by first determining the specific viscosity calculated by the following formula from a solution of 0.7 g of polycarbonate resin in 100 ml of methylene chloride using an Ostwald viscometer. The specific viscosity is inserted by the following formula to obtain the viscosity average molecular weight M.

Specific viscosity (η _SP ) = (t-t ₀ ) / t ₀
[T ₀ is the number of seconds for methylene chloride to fall, t is the number of seconds for the sample solution to fall]
η _SP / c = [η] + 0.45 × ^{[η] 2} c (however, [η] is the ultimate viscosity)
[Η] = 1.23 × 10 ^-4 M ^0.83
c = 0.7

The total amount of Cl (chlorine) in the polycarbonate resin used as the component A of the present invention is preferably 0 to 200 ppm, more preferably 0 to 150 ppm. If the total amount of Cl in the polycarbonate resin exceeds 200 ppm, the hue and thermal stability may deteriorate.

<Component B: Polycarbonate-polydiorganosiloxane copolymer resin>
The polycarbonate-polydiorganosiloxane copolymer resin used as the B component of the present invention is a polycarbonate composed of a polycarbonate block represented by the following general formula [1] and a polydiorganosiloxane block represented by the following general formula [3]. -Preferably a polycarbonate siloxane copolymer resin.

［上記一般式〔１〕において、Ｒ^１及びＲ^２は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１８のアルキル基、炭素原子数１〜１８のアルコキシ基、炭素原子数６〜２０のシクロアルキル基、炭素原子数６〜２０のシクロアルコキシ基、炭素原子数２〜１０のアルケニル基、炭素原子数６〜１４のアリール基、炭素原子数６〜１４のアリールオキシ基、炭素原子数７〜２０のアラルキル基、炭素原子数７〜２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、それぞれ複数ある場合はそれらは同一でも異なっていても良く、ａ及びｂは夫々１〜４の整数であり、Ｗは単結合もしくは下記一般式〔２〕で表される基からなる群より選ばれる少なくとも一つの基である。

[In the above general formula [1], R ¹ and R ² are independently hydrogen atom, halogen atom, alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, and 6 to 6 carbon atoms, respectively. 20 cycloalkyl groups, 6 to 20 carbon atoms cycloalkoxy groups, 2 to 10 carbon atoms alkenyl groups, 6 to 14 carbon atoms aryl groups, 6 to 14 carbon atoms aryloxy groups, carbon atoms Represents a group selected from the group consisting of an aralkyl group having a number of 7 to 20, an aralkyloxy group having a carbon atom number of 7 to 20, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. A and b are each an integer of 1 to 4, and W is at least one group selected from the group consisting of a single bond or a group represented by the following general formula [2].

（上記一般式〔２〕においてＲ^１１，Ｒ^１２，Ｒ^１３，Ｒ^１４，Ｒ^１５，Ｒ^１６，Ｒ^１７及びＲ^１８は夫々独立して水素原子、炭素原子数１〜１８のアルキル基、炭素原子数６〜１４のアリール基及び炭素原子数７〜２０のアラルキル基からなる群から選ばれる基を表し、Ｒ^１９及びＲ^２０は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１８のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数６〜２０のシクロアルキル基、炭素原子数６〜２０のシクロアルコキシ基、炭素原子数２〜１０のアルケニル基、炭素原子数６〜１４のアリール基、炭素原子数６〜１０のアリールオキシ基、炭素原子数７〜２０のアラルキル基、炭素原子数７〜２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、複数ある場合はそれらは同一でも異なっていても良く、ｃは１〜１０の整数、ｄは４〜７の整数である。）］

(In the above general formula [2], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are independently hydrogen atoms, alkyl groups having 1 to 18 carbon atoms, and carbon. Represents a group selected from the group consisting of an aryl group having 6 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ are independent hydrogen atoms, halogen atoms, and carbon atoms 1 to 18 respectively. Aryl group, alkoxy group with 1 to 10 carbon atoms, cycloalkyl group with 6 to 20 carbon atoms, cycloalkoxy group with 6 to 20 carbon atoms, alkenyl group with 2 to 10 carbon atoms, 6 carbon atoms From an aryl group of ~ 14, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group. Represents a group selected from the group, and if there are a plurality of groups, they may be the same or different, and c is an integer of 1 to 10 and d is an integer of 4 to 7.)]

（上記一般式〔３〕において、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、各々独立に水素原子、炭素数１〜１２のアルキル基又は炭素数６〜１２の置換若しくは無置換のアリール基であり、Ｒ^９及びＲ^１０は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基であり、ｅ及びｆは夫々１〜４の整数であり、ｐは自然数であり、ｑは０又は自然数であり、ｐ＋ｑは４以上１５０以下の自然数である。Ｘは炭素数２〜８の二価脂肪族基である。）

(In the above general formula [3], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently substituted with a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or 6 to 12 carbon atoms, respectively. Alternatively, they are unsubstituted aryl groups, and R ⁹ and R ¹⁰ are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 10 carbon atoms, and e and f. Is an integer of 1 to 4, p is a natural number, q is 0 or a natural number, p + q is a natural number of 4 or more and 150 or less. X is a divalent aliphatic group having 2 to 8 carbon atoms. .)

Examples of the divalent phenol (I) for deriving the carbonate constituent unit represented by the above general formula [1] include 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, and 1,1-bis ( 4-Hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methyl) Phenyl) propane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3'-biphenyl) propane, 2,2-bis ( 4-Hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4) -Hydroxyphenyl) octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-) Cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene, 9, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 4,4'-dihydroxydiphenyle -Tel, 4,4'-dihydroxy-3,3'-dimethyldiphenylester, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfide, 2, 2'-Dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide, 2,2' -Diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenylsulfide, 1,3-bis { 2- (4-Hydroxyphenyl) propyl} benzene, 1,4-bis {2- (4-hydroxyphenyl) propyl} Benzene, 1,4-bis (4-hydroxyphenyl) cyclohexane, 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6 ] Decane, 4,4'-(1,3-adamantaneyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane and the like.

Among them, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl- 4,4'-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, and 1,4-bis {2- (4-Hydroxyphenyl) propyl} benzene is preferred, especially 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-sulfonyldi. Phenol and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene are preferred. Of these, 2,2-bis (4-hydroxyphenyl) propane, which has excellent strength and good durability, is most preferable. Moreover, these may be used individually or in combination of 2 or more types.

In the carbonate constituent unit represented by the above general formula [3], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently hydrogen atoms, alkyl groups having 1 to 12 carbon atoms or carbons, respectively. It is a substituted or unsubstituted aryl group of number 6 to 12, preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and is a hydrogen atom or carbon. Alkyl groups or phenyl groups of numbers 1 to 6 are particularly preferable. R ⁹ and R ¹⁰ are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 10 carbon atoms, preferably hydrogen atoms and 1 to 10 carbon atoms. It is an alkyl group, and an alkyl group having a hydrogen atom and 1 to 4 carbon atoms is particularly preferable. As the dihydroxyaryl-terminated polydiorganosiloxane (II) for deriving the carbonate constituent unit represented by the above formula [3], for example, a compound represented by the following general formula (I) is preferably used.

P representing the degree of polymerization of diorganosiloxane is a natural number, q is 0 or a natural number, p + q is a natural number of 4 or more and 150 or less, preferably 4 to 120, more preferably 30 to 120, and further 30 to 100. It is preferable, and 30 to 60 is most preferable.

The content of the polydiorganosiloxane block represented by the following general formula [4] contained in the above general formula [3] of the present invention is preferably 1.0% by weight or more based on the total weight of the polycarbonate resin composition. , 1.0% by weight to 10.0% by weight, more preferably 2.0% by weight to 10.0% by weight, and particularly preferably 3.0% by weight to 8.0% by weight. Most preferably, it is 4.0% by weight to 8.0% by weight. If the content of the polydiorganosiloxane component is less than 1.0% by weight, the weather resistance (hue and phosphorescence) may not be sufficient. The degree of polymerization of diorganosiloxane and the content of polydiorganosiloxane components ^{can be calculated by 1} H-NMR measurement.

（上記一般式〔４〕において、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、各々独立に水素原子、炭素数１〜１２のアルキル基又は炭素数６〜１２の置換若しくは無置換のアリール基であり、ｐは自然数であり、ｑは０又は自然数であり、ｐ＋ｑは４以上１５０以下の自然数である。）

(In the above general formula [4], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently substituted with a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or 6 to 12 carbon atoms, respectively. Alternatively, it is an unsubstituted aryl group, p is a natural number, q is 0 or a natural number, and p + q is a natural number of 4 or more and 150 or less.)

Next, a method for producing the above-mentioned preferable polycarbonate-polydiorganosiloxane copolymer resin will be described below. By the reaction of dihydric phenol (I) with a chloroformate-forming compound such as chloroformate of phosgene or dihydric phenol (I) in a mixed solution of an organic solvent insoluble in water and an alkaline aqueous solution in advance, A mixed solution of a chloroformate compound containing a chloroformate of the dihydric phenol (I) and / or a carbonate oligomer of the dihydric phenol (I) having a terminal chloroformate group is prepared. Phosgene is suitable as the chloroformate-forming compound.

In producing the chloroformate compound from the dihydric phenol (I), the entire amount of the divalent phenol (I) that induces the carbonate constituent unit represented by the above general formula [1] can be used as the chloroformate compound at a time. Well, or a part of it may be added as a reaction raw material to the interfacial polycondensation reaction in the subsequent stage as a post-addition monomer. The post-added monomer is added to allow the polycondensation reaction in the subsequent stage to proceed rapidly, and it is not necessary to add it when it is not necessary. The method of this chloroformate compound production reaction is not particularly limited, but a method of carrying out the reaction in the presence of an acid binder in a solvent is usually preferable. Further, if desired, a small amount of an antioxidant such as sodium sulfite and hydrosulfide may be added, and it is preferable to add the antioxidant. The ratio of the chloroformate-forming compound used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. When phosgene, which is a suitable chloroformate-forming compound, is used, a method of blowing gasified phosgene into the reaction system can be preferably adopted.

Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Is used.

Similarly to the above, the ratio of the acid binder used may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, per mol of divalent phenol (I) used to form the chloroformate compound of dihydric phenol (I) (usually 1 mol corresponds to 2 equivalents), 2 equivalents or slightly excess. It is preferable to use an acid binder.

As the solvent, a solvent inert to various reactions such as those used in the production of known polycarbonate may be used alone or as a mixed solvent. Typical examples include hydrocarbon solvents such as xylene and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. In particular, a halogenated hydrocarbon solvent such as methylene chloride is preferably used.

The pressure in the reaction for producing the chloroformate compound is not particularly limited and may be normal pressure, pressurization, or reduced pressure, but it is usually advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of -20 to 50 ° C., and in many cases, heat is generated during the reaction, so water cooling or ice cooling is desirable. The reaction time depends on other conditions and cannot be unconditionally defined, but is usually 0.2 to 10 hours.

As the pH range in the reaction for producing the chloroformate compound, known interfacial reaction conditions can be used, and the pH is usually adjusted to 10 or more.

In the production of the polycarbonate-polydiorganosiloxane copolymer resin used as the B component of the present invention, the divalent phenol (I) having a chloroformate of the dihydric phenol (I) and a terminal chloroformate group is thus produced. After preparing a mixed solution of the chloroformate compound containing the carbonate oligomer of the above, dihydroxyaryl-terminated polydiorganosiloxane (II) for deriving the carbonate structural unit represented by the general formula [3] while stirring the mixed solution is obtained. The dihydroxyaryl-terminated polydiorganosiloxane (II) and the chlorohomate compound were added at a rate of 0.01 mol / min or less per 1 mol of the amount of dihydric phenol (I) charged in preparing the mixed solution. By interfacial polycondensation, a polycarbonate-polydiorganosiloxane copolymer resin is obtained.

The polycarbonate-polydiorganosiloxane copolymer resin used as the B component of the present invention can be a branched polycarbonate-polydiorganosiloxane copolymer resin by using a branching agent in combination with a divalent phenolic compound. Examples of the trifunctional or higher polyfunctional aromatic compound used in such a branched polycarbonate resin include fluoroglusin, fluorogluside, or 4,6-dimethyl-2,4,6-tris (4-hydrokidiphenyl) hepten-2, 2. , 4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Etan, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4-[ 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, trisphenol such as α-dimethylbenzylphenol, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1, Examples thereof include 4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and their acid chlorides, among which 1,1,1-tris (4-hydroxy) Phenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable.

The method for producing such a branched polycarbonate-polydiorganosiloxane copolymer resin is interfacial polycondensation after the completion of the production reaction, even if the branching agent is contained in the mixed solution during the production reaction of the chloroformate compound. A method in which a branching agent is added during the reaction may be used. The proportion of the carbonate constituent units derived from the branching agent is preferably 0.005 to 1.5 mol%, more preferably 0.01 to 1.2 mol%, based on the total amount of the carbonate constituent units constituting the copolymer resin. Particularly preferably, it is 0.05 to 1.0 mol%. The amount of the branched structure ^{can be calculated by 1 1} H-NMR measurement.

The pressure in the system in the polycondensation reaction can be reduced pressure, normal pressure, or pressurization, but usually, normal pressure or the self-pressure of the reaction system can be preferably used. The reaction temperature is selected from the range of -20 to 50 ° C., and in many cases, heat is generated during polymerization, so it is desirable to cool with water or ice. The reaction time varies depending on other conditions such as the reaction temperature and cannot be unconditionally specified, but is usually 0.5 to 10 hours. In some cases, the obtained polycarbonate-polydiorganosiloxane copolymer resin is appropriately subjected to physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, cross-linking treatment, partial decomposition treatment, etc.) to reduce the desired amount. It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity [η _{SP / c].} The obtained reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin having a desired purity (purification degree) by subjecting various post-treatments such as a known separation and purification method.

The viscosity average molecular weight of the polycarbonate-polydiorganosiloxane copolymer resin used as the B component of the present invention is preferably in the range of 13,000 to 25,000, more preferably 13,000 to 23,000, and 18,000 to 22, The range of 000 is more preferable, and the range of 19,000 to 21,000 is most preferable. If the molecular weight exceeds 25,000, the melt viscosity may become too high and the moldability may be inferior, and if the molecular weight is less than 13,000, a problem may occur in mechanical strength.

The viscosity average molecular weight of the polycarbonate-polydiorganosiloxane copolymer resin used as the B component of the present invention is calculated as follows. First, the specific viscosity (η _SP ) calculated by the following formula was determined from a solution prepared by dissolving 0.7 g of a polycarbonate-polydiorganosiloxane copolymer resin in 100 ml of methylene chloride at 20 ° C. using an Ostwald viscometer.
Specific viscosity (η _SP ) = (t-t ⁰ ) / t ⁰
[T ⁰ is the number of seconds for methylene chloride to fall, t is the number of seconds for the sample solution to fall]
From the obtained specific viscosity (η _SP ), the viscosity average molecular weight Mv is calculated by the following formula.
η _SP / c = [η] + 0.45 × ^{[η] 2 c} (however, [η] is the ultimate viscosity)
[Η] = 1.23 × 10 ^-4 Mv ^0.83
c = 0.7

The content of the B component is adjusted so that the content of the polydiorganosiloxane block represented by the above general formula [4] contained in the B component is within the above-mentioned preferable range, but 10 out of 100 parts by weight of the resin component. It is preferably ~ 90 parts by weight, more preferably 20 to 90 parts by weight, further preferably 30 to 90 parts by weight, and particularly preferably 40 to 90 parts by weight.

(C component; phosphorescent material)
In the present invention, the phosphorescent material used as the C component is not particularly limited as long as it is a phosphorescent material usually used as a phosphorescent material of a synthetic resin. For example, sulfide-based phosphorescent materials such as CaS: Bi, CaSrS: Bi, ZnCdS: Cu, zinc sulfide-based phosphorescent materials such as ZnS: Cu, silicic acid-based phosphorescent materials such as _{Sr 2} MgSi ₂ O _{7: Eu, Dy, etc.} MalaOb: X (M is one or more metal elements selected from calcium, strontium and barium. A and b are natural numbers. X is an activator and is an activator, europium, lantern, cerium, placeodium, neodium, samarium, gadrinium, terbium. , Dysprosium, formium, erbium, strontium, itterbium, ruthenium, manganese, tin, bismuth. The content of X is usually 10 mol% or less, for example, 10 mol% or less with respect to the metal element represented by M. Aluminic acid-based compounds represented by 0.001 to 10 mol%) and the like can be mentioned. From the viewpoint of hydrolyzability and afterglow properties, it is preferably an aluminate-based compound, and more preferably, a strontium aluminate-based compound using strontium as a metal element, europium as an activator, and dysprosium.

Further, the phosphorescent material preferably has a D50 particle size of 1 to 100 μm. More preferably, it is in the range of 5 to 50 μm. The D50 particle size indicates a diameter in which the large side and the small side have equal amounts when the powder is divided into two from a certain particle size. If the D50 particle size is less than 1 μm, it is difficult to manufacture, and it is not practical and difficult to obtain, which is not preferable. On the other hand, if it exceeds 100 μm, the optical characteristics and appearance may be impaired. Further, two or more types of phosphorescent materials having different average particle diameters, particle size distributions and types may be used in combination, and those having a non-uniform particle size distribution and two or more particle size distributions may be used alone or in combination. Can also be used.

As the absorption wavelength of the phosphorescent material, it is desirable that the absorption maximum value is in the range of 300 nm to 500 nm. This is because the wavelength of light that is easy for the human eye to catch is around 550 nm, and as a characteristic of the phosphorescent material, the radiation maximum always shifts to the long wavelength side rather than the absorption maximum. This is because it becomes extremely difficult to see. Further, the phosphorescent material preferably has one end (maximum emission value) on the long wavelength side of 430 nm to 680 nm in the wavelength region of the emitted light.

The content of the C component is 1 to 35 parts by weight, preferably 5 to 20 parts by weight, and more preferably 8 to 10 parts by weight with respect to 100 parts by weight of the resin component composed of the A component and the B component. is there. If the content is less than 1 part by weight, the light emission time becomes extremely short. On the other hand, if it exceeds 35 parts by weight, the extrudability is extremely deteriorated.

<D component: light diffusing agent>
The light diffusing agent used as the D component of the present invention may be either organic fine particles typified by polymer fine particles or inorganic fine particles. Typical examples of the polymer fine particles are organic crosslinked particles obtained by polymerizing a non-crosslinkable monomer and a crosslinkable monomer. Further, copolymerizable monomers other than such monomers can also be used. In addition, examples of other organic crosslinked particles include silicone crosslinked particles typified by polyorganosylsesquioxane. Among them, polymer fine particles are preferable, and organic crosslinked particles can be particularly preferably used. Examples of the monomer used as the non-crosslinkable monomer in such organic crosslinked particles include non-crosslinkable vinyl-based monomers such as acrylic monomer, styrene-based monomer, and acrylonitrile-based monomer, and olefin-based monomer. As the acrylic monomer, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate and the like are used alone or mixed. It is possible to use it. Of these, methyl methacrylate is particularly preferable. Further, as the styrene-based monomer, alkyl styrene such as styrene, α-methyl styrene, methyl styrene (vinyl toluene), and ethyl styrene, and halogenated styrene such as bromoized styrene can be used, and styrene is particularly preferable. .. As the acrylonitrile-based monomer, acrylonitrile and methacrylonitrile can be used. Further, as the olefin-based monomer, ethylene, various norbornene-type compounds and the like can be used. Further, as other copolymerizable monomers, glycidyl methacrylate, N-methylmaleimide, maleic anhydride and the like can be exemplified. The organic crosslinked particles of the present invention can also have units such as N-methylglutarimide as a result. On the other hand, examples of the crosslinkable monomer for such a non-crosslinkable vinyl-based monomer include divinylbenzene, allyl methacrylate, triallyl cyanurate, triallyl isocyanate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and propylene glycol. (Meta) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane (meth) acrylate, pentaerythritol tetra (meth) acrylate, bisphenol A di (meth) acrylate, dicyclopentanyl di (meth) acrylate , Dicyclopentenyldi (meth) acrylate, N-methylol (meth) acrylamide and the like.

The average particle size of the light diffusing agent used as the D component of the present invention is preferably 1 to 20 μm, more preferably 1 to 10 μm, still more preferably 1 to 5 μm. If the average particle size is less than 1 μm or more than 20 μm, the light diffusivity may be insufficient. The average particle size may be obtained by any of the laser diffraction / scattering method, the coal tar method, and the centrifugal sedimentation method, and is represented by a 50% value (D50) of the integrated distribution of the particle size. The particle size distribution may be single or plural. That is, it is possible to combine two or more kinds of light diffusing agents having different average particle diameters. However, a more preferred light diffusing agent has a narrow particle size distribution. It is more preferable to have a distribution in which 70% by weight or more of the particles are contained in the range of 2 μm before and after the average particle size. From the viewpoint of light diffusivity, the shape of the light diffusing agent is preferably a shape close to a spherical shape, and more preferably a shape close to a true spherical shape. Such a sphere includes an ellipsoidal sphere. The refractive index of the light diffusing agent used as the D component of the present invention is usually preferably in the range of 1.30 to 1.80, more preferably 1.33 to 1.70, and further preferably 1.35 to 1. It is in the range of 65. These exhibit a sufficient light diffusing function when blended in the resin composition.

The content of the D component is 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the resin component composed of the A component and the B component. It is a part by weight. If the D component is less than 0.05 parts by weight, the light emitted from the phosphorescent material is not sufficiently diffused, resulting in uneven emission intensity. Therefore, the emission intensity is not sufficient as a whole and the phosphorescence is inferior. If it exceeds 10 parts by weight, a large amount of gas is generated, which leads to poor appearance and mold contamination.

<Component E: UV absorber>
The polycarbonate resin composition of the present invention contains an ultraviolet absorber as an E component. Examples of the ultraviolet absorber include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide, benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, ogizanylide compounds, and malonic acid ester compounds. Examples thereof include organic ultraviolet absorbers such as hindered amine compounds and oxalic acid anilide compounds. Among these, an organic ultraviolet absorber is preferable, and a benzotriazole-based compound (a compound having a benzotriazole structure) is more preferable. Specific examples of benzotriazole compounds include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- [2'-hydroxy-3', 5'-bis (α, α-dimethyl). Benzyl) phenyl] -benzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butyl-phenyl) -benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5 '-Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2'-hydroxy- 3', 5'-di-tert-amyl) -benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3) , 3-Tetramethylbutyl) -6- (2N-benzotriazole-2-yl) phenol] and the like. Among these, compounds having a molecular weight of less than 500 are preferable, and examples of such benzotriazole-based compounds include "Seesorb 701" and "Seesorb 703" manufactured by Cipro Kasei Co., Ltd., and "Chemisorb 79" manufactured by Chemipro Kasei Co., Ltd. Examples include "Chinubin 234" and "Chinubin 350" manufactured by Ciba Specialty Chemicals Co., Ltd.

The molecular weight of the E component is preferably less than 500. When the molecular weight of the ultraviolet absorber is 500 or more, it is difficult to transfer to the surface of the molded product, and the weather resistance (hue and phosphorescence) may not be sufficient.

The content of the E component is 0.01 to 1 part by weight, preferably 0.2 to 1 part by weight, and more preferably 0.2, based on 100 parts by weight of the resin component composed of the A component and the B component. ~ 0.6 parts by weight. If the content is less than 0.01 parts by weight, sufficient weather resistance (hue and phosphorescence) will not be exhibited, and if it exceeds 1 part by weight, a large amount of gas will be generated during molding, resulting in poor appearance and mold contamination. And so on. The ultraviolet absorber may contain one type or two or more types in any combination and ratio.

(Other additives)
In order to improve the thermal stability, flame retardancy, and design of the polycarbonate resin composition of the present invention, the additives used for these improvements are advantageously used. Hereinafter, these additives will be specifically described.

(I) Heat Stabilizer Various known stabilizers can be blended in the polycarbonate resin composition of the present invention.
Examples of the stabilizer include a phosphorus-based stabilizer and a hindered phenol-based antioxidant.

(I) Phosphorus-based stabilizer The resin composition of the present invention preferably contains a phosphorus-based stabilizer to the extent that hydrolyzability is not promoted. Such phosphorus-based stabilizers improve thermal stability during manufacturing or molding, and improve mechanical properties, hue, and molding stability. Examples of phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid and esters thereof, and tertiary phosphine. Specifically, examples of the phosphite compound include triphenylphosphite, tris (nonylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, and dioctylmonophenyl. Phenylphosphite, diisopropylmonophenylphosphenyl, monobutyldiphenylphosphenyl, monodecyldiphenylphosphite, monooctyldiphenylphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, tris ( Diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2, 6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl) -4-Methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis (nonylphenyl) penta Examples thereof include erythritol diphosphite and dicyclohexylpentaerythritol diphosphite. Further, as another phosphite compound, a compound which reacts with divalent phenols and has a cyclic structure can also be used. For example, 2,2'-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2'-methylenebis (4,6-di-tert-). Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2'-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite , 2,2'-Etilidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and the like. Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, and so on. Examples thereof include diisopropyl phosphate, preferably triphenyl phosphate and trimethyl phosphate.

Phosphonite compounds include tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite and tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite , Tetrakiss (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di) -N-Butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) Examples thereof include -3-phenyl-phenylphosphonite, tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite are preferable, and tetrakis (2, 4-Di-tert-butylphenyl) -biphenylenediphosphonite and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite are more preferred. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which the alkyl group is substituted by 2 or more. Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. Tertiary phosphines include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, and tri-p-tolyl. Examples include phosphine, triphenylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine. The phosphorus-based stabilizer can be used not only by one type but also by mixing two or more types. Among the phosphorus-based stabilizers, it is preferable that an alkyl phosphate compound typified by trimethyl phosphate is blended. It is also a preferred embodiment to use such an alkyl phosphate compound in combination with a phosphite compound and / or a phosphonite compound.

(Ii) Hindered Phenol Stabilizer The resin composition of the present invention may be further blended with a hindered phenol stabilizer. Such a formulation has an effect of suppressing deterioration of hue during molding processing and deterioration of hue during long-term use, for example. Examples of the hindered phenol-based stabilizer include α-tocopherol, butylhydroxytoluene, cinapyl alcohol, vitamin E, n-octadecyl-β- (4'-hydroxy-3', 5'-di-tert-butylfel). Propionate, 2-tert-butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N) , N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'- Methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2, 2'-dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4- Methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-) Methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3) -Tert-Butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1 , 1,-Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-thiobis (3-Methyl-6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4 , 4'-di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butylpheno) , 2,2-thiodiethylenebis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-) Hydroxy-3', 5'-di-tert-butylanilino) -1,3,5-triazine, N, N'-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide) , N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-) Butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl- 4-Hydroxyphenyl) isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6- Dimethylbenzyl) isocyanurate, 1,3,5-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, and tetrakis [methylene-3- (3', 3',). 5'-di-tert-butyl-4-hydroxyphenyl) propionate] methane and the like are exemplified. All of these are readily available. The above hindered phenolic stabilizers can be used alone or in combination of two or more. The blending amounts of the phosphorus-based stabilizer and the hindered phenol-based stabilizer are preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.5 part by weight, still more preferably, with respect to 100 parts by weight of the resin component. Is 0.005 to 0.3 parts by weight.

(Iii) Heat Stabilizers Other Than The Phosphorus Stabilizers and Hindered Phenol Stabilizers Other than the Phosphorus Stabilizers and Hindered Phenol Stabilizers can be added to the resin composition of the present invention. As such other heat stabilizers, for example, lactone-based stabilizers typified by the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene are preferably exemplified. Will be done. Details of such stabilizers are described in JP-A-7-233160. Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and the compound can be used. Further, stabilizers obtained by mixing the compound with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the above-mentioned company is preferably exemplified. The blending amount of the lactone-based stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, based on 100 parts by weight of the resin component. Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Illustrated. The blending amount of the sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, based on 100 parts by weight of the resin component. An epoxy compound can be added to the resin composition of the present invention, if necessary. Such an epoxy compound is blended for the purpose of suppressing mold corrosion, and basically all compounds having an epoxy functional group can be applied. Specific examples of preferable epoxy compounds include 3,4-epoxycyclohexylmethyl-3', 4-'-epoxycyclohexylcarboxylate, and 1,2-epoxy-4-butanol of 2,2-bis (hydroxymethyl) -1-butanol. Examples thereof include a (2-oxylanyl) cyclosexane adduct, a copolymer of methyl methacrylate and glycidyl methacrylate, a copolymer of styrene and glycidyl methacrylate, and the like. The amount of the epoxy compound added is preferably 0.003 to 0.2 parts by weight, more preferably 0.004 to 0.15 parts by weight, still more preferably 0.005, based on 100 parts by weight of the resin component. ~ 0.1 parts by weight.

(II) Flame Retardant The resin composition of the present invention may contain various compounds known as flame retardants for polycarbonate resins. The formulation of such a compound brings about an improvement in flame retardancy, but other than that, based on the properties of each compound, for example, an improvement in antistatic property, fluidity, rigidity, and thermal stability is brought about. Examples of such flame retardants include (i) organometal salt flame retardants (for example, organosulfonic acid alkali (earth) metal salts, organoboric acid metal salt flame retardants, and organophosphorus metal salt flame retardants), ( ii) Organophosphorus flame retardants (for example, organic group-containing monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds), (iii) Silicone flame retardants consisting of silicone compounds. , (Iv) fibrillated PTFE, among which organometal salt flame retardants and organophosphorus flame retardants are preferred.

(I) Organic metal salt-based flame retardant The organic metal salt compound is an alkaline (earth) metal salt of an organic acid having 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms, preferably an alkaline (earth) metal salt of an organic sulfonic acid. Is preferable. This organic sulfonic acid alkali (earth) metal salt includes a fluorine-substituted alkyl sulfone such as a metal salt of a perfluoroalkyl sulfonic acid having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms and an alkali metal or an alkaline earth metal. Includes metal salts of acids, as well as metal salts of aromatic sulfonic acids with 7-50, preferably 7-40 carbon atoms and alkali metals or alkaline earth metals. Examples of the alkali metal constituting the metal salt include lithium, sodium, potassium, rubidium and cesium, and examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium and barium. More preferably, it is an alkali metal. Among such alkali metals, rubidium and cesium having a larger ionic radius are preferable when the demand for transparency is higher, but they are not versatile and difficult to purify, resulting in cost. It may be disadvantageous. On the other hand, metals with smaller ionic radii such as lithium and sodium may be disadvantageous in terms of flame retardancy. In consideration of these, the alkali metal in the sulfonic acid alkali metal salt can be used properly, but in all respects, the potassium sulfonic acid salt having an excellent balance of characteristics is the most suitable. Such a potassium salt and a sulfonic acid alkali metal salt composed of another alkali metal can also be used in combination.

Specific examples of the alkali metal salt of perfluoroalkyl sulfonic acid include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, and perfluoro. Sodium butane sulfonate, sodium perfluorooctane sulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutane sulfonate, lithium perfluoroheptane sulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutane sulfonate, perfluorooctane sulfonic acid Examples thereof include cesium, cesium perfluorohexanesulfonate, rubidium perfluorobutanesulfonate, and rubidium perfluorohexanesulfonate, and these can be used alone or in combination of two or more. Here, the number of carbon atoms of the perfluoroalkyl group is preferably in the range of 1 to 18, more preferably in the range of 1 to 10, and even more preferably in the range of 1 to 8. Of these, potassium perfluorobutane sulfonate is particularly preferable. ^{Fluoride ions (F −} ) are usually mixed in the alkali (earth) metal salt of perfluoroalkyl sulfonic acid composed of alkali metal. Since the presence of such fluoride ions can be a factor for lowering the flame retardancy, it is preferable to reduce it as much as possible. The ratio of such fluoride ions can be measured by an ion chromatography method. The fluoride ion content is preferably 100 ppm or less, more preferably 40 ppm or less, and particularly preferably 10 ppm or less. Further, it is preferable that the production efficiency is 0.2 ppm or more. The perfluoroalkylsulfonic acid alkali (earth) metal salt having a reduced amount of fluoride ion is contained in a raw material for producing a fluorine-containing organic metal salt using a known production method. A method of reducing the amount of fluoride ions, a method of removing hydrogen fluoride obtained by the reaction by gas generated during the reaction or by heating, and a purification method of recrystallizing and reprecipitating a fluorine-containing organic metal salt for production. It can be produced by a method of reducing the amount of fluoride ions or the like using. In particular, organic metal salt-based flame retardants are relatively soluble in water, so ion-exchanged water, especially water satisfying an electrical resistance value of 18 MΩ · cm or more, that is, an electrical conductivity of about 0.55 μS / cm or less is used. It is preferable to carry out the production by a step of melting at a temperature higher than normal temperature, washing, and then cooling and recrystallization. Specific examples of the aromatic sulfonic acid alkali (earth) metal salt include, for example, diphenylsulfide-4,4'-disodium disulfonate, diphenylsulfide-4,4'-dipotassium disulfonate, potassium 5-sulfoisophthalate, and the like. Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, poly (2,6-dimethylphenylene oxide) polysodium polysulfonate , Poly (1,3-phenylene oxide) poly sulfonate polysodium, poly (1,4-phenylene oxide) poly sulfonate polysodium, poly (2,6-diphenylphenylene oxide) poly sulfonate polypotassium, poly (2-fluoro-) 6-Butylphenylene oxide) Lithium polysulfonate, potassium benzenesulfonate sulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, dipotassium naphthalene-2,6-disulfonate, biphenyl -3,3'-Calcium disulfonate, sodium diphenylsulfon-3-sulfonate, potassium diphenylsulfon-3-sulfonate, diphenylsulfon-3,3'-dipotassium disulfonate, diphenylsulfon-3,4'-disulfonic acid Dipotassium, α, α, α-sodium trifluoroacetophenone-4-sulfonate, dipotassium benzophenone-3,3′-disulfonate, disodium thiophene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate, Calcium thiophene-2,5-disulfonate, sodium benzothiophene sulfonate, potassium diphenylsulfoxide-4-sulfonate, formalin condensate of sodium naphthalene sulfonate, formalin condensate of sodium anthracene sulfonate, etc. may be mentioned. it can. Among these aromatic sulfonic acid alkali (earth) metal salts, potassium salts are particularly preferable. Among these aromatic sulfonic acid alkali (earth) metal salts, potassium diphenylsulfone-3-sulfonate and dipotassium diphenylsulfone-3,3'-disulfonate are preferable, and mixtures thereof (the former and the latter) are particularly preferable. The weight ratio of 15/85 to 30/70) is preferable.

As the organic metal salt other than the alkali (earth) metal salt of sulfonic acid, an alkali (earth) metal salt of a sulfate ester and an alkali (earth) metal salt of an aromatic sulfonamide are preferably exemplified. Examples of the alkali (earth) metal salt of the sulfate ester include an alkali (earth) metal salt of the sulfate ester of monovalent and / or polyhydric alcohols, such monovalent and / or polyhydric alcohols. Sulfate esters include methyl sulfate ester, ethyl sulfate ester, lauryl sulfate ester, hexadecyl sulfate ester, polyoxyethylene alkylphenyl ether sulfate ester, pentaerythritol mono, di, tri, tetrasulfate ester, and lauric acid monoglyceride sulfate. Examples thereof include an ester, a sulfate ester of palmitate monoglyceride, and a sulfate ester of stearate monoglyceride. The alkaline (earth) metal salt of these sulfate esters is preferably an alkaline (earth) metal salt of lauryl sulfate ester. Alkali (earth) metal salts of aromatic sulfonamides include, for example, saccharin, N- (p-tolylsulfonyl) -p-toluenesulfoimide, N- (N'-benzylaminocarbonyl) sulfanylimide, and N- ( Examples thereof include alkali (earth) metal salts of phenylcarboxyl) sulfanylimide. The content of the organic metal salt-based flame retardant is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, still more preferably 0.01 to 0, based on 100 parts by weight of the resin component. .3 parts by weight, particularly preferably 0.03 to 0.15 parts by weight.

(Ii) Organophosphorus flame retardant As the organophosphorus flame retardant, an aryl phosphate compound is suitable. This is because such phosphate compounds are generally excellent in hue. Further, since the phosphate compound has a plasticizing effect, it is advantageous in that the molding processability can be improved. As such a phosphate compound, various phosphate compounds conventionally known as flame retardants can be used. The blending amount of the organic phosphorus flame retardant is preferably 0.01 to 20 parts by weight, more preferably 2 to 10 parts by weight, and further preferably 2 to 7 parts by weight with respect to 100 parts by weight of the resin component.

(Iii) Silicone-based flame retardant A silicone compound used as a silicone-based flame retardant improves flame retardancy by a chemical reaction during combustion. As the compound, various compounds conventionally proposed as flame retardants for aromatic polycarbonate resins can be used. The silicone compound imparts a flame-retardant effect to the polycarbonate resin by forming a structure by itself or by combining with a component derived from the resin at the time of combustion, or by a reduction reaction at the time of forming the structure. It is considered. Therefore, it preferably contains a group having high activity in such a reaction, and more specifically, it contains a predetermined amount of at least one group selected from an alkoxy group and a hydrogen (that is, Si—H group). preferable. The content ratio of such groups (alkoxy group, Si—H group) is preferably in the range of 0.1 to 1.2 mol / 100 g, more preferably in the range of 0.12 to 1 mol / 100 g, and 0.15 to 0. The range of 6 mol / 100 g is more preferable. Such a ratio is obtained by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound by the alkaline decomposition method. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group. Generally, the structure of a silicone compound is formed by arbitrarily combining four types of siloxane units shown below. That is, M unit: (CH ₃ ) ₃ SiO _1/2 , H (CH ₃ ) ₂ SiO _1/2 , H ₂ (CH ₃ ) SiO _1/2 , (CH ₃ ) ₂ (CH ₂ = CH) SiO _{1 / 2} , (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 , (CH ₃ ) (C ₆ H ₅ ) (CH ₂ = CH) SiO _1/2, etc. monofunctional siloxane unit, D unit: (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ = CH) SiO, (C ₆ H ₅ ) ₂ SiO, etc. 2 Functional siloxane unit, T unit: (CH ₃ ) SiO _3/2 , (C ₃ H ₇ ) SiO _3/2 , HSiO _3/2 , (CH ₂ = CH) SiO _3/2 , (C ₆ H ₅ ) _{Trifunctional} siloxane unit such as SiO 3/2, Q unit: A tetrafunctional siloxane unit represented by SiO ₂ . Specific examples of the structure of the silicone compound used in the silicone flame retardant include Dn, Tp, MmDn, MmTp, MmQq, MmDnTp, MmDnQq, MmTpQq, MmDnTpQq, DnTp, DnQq and DnTpQq. Among them, the preferable structure of the silicone compound is MmDn, MmTp, MmDnTp, MmDnQq, and the more preferable structure is MmDn or MmDnTp.

Here, the coefficients m, n, p, and q in the formulas are integers of 1 or more representing the degree of polymerization of each siloxane unit, and the total of the coefficients in each formula is the average degree of polymerization of the silicone compound. .. The average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 3 to 80, still more preferably in the range of 3 to 60, and particularly preferably in the range of 4 to 40. The more suitable the range, the better the flame retardancy. Further, as will be described later, the silicone compound containing a predetermined amount of aromatic group is excellent in transparency and hue. As a result, good reflected light can be obtained. When any of m, n, p, and q is a numerical value of 2 or more, the siloxane unit with the coefficient can be two or more types of siloxane units having different hydrogen atoms or organic residues to be bonded. .. The silicone compound may be linear or have a branched structure. The organic residue bonded to the silicon atom is preferably an organic residue having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Specific examples of such organic residues include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, and decyl group, cycloalkyl groups such as cyclohexyl group, and aryl groups such as phenyl group. Also, an aralkyl group such as a trill group can be mentioned. More preferably, it is an alkyl group having 1 to 8 carbon atoms, an alkenyl group or an aryl group. As the alkyl group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group is particularly preferable. Further, the silicone compound used as the silicone flame retardant preferably contains an aryl group. On the other hand, the silane compound and the siloxane compound as the organic surface treatment agent for the titanium dioxide pigment are clearly distinguished from the silicone-based flame retardant in the preferred embodiment in that a preferable effect can be obtained when the mixture does not contain an aryl group. .. The silicone compound used as a silicone-based flame retardant may contain a reactive group in addition to the Si—H group and the alkoxy group, and the reactive group includes, for example, an amino group, a carboxyl group, an epoxy group, and vinyl. Examples include groups, mercapto groups, and methacryloxy groups.

The blending amount of the silicone-based flame retardant is preferably 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and further preferably 1 to 5 parts by weight with respect to 100 parts by weight of the resin component.

(Iv) Polytetrafluoroethylene having the ability to form fibrils (fibrillated PTFE)
The fibrillated PTFE may be fibrillated PTFE alone or a mixed form of fibrillated PTFE, that is, a polytetrafluoroethylene-based mixture composed of fibrillated PTFE particles and an organic polymer. The fibrillated PTFE has an extremely high molecular weight and tends to bond the PTFE to each other to form a fibrous form due to an external action such as a shearing force. Its number average molecular weight ranges from 1.5 million to tens of millions. The lower limit is more preferably 3 million. Such a number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380 ° C. as disclosed in Japanese Patent Application Laid-Open No. 6-145520. That is, in the fibrillated PTFE of the component B, the melt viscosity at 380 ° C. measured by the method described in such publication is in ^{the range of 10 7} to 10 ¹³ poise, preferably in the range of 10 ⁸ to 10 ¹² poise. .. As the PTFE, not only a solid form but also an aqueous dispersion form can be used. It is also possible to use such a fibrillated PTFE mixture in a mixed form with another resin in order to improve the dispersibility in the resin and to obtain better flame retardancy and mechanical properties. Further, as disclosed in Japanese Patent Application Laid-Open No. 6-145520, a structure having such a fibrillated PTFE as a core and a low molecular weight polytetrafluoroethylene as a shell is also preferably used. Examples of commercially available products of such fibrillated PTFE include Teflon (registered trademark) 6J of Mitsui-DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500 and F-201L of Daikin Chemical Industry Co., Ltd. Examples of the fibrillated PTFE in the mixed form include (1) a method of mixing an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer and co-precipitating to obtain a coaggregating mixture (Japanese Patent Laid-Open No. 60-258263). (A method described in Japanese Patent Application Laid-Open No. 63-154744, etc.), (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (Japanese Patent Laid-Open No. 4-272957). The method described), (3) A method of uniformly mixing an aqueous dispersion of fibrillated PTFE and an organic polymer particle solution and simultaneously removing each medium from such a mixture (Japanese Patent Laid-Open No. 06-220210, Japanese Patent Application Laid-Open No. 06-220210). 08-188653, etc.), (4) A method for polymerizing a monomer that forms an organic polymer in an aqueous dispersion of fibrillated PTFE (Japanese Patent Laid-Open No. 9-95583). Method) and (5) A method in which an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, and then a vinyl-based monomer is further polymerized in the mixed dispersion to obtain a mixture (Japanese Patent Laid-Open No. 11-). The one obtained by the method described in Japanese Patent Application Laid-Open No. 29679 etc.) can be used. Commercially available products of these mixed forms of fibrillated PTFE include Mitsubishi Rayon Co., Ltd.'s "Metabrene A3000" (trade name), "Metabren A3700" (trade name), and "Metabren A3800" (trade name). Examples thereof include the A series, SN3300B7 (trade name) manufactured by Shine Composer, and "BLENDEX B449" (trade name) manufactured by GE Specialty Chemicals.

The proportion of fibrillated PTFE in the mixed form is preferably 1% to 95% by weight, more preferably 10% to 90% by weight, 20% by weight, based on 100% by weight of the mixture. Most preferably from% to 80% by weight.

Good dispersibility of fibrillated PTFE can be achieved when the proportion of fibrillated PTFE in the mixed form is in such a range. The blending amount of the fibrillated PTFE is preferably 0.001 to 0.5 parts by weight, more preferably 0.01 to 0.5 parts by weight, and 0.1 to 0 parts by weight with respect to 100 parts by weight of the resin component. 5 parts by weight is more preferable.

(III) Dyeing Pigment The polycarbonate resin composition of the present invention can further provide a molded product containing various dyeing pigments and exhibiting various designs. The dyes used in the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthracinone dyes, thioxanthone dyes, ferrocyanides such as navy blue, perinone dyes, quinoline dyes, and quinacridone dyes. Examples thereof include dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Further, the polycarbonate resin composition of the present invention can also be blended with a metallic pigment to obtain a better metallic color. Aluminum powder is suitable as the metallic pigment. Further, by blending a fluorescent whitening agent or a fluorescent dye that emits light other than that, it is possible to impart a better design effect that makes the best use of the emitted color.

(IV) Fluorescent whitening agent In the resin composition of the present invention, the fluorescent whitening agent is not particularly limited as long as it is used to improve the color tone of the resin or the like to white or bluish white. For example, stilbene or benz. Examples thereof include imidazole-based, benzoxazole-based, naphthalimide-based, rhodamine-based, coumarin-based, and oxazine-based compounds. Specific examples thereof include CI Fluorescent Fluorescent 219: 1, EASTOBRITE OB-1 manufactured by Eastman Chemical Company, and "Hackor PSR" manufactured by Hakkol Chemical Co., Ltd. Here, the fluorescent whitening agent has an action of absorbing the ultraviolet energy of light rays and radiating this energy to the visible portion. The content of the fluorescent whitening agent is preferably 0.001 to 0.1 parts by weight, more preferably 0.001 to 0.05 parts by weight, based on 100 parts by weight of the resin component. Even if it exceeds 0.1 parts by weight, the effect of improving the color tone of the composition is small.

(V) Antistatic Agent The polycarbonate resin composition of the present invention may be required to have antistatic performance, and in such a case, it is preferable to include an antistatic agent. Examples of such an antioxidant include (1) an aryl sulfonic acid phosphonium salt typified by a dodecylbenzene sulfonic acid phosphonium salt, an organic sulfonic acid phosphonium salt such as an alkyl sulfonic acid phosphonium salt, and a tetrafluoroborate phosphonium salt. Phosphonium borate salt can be mentioned. The content of the phosphonium salt is preferably 5 parts by weight or less based on 100 parts by weight of the resin component, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, still more preferably 1. It is in the range of 5 to 3 parts by weight. Examples of the antistatic agent include (2) lithium organic sulfonate, sodium organic sulfonate, potassium organic sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. Organic sulfonic acid alkali (earth) metal salts such as. As described above, such a metal salt is also used as a flame retardant. More specifically, examples of such a metal salt include a metal salt of dodecylbenzenesulfonic acid and a metal salt of perfluoroalkanesulfonic acid. The content of the organic sulfonic acid alkali (earth) metal salt is preferably 0.5 parts by weight or less, preferably 0.001 to 0.3 parts by weight, and more preferably 0, based on 100 parts by weight of the resin component. .005 to 0.2 parts by weight. Alkali metal salts such as potassium, cesium, and rubidium are particularly suitable.

Examples of the antistatic agent include (3) ammonium salt of alkyl sulfonic acid and ammonium salt of organic sulfonic acid such as ammonium salt of aryl sulfonic acid. It is appropriate that the ammonium salt is 0.05 parts by weight or less based on 100 parts by weight of the resin component. Examples of the antistatic agent include polymers containing a poly (oxyalkylene) glycol component such as (4) polyether ester amide as a component thereof. It is appropriate that the polymer is 5 parts by weight or less based on 100 parts by weight of the resin component.

(VI) Filler The polycarbonate resin composition of the present invention can be blended with various known fillers as reinforcing fillers. As such a filler, various fibrous fillers, plate-like fillers, and granular fillers can be used. Here, the fibrous filler has a fibrous shape (including a rod-like shape, a needle-like shape, or a shape in which the axis extends in a plurality of directions), and the plate-like filler has a plate-like shape (surface). (Including those having irregularities and those having curved plates). The granular filler is a filler having a shape other than these, including an indefinite shape. The fibrous or plate-like shape is often clear from the shape observation of the filler, but for example, the difference from the so-called amorphous shape is that a fibrous or plate-like shape having an aspect ratio of 3 or more can be said to be fibrous or plate-like.

As the plate-shaped filler, glass flakes, talc, mica, kaolin and metal flakes, and a plate-shaped filler in which a different material such as a metal or a metal oxide is surface-coated with respect to these fillers are preferably exemplified. To. The particle size is preferably in the range of 0.1 to 300 μm. Such a particle size refers to a value based on the median diameter (D50) of the particle size distribution measured by the X-ray transmission method, which is one of the liquid phase sedimentation methods, in the region up to about 10 μm, and laser diffraction in the region of 10 to 50 μm. -The value by the median diameter (D50) of the particle size distribution measured by the scattering method, and the value by the vibration type sieving method in the region of 50 to 300 μm. Such a particle size is the particle size in the resin composition. The plate-shaped filler may be surface-treated with various coupling agents such as silane-based, titanate-based, aluminate-based, and zirconate-based, and may be surface-treated, and may be olefin-based resin, styrene-based resin, acrylic-based resin, polyester-based resin. , An epoxy resin, various resins such as a urethane resin, a higher fatty acid ester, or the like, or a granulated product which has been subjected to a focusing treatment or a compression treatment.

The fibrous filler preferably has a fiber diameter in the range of 0.1 to 20 μm. The upper limit of the fiber diameter is more preferably 13 μm, further preferably 10 μm. On the other hand, the lower limit of the fiber diameter is more preferably 1 μm. The fiber diameter here refers to a number average fiber diameter. The number average fiber diameter is obtained by scanning the residue collected after decomposing the molded product in a solvent or the resin with a basic compound, and the ashing residue collected after ashing in a crucible. It is a value calculated from an image observed with an electron microscope. Examples of such fibrous fillers include glass fiber, flat cross-section glass fiber, glass milled fiber, metal fiber, asbestos, rock wool, ceramic fiber, slag fiber, potassium titanate whisker, boron whisker, aluminum borate whisker, and carbonic acid. Fibrous heat resistant typified by fibrous inorganic fillers such as calcium whisker, titanium oxide whisker, wallastnite, zonotrite, parigolskite (atapargite), and sepiolite, and heat resistant organic fibers such as aramid fiber, polyimide fiber and polybenzthiazole fiber. Examples thereof include organic fillers and fibrous fillers in which different materials such as metals and metal oxides are surface-coated with respect to these fillers. Examples of the filler surface-coated with different materials include metal-coated glass fibers, metal-coated glass flakes, titanium oxide-coated glass flakes, and metal-coated carbon fibers. The surface coating method for dissimilar materials is not particularly limited, and for example, various known plating methods (for example, electrolytic plating, electroless plating, hot-dip plating, etc.), vacuum deposition method, ion plating method, and CVD method ( For example, thermal CVD, MOCVD, plasma CVD, etc.), PVD method, sputtering method and the like can be mentioned. Here, the fibrous filler refers to a fibrous filler having an aspect ratio of 3 or more, preferably 5 or more, and more preferably 10 or more. The upper limit of the aspect ratio is about 10,000, preferably 200. The aspect ratio of such a filler is a value in the resin composition. The flat cross-section glass fiber has an average value of the major axis of the fiber section of 10 to 50 μm, preferably 15 to 40 μm, more preferably 20 to 35 μm, and the average value of the ratio of the major axis to the minor axis (major axis / minor axis) is 1. .5-8, preferably 2-6, more preferably 2.5-5 glass fibers. Like the plate-shaped filler, the fibrous filler may be surface-treated with various coupling agents, focused with various resins, or granulated by compression treatment. The content of the filler is preferably 200 parts by weight or less, more preferably 100 parts by weight or less, still more preferably 50 parts by weight or less, and particularly preferably 30 parts by weight or less, based on 100 parts by weight of the resin component.

(VII) Others The polycarbonate resin composition of the present invention may contain other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalytic antifouling agents, photochromic agents and the like. Further, the polycarbonate resin composition of the present invention is excellent in good impact resistance and coating resistance without adding an impact modifier, but when other additives are added, impact is required. A modifier can be added.

The resin composition of the present invention can be pelletized by melt-kneading using an extruder such as a single-screw extruder or a twin-screw extruder. In producing such pellets, the above-mentioned various flame retardants, strengthening fillers and additives can also be blended. The resin composition of the present invention can usually produce various products by injection molding pellets produced as described above. Further, it is also possible to directly convert the resin melt-kneaded by the extruder into a sheet, a film, a modified extrusion molded product, a direct blow molded product, and an injection molded product without passing through pellets. Further, the resin composition of the present invention can also be used in the form of various deformed extrusion-molded products, sheets, films and the like by extrusion molding. Inflation method, calendar method, casting method, etc. can also be used for forming sheets and films. Further, it can be molded as a heat-shrinkable tube by applying a specific stretching operation. Further, the resin composition of the present invention can be made into a molded product by rotary molding, blow molding or the like.

<Manufacturing of resin composition>
Any method is adopted for producing the resin composition of the present invention. For example, components A to E and optionally other components are sufficiently mixed using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical device, and an extrusion mixer, and then an extrusion granulator if necessary. There is a method of granulating with a briquetting machine or the like, then melt-kneading with a melt-kneader typified by a vent-type twin-screw ruder, and pelletizing with a device such as a pelletizer.

<Manufacturing of molded products>
In the resin composition of the present invention, such pellets are usually injection-molded to obtain a molded product. In such injection molding, it is possible to manufacture by a hot runner that enables runner-less as well as a usual cold runner type molding method. Also, in injection molding, not only ordinary molding methods, but also gas-assisted injection molding, injection compression molding, ultra-high-speed injection molding, injection press molding, two-color molding, sandwich molding, in-mold coating molding, insert molding, foam molding (ultra). (Including those using a critical fluid), rapid heating and cooling mold molding, heat insulating mold molding and in-mold remelt molding, and a molding method consisting of a combination thereof can be used. Further, the molded product formed from the resin composition can be subjected to various surface treatments. Surface treatments include decorative coating, hard coat, water / oil repellent coat, hydrophilic coat, ultraviolet absorption coat, infrared absorption coat, electromagnetic wave absorption coat, heat generation coat, antistatic coat, antistatic coat, conductive coat, and meta. Various surface treatments such as rising (plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), spraying, etc.) can be performed. In particular, a transparent sheet coated with a transparent conductive layer is preferable.

The molded product made of the polycarbonate resin composition of the present invention maintains excellent hue and phosphorescence even after the weather resistance test, and is useful for outdoor night display applications such as car stops, road signs, and evacuation guidance signs. , The industrial effect it produces is exceptional.

The embodiment of the present invention, which the present inventor considers to be the best at present, is a collection of preferable ranges of the above-mentioned requirements. For example, a representative example thereof will be described in the following examples. Of course, the present invention is not limited to these forms.

1. 1. Evaluation of Polycarbonate-Polydiorganosiloxane Copolymer (1) Polydiorganosiloxane Component Content Using JNM-AL400 manufactured by JEOL Ltd., ¹ H-NMR spectrum of the polycarbonate-polydiorganosiloxane copolymer resin was measured. It was calculated by comparing the integral ratio of the peak derived from the valent phenol (I) with the integral ratio of the peak derived from the dihydroxyaryl-terminated polydiorganosiloxane (II).
Polydiorganosiloxane component content (wt%) = [A / (A + B)] x 100
A: [integral ratio of the ^{1 H} one minute peak dihydroxy-terminated polydiorganosiloxane (II)] × [molecular weight of the polydiorganosiloxane moiety]
B: [integral ratio of the ^{1 H} one minute peak dihydric phenol (I)] × [molecular weight of the dihydric phenol]

2. Evaluation of Polycarbonate Resin Composition (1) Luminescent property Using an SG-150U molding machine of Sumitomo Heavy Industries, Ltd., a test piece (50 mm (width) x 90 mm (length)" was used at a cylinder temperature of 280 ° C and a mold temperature of 80 ° C. ), A three-stage plate having a thickness of 1 mm, 2 mm and 3 mm) was prepared. The test piece was stored in the dark for 24 hours to completely quench the phosphorescent agent. Then, using a D65 light source, the test piece was vertically irradiated for 12 hours at an illuminance of 2000 lux to excite the test piece. The emission intensity 10 seconds after the light source was turned off was measured with a LUMINANCE COROLIMITER BM-7 manufactured by TOPCON CORPORATION in a dark place.
(2) Weather resistance Using an SG-150U molding machine manufactured by Sumitomo Heavy Industries, Ltd., a test piece (50 mm (width) x 90 mm (length) with a thickness of 1 mm, at a cylinder temperature of 280 ° C and a mold temperature of 80 ° C, 2 mm and 3 mm three-stage plates) were prepared. A weather resistance test was conducted on this test piece for 500 hours, and the change in E value (ΔE) before and after the weather resistance test and the phosphorescent property after the weather resistance test were measured. The weather resistance test and the measurement of the E value were carried out by the following methods.
Weather resistance test: Atlas Ci4000 (manufactured by Toyo Seiki Seisakusho Co., Ltd.) set at a black panel temperature of 63 ° C., humidity of 50%, and irradiance of 0.35 W / m ² (340 nm) was installed so as to irradiate the back surface of the test piece for 500 hours. I took it out later.
Measurement of E value: A spectrophotometer CE-7000A manufactured by Sakata Inx Engineering Co., Ltd. was used for measurement by a D65 light source and a two-degree field of view transmission method.
(3) Extrudability The extrudability was evaluated based on the presence or absence of thread breakage when extrusion was performed using a vent-type twin-screw extruder. “Good” indicates that no thread breakage has occurred, and “bad” indicates that thread breakage has occurred.
(4) Appearance The appearance of a test piece (a three-stage plate of 50 mm (width) × 90 mm (length) and thickness of 1 mm, 2 mm and 3 mm) prepared for light resistance evaluation was visually evaluated. “Good” indicates that no silver was generated, and “bad” indicates that silver was generated.

[Examples 1 to 9 and Comparative Examples 1 to 7]
The components A to E and other components were mixed in each blending amount shown in Table 1 with a blender, and then melt-kneaded using a bent twin-screw extruder to obtain pellets. The vent type twin-screw extruder was manufactured by The Japan Steel Works, Ltd .: TEX30α (complete meshing, rotating in the same direction, double-threaded screw). The extrusion conditions are a discharge rate of 20 kg / h, a screw rotation speed of 150 rpm, a vent vacuum degree of 3 kPa, and an extrusion temperature of 290 ° C from the first supply port to the second supply port and 295 ° C from the second supply port to the die portion. did. Each of the above evaluations was carried out using the obtained pellets. The results are shown in Table 1.

The details of each component used are as follows.
(Component A) Polycarbonate resin powder obtained by the following manufacturing method [Manufacturing method]
2340 parts of ion-exchanged water, 947 parts of 25% sodium hydroxide aqueous solution, and 0.7 part of hydrosphenol were charged into a thermometer, agitator, and a reactor with a reflux cooler, and 2,2-bis (4-hydroxyphenyl) was added under stirring. ) 710 parts of propane (hereinafter sometimes referred to as "bisphenol A") is dissolved (bisphenol A solution), then 2299 parts of methylene chloride and 112 parts of 48.5% sodium hydroxide aqueous solution are added, and the temperature is 15 to 25 ° C. A phosgenation reaction was carried out by blowing 354 parts of phosgen over about 90 minutes. After completion of phosgenation, 148 parts of methylene chloride solution of 11% concentration p-tert-butylphenol and 88 parts of 48.5% sodium hydroxide aqueous solution were added, stirring was stopped, and the mixture was left to stand for 10 minutes and then stirred. After 5 minutes of emulsification, it was treated with a homomixer (Special Machinery Chemical Industry Co., Ltd.) at a rotation speed of 1200 rpm and a number of passes of 35 times to obtain a highly emulsified dope. The highly emulsified dope was reacted in a polymerization tank (with a stirrer) at a temperature of 35 ° C. for 3 hours under non-stirring conditions to complete the polymerization. After completion of the reaction, the organic phase is separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water, and when the conductivity of the aqueous phase becomes almost the same as that of ion-exchanged water, it is poured into a kneader filled with warm water. Methylene chloride was evaporated with stirring to obtain a polycarbonate powder. After dehydration, it was dried at 120 ° C. for 12 hours with a hot air circulation type dryer to obtain a polycarbonate resin powder.
(Component B) Polycarbonate-polydiorganosiloxane copolymer resin powder obtained by the following manufacturing method [Manufacturing method]
Put 21591 parts of ion-exchanged water and 3674 parts of 48.5% sodium hydroxide aqueous solution into a reactor with a thermometer, agitator and a reflux condenser, and 3880 parts of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). After dissolving 7.6 parts of hydrosulfite, 14565 parts of methylene chloride (14 mol with respect to 1 mol of dihydroxy compound (I)) was added, and 1900 parts of phosgen was required for 60 minutes at 22 to 30 ° C. under stirring. I blew it in. Next, a solution prepared by dissolving 1131 parts of a 48.5% sodium hydroxide aqueous solution and 105 parts of p-tert-butylphenol in 800 parts of methylene chloride was added, and the polydiorganosiloxane compound represented by the following formula [8] was added with stirring. A solution prepared by dissolving 430 parts of the average number of repetitions p = about 37) in 1600 parts of methylene chloride in a solution containing 0.0008 mol of dihydroxyaryl-terminated polydiorganosiloxane (II) per mol of divalent phenol (I). After adding at a rate of / min to an emulsified state, the mixture was vigorously stirred again. Under such stirring, 4.3 parts of triethylamine was added while the reaction solution was at 26 ° C., and stirring was continued at a temperature of 26 to 31 ° C. for 45 minutes to complete the reaction. After completion of the reaction, the organic phase is separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water, and when the conductivity of the aqueous phase becomes almost the same as that of ion-exchanged water, it is poured into a kneader filled with warm water. Then, methylene chloride was evaporated with stirring to obtain a powder of a polycarbonate-polydiorganosiloxane copolymer resin. After dehydration, it was dried at 120 ° C. for 12 hours with a hot air circulation type dryer to obtain a polycarbonate-polydiorganosiloxane copolymer resin powder. The content of the polydiorganosiloxane component in the obtained polycarbonate-polydiorganosiloxane copolymer resin powder was 8.4% by weight.

(C component) P-170 (manufactured by Ryoko Co., Ltd., chemical composition = Sr ₂ MgSi ₂ O ₇ : Eu, Dy)
(Component D) TSR9002 (manufactured by Momentive Performance Materials Japan GK, average particle size 2 μm)
(E component)
E-1: Chinubin 234 (manufactured by Ciba Specialty Chemicals Co., Ltd., molecular weight = 446)
E-2: Chemisorb 79 (manufactured by Cipro Kasei Co., Ltd., molecular weight = 323)
(Other ingredients)
F: Trimethylphosphate (manufactured by Daihachi Chemical Industry Co., Ltd.)

Claims (6)

(A) Polycarbonate-based phosphorescent material (C component) 1 to 35 with respect to 100 parts by weight of the resin component composed of (A) polycarbonate resin (A component) and (B) polycarbonate-polydiorganosiloxane copolymer resin (B component). A polycarbonate resin composition containing 0.05 to 10 parts by weight of (D) a light diffusing agent (D component) and 0.01 to 1 part by weight of (E) an ultraviolet absorber (E component). The claim is characterized in that the component B is a polycarbonate-polydiorganosiloxane copolymer resin composed of a polycarbonate block represented by the following general formula [1] and a polydiorganosiloxane block represented by the following general formula [3]. The polycarbonate resin composition according to 1.

[In the above general formula [1], R ¹ and R ² are independently hydrogen atom, halogen atom, alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, and 6 to 6 carbon atoms, respectively. 20 cycloalkyl groups, 6 to 20 carbon atoms cycloalkoxy groups, 2 to 10 carbon atoms alkenyl groups, 6 to 14 carbon atoms aryl groups, 6 to 14 carbon atoms aryloxy groups, carbon atoms Represents a group selected from the group consisting of an aralkyl group having a number of 7 to 20, an aralkyloxy group having a carbon atom number of 7 to 20, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. A and b are each an integer of 1 to 4, and W is at least one group selected from the group consisting of a single bond or a group represented by the following general formula [2].

(In the above general formula [2], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are independently hydrogen atoms, alkyl groups having 1 to 18 carbon atoms, and carbon. Represents a group selected from the group consisting of an aryl group having 6 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ are independent hydrogen atoms, halogen atoms, and carbon atoms 1 to 18 respectively. Aryl group, alkoxy group with 1 to 10 carbon atoms, cycloalkyl group with 6 to 20 carbon atoms, cycloalkoxy group with 6 to 20 carbon atoms, alkenyl group with 2 to 10 carbon atoms, 6 carbon atoms From an aryl group of ~ 14, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group. Represents a group selected from the group, and if there are a plurality of groups, they may be the same or different, and c is an integer of 1 to 10 and d is an integer of 4 to 7.)]

(In the above general formula [3], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently substituted with a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or 6 to 12 carbon atoms, respectively. Alternatively, they are unsubstituted aryl groups, and R ⁹ and R ¹⁰ are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 10 carbon atoms, and e and f. Is an integer of 1 to 4, p is a natural number, q is 0 or a natural number, p + q is a natural number of 4 or more and 150 or less. X is a divalent aliphatic group having 2 to 8 carbon atoms. .) Based on the total weight of the polycarbonate resin composition, the content of the polydiorganosiloxane block represented by the following general formula [4] contained in the above general formula [3] is 1.0% by weight or more. The polycarbonate resin composition according to claim 1 or 2.

(In the above general formula [4], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently substituted with a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or 6 to 12 carbon atoms, respectively. Alternatively, it is an unsubstituted aryl group, p is a natural number, q is 0 or a natural number, and p + q is a natural number of 4 or more and 150 or less.) The polycarbonate resin composition according to any one of claims 1 to 3, wherein the component E is an ultraviolet absorber containing a compound having a benzotriazole skeleton and a molecular weight of less than 500 as a main component. The polycarbonate resin composition according to any one of claims 1 to 4, wherein the average particle size of the D component is 1 to 20 μm. A molded product obtained by molding the polycarbonate resin composition according to any one of claims 1 to 5.