JP2023149670A - Polycarbonate resin composition and molding thereof - Google Patents

Abstract

To provide a polycarbonate resin composition with superior light guide performance, minimal yellowing during molding, minimal degradation under a hygrothermal environment, and superior fluidity, and a molding of the same.SOLUTION: The present invention provides a polycarbonate resin composition having light guide performance. Relative to 100 pts.wt. of (A) polycarbonate resin (A component), the polycarbonate resin composition contains 0.2-1.5 pts.wt. of (B) a polyether polymer having an alkyl group in at least one end with a number average molecular weight of 300-3,500 (B component).SELECTED DRAWING: None

Description

The present invention relates to a polycarbonate resin composition having light-guiding properties and a molded article made from the same. More specifically, it is suitable for optical elements such as light guide plates, which have excellent light guiding properties, little yellowing during molding, little deterioration in humid heat environments, and excellent fluidity, or covers for display panels and lighting. The present invention relates to a polycarbonate resin composition that can be used for, and a molded article made from the same.

Light sources using LEDs are attracting attention as next-generation light sources due to their power saving and long life.Since the development of blue light emitting diodes in the 1990s, the practical possibility of white light illumination using LEDs has increased. , commercially available products centered on local lighting have rapidly appeared. In addition, regarding surface light sources such as displays, LED light sources are more effective than the colors (red, green, and blue) obtained by transmitting the white light emitted by cold cathode tubes through color filters. LED light sources are increasingly being used because they have the advantage of high color purity and the ability to greatly expand the color reproduction range.

On the other hand, since LEDs are point light sources, in order to illuminate a large area, it is necessary to install many LEDs on the back of the light source (backlight method), each of which appears as a point light source, which causes unevenness. There is a drawback that it is easy to occur. Recently, with the aim of eliminating this unevenness, lowering costs, further saving power, and making products thinner, so-called edge-light light sources, in which LEDs are placed on the end faces of the light source, have been increasing. .

In an edge-light type light source, a light guide that transmits light over a long distance is used to achieve uniform surface luminescence. However, the edge-light type light source has a problem in that it becomes darker as it gets farther from the light source. Therefore, materials for molded bodies with light-guiding properties are required to have characteristics that reduce the attenuation of light from the light source, that is, light-guiding properties. ) has been used as the most suitable material. However, PMMA does not necessarily have sufficient impact resistance, thermal stability, etc., and there is a problem in that the environment in which it can be used is restricted in the above-mentioned applications. In addition, with the shift to LED light sources, light guides are now required to have heat resistance in addition to the above characteristics. Therefore, techniques for improving the light guiding properties of polycarbonate resins, which are excellent in terms of heat resistance and impact resistance, have been attracting attention. In addition, in order to make the product thinner, the molten resin has high fluidity so that it can be easily processed by injection molding, extrusion molding, or compression molding while maintaining improved light guiding properties. is required.

As an example of improving the light guide properties of polycarbonate, Patent Document 1 describes an aromatic light guide plate prepared by blending a specific phosphorus stabilizer and a mold release agent with a polycarbonate resin having a viscosity average molecular weight of 13,000 to 15,000. Polycarbonate resin compositions have been reported. However, in addition to having problems with strength, there is also the problem of reduced heat and humidity resistance due to the presence of phosphorus stabilizers, which limits its uses.

Patent Documents 2 and 3 report aromatic polycarbonate resin compositions for light guide plates that contain a small amount of a specific siloxane compound. However, silicone-based compounds may generate low-molecular-weight silicone gas under high-temperature conditions.

Patent Document 4 reports a light guide plate in which a light scattering layer is provided on the front or back surface of a plate-shaped molded body formed using a resin composition made of polycarbonate and an acrylic resin. Patent Document 5 reports an aromatic polycarbonate resin composition comprising an aromatic polycarbonate resin and another thermoplastic resin having a difference in refractive index from the aromatic polycarbonate resin of 0.001 or more. However, since an acrylic resin that is originally incompatible with polycarbonate resin is added, the amount added is limited, and light guiding properties may not be sufficiently exhibited.

Japanese Patent Application Publication No. 2007-204737 Japanese Patent Application Publication No. 2004-250557 Japanese Patent Application Publication No. 2015-157901 Japanese Patent Application Publication No. 10-73725 Japanese Patent Application Publication No. 2002-60609

An object of the present invention is to provide a polycarbonate resin composition that has excellent light guiding properties, little yellowing during molding, little deterioration in a moist heat environment, and excellent fluidity, and a molded article made from the same.

As a result of intensive research aimed at achieving the above object, the present inventors have identified a specific polyether polymer and/or polyoxyalkylene bisphenol A ether, preferably a specific phosphorus compound, for polycarbonate resin. It has been discovered that a polycarbonate resin composition blended in the same proportions achieves the above object, and the present invention has been achieved.
That is, according to the present invention, the following configurations (1) to (6) are provided.

(1) For 100 parts by weight of (A) polycarbonate resin (component A), (B) a polyether polymer having an alkyl group at at least one end and having a number average molecular weight of 300 to 3,500 and/or A polycarbonate resin composition having light guiding performance characterized by containing 0.2 to 1.5 parts by weight of polyoxyalkylene bisphenol A ether (component B) having a number average molecular weight of 300 to 2,000.
(2) Component B is at least one polyether polymer selected from the group consisting of polyethers having an alkyl group at at least one end represented by the following formula [1] and/or the following formula [2] A polycarbonate resin composition having the light guiding performance according to the above item 1.

(In the formula, m is an integer of 10 to 18, and n is an integer of 5 to 40.)

(In the formula, m is an integer from 12 to 18, and n is an integer from 4 to 50.)
(3) The polycarbonate resin composition having the light guide performance according to the above item 1, wherein component B is polyoxyalkylene bisphenol A ether represented by the following formula [3].

(In the formula, OR' represents ethylene oxide or propylene oxide, and n is an integer from 3 to 20.)
(4) The polymer according to the preceding item 1, which contains 0.01 to 0.1 parts by weight of (C) a phosphorus compound having a phenyl group (component C) per 100 parts by weight of the polycarbonate resin (component A). Polycarbonate resin composition with optical performance.
(5) The polycarbonate resin composition having the light guide performance as described in the above item (4), wherein component C is a phosphorus compound having three phenyl groups represented by the following formula [4].

(6) A molded article made of a polycarbonate resin composition having the light guide performance described in 1 above.

The polycarbonate resin composition of the present invention has excellent light guiding properties, less yellowing during molding, less deterioration in a humid heat environment, and excellent fluidity. Since the polycarbonate resin composition of the present invention has the above-mentioned effects, it is extremely useful for various industrial applications such as the lighting field including LED lighting, the OA equipment field, the electrical and electronic equipment field, and the automobile field. The effect is extremely large.

The details of the present invention will be explained below.

<Component A: Polycarbonate resin>
The polycarbonate resin used as 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 melt transesterification method, or by reacting a carbonate prepolymer with a solid phase transesterification method. or by ring-opening polymerization of a cyclic carbonate compound.

The dihydroxy component used here may be one that is normally used as a dihydroxy component of polycarbonate resins, and may be bisphenols or aliphatic diols.

Examples of bisphenols include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 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-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)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'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy- 3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3, 3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 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-adamantanediyl)diphenol, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane and the following formula [5] Examples include bisphenol compounds having a siloxane structure represented by:

[In the formula, R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and p and q are each 1 ˜4, e is a natural number, f is 0 or a natural number, and e+f is a natural number less than 100. X is a divalent aliphatic group having 2 to 8 carbon atoms. ]

Examples of aliphatic diols include 2,2-bis-(4-hydroxycyclohexyl)-propane, 1,14-tetradecanediol, octaethylene glycol, 1,16-hexadecanediol, 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 -isopropylphenyl}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}decane, 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-cyclohexyl-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-dimethyladamantane, 3,9-bis(2-hydroxy-1,1-dimethyl) ethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, 1,4:3,6-dianhydro-D-sorbitol (isosorbide), 1,4:3,6-dianhydro-D- Examples include mannitol (isomannide), 1,4:3,6-dianhydro-L-iditol (isooidide), and the like.

Among these, aromatic bisphenols are preferred, and among them, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, and 2,2-bis(4-hydroxyphenyl)propane. -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, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, and the bisphenol compound represented by the above general formula [4], particularly 2,2-bis(4-hydroxyphenyl)benzene. ) propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, and the above general formula [4] The bisphenol compounds represented are preferred. Among them, 2,2-bis(4-hydroxyphenyl)propane, which has excellent strength and good durability, is most suitable. Further, these may be used alone or in combination of two or more.

The polycarbonate resin used as component A of the present invention may be made into 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 phloroglucin, phloroglucide, or 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)heptene-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) Ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 26-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-{4-[1, Trisphenol such as 1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4- Examples include bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and their acid chlorides, among which 1,1,1-tris(4-hydroxyphenyl) Ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

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

In reactions 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. Further, catalysts such as tertiary amines or quaternary ammonium salts can also be used to promote the reaction. At this 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 carbonate diester as a carbonate precursor is carried out by heating and stirring a predetermined proportion of an aromatic dihydroxy component with a carbonate diester under an inert gas atmosphere, and distilling off the alcohol or phenol produced. . 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 under reduced pressure from the initial stage to distill out the alcohol or phenol produced. Furthermore, a catalyst commonly used in transesterification reactions can also be used to promote the reaction. Examples of the diester carbonate used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Among these, diphenyl carbonate is particularly preferred.

In the present invention, a terminal capping agent is used in the polymerization reaction. A terminal capping agent is used to control the molecular weight, and the resulting polycarbonate resin has superior thermal stability compared to a resin that is not terminal-capped. Such terminal capping agents include monofunctional phenols represented by the following formulas [6] to [8].

[Formula [6], 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 part is 1 to 9), a phenyl group, or a phenylalkyl group (the number of carbon atoms in the alkyl part is 1 to 9). the number of atoms is 1 to 9), and r is an integer of 1 to 5, preferably 1 to 3. ]

[In formula [8], Y is -R-O-, -R-CO-O- or -R-O-CO-, where R is a single bond or has 1 to 10 carbon atoms, preferably 1 ~5 divalent aliphatic hydrocarbon group, and n represents an integer of 10 to 50. ]

Specific examples of monofunctional phenols represented by the above formula [6] include phenol, isopropylphenol, p-tert-butylphenol, p-cresol, p-cumylphenol, 2-phenylphenol, 4-phenylphenol. , and isooctylphenol.

Furthermore, the monofunctional phenols represented by the above formula [7] or [8] are phenols having long-chain alkyl groups or aliphatic ester groups as substituents, and these are used to terminate the terminals of polycarbonate resins. When capped, these not only function as end capping agents or molecular weight regulators, but also improve the melt flowability of the resin, making molding easier, and are also effective in lowering the water absorption rate of the resin, so they are preferably used. be done.

The substituted phenols of the above formula [7] are preferably those in which n is 10 to 30, particularly 10 to 26, and specific examples include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eiko Examples include silphenol, docosylphenol and triacontylphenol.

Further, as the substituted phenols of the above formula [8], compounds in which Y is -R-COO- and R is a single bond are suitable, and those in which n is 10 to 30, particularly 10 to 26 are suitable. Specific examples include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate, and triacontyl hydroxybenzoate.

Among these monofunctional phenols, monofunctional phenols represented by the above formula [6] are preferred, alkyl-substituted or phenylalkyl-substituted phenols are more preferred, and p-tert-butylphenol and p-tert-butylphenol are particularly preferred. It is cumylphenol or 2-phenylphenol.

It is desirable that these monofunctional phenolic end-stopping agents be introduced at least 5 mol%, preferably at least 10 mol%, at the ends of the obtained polycarbonate resin, and the end-stopping agent may be introduced alone. They may be used alone or in combination of two or more.

The polycarbonate resin used as component A of the present invention may be a polyester carbonate copolymerized with an aromatic dicarboxylic acid, such as terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, or a derivative thereof, as long as it does not impair the spirit of the present invention. good.

The viscosity average molecular weight of the polycarbonate resin used as component A of the present invention is preferably in the range of 11,500 to 50,000, more preferably in the range of 12,500 to 40,000, and more preferably in the range of 13,500 to 35,000. More preferably, the range is from 15,000 to 30,000. If the molecular weight exceeds 50,000, the melt viscosity may become too high, resulting in poor moldability, while if the molecular weight is less than 11,500, problems may arise in mechanical strength. The viscosity average molecular weight in the present invention was first determined by using an Ostwald viscometer to determine the specific viscosity calculated by the following formula from a solution of 0.7 g of polycarbonate resin dissolved in 100 ml of methylene chloride at 20°C. Insert the specific viscosity into the following equation to determine the viscosity average molecular weight Mv.
Specific viscosity (η _SP )=(t−t ₀ )/t ₀
[ _t0 is the number of seconds that methylene chloride falls, t is the number of seconds that the sample solution falls]
η _SP /c=[η]+0.45×[η] ² c (however, [η] is the limiting viscosity)
[η]=1.23×10 ⁻⁴ Mv ^0.83
c=0.7

The polycarbonate resin used as component A of the present invention preferably has a total Cl (chlorine) content of 0 to 500 ppm, more preferably 0 to 350 ppm. It is preferable that the total amount of Cl in the polycarbonate resin is within the above range because it has excellent hue and thermal stability.

<Component B: Specific polyether polymer and/or polyoxyalkylene bisphenol A ether>
The polycarbonate resin composition of the present invention comprises a polyether polymer having a number average molecular weight of 300 to 3,500, which has an alkyl group at at least one end (preferably has a structure end-capped with an alkyl group), and/or Or it contains polyoxyalkylene bisphenol A ether having a number average molecular weight of 300 to 2,000.

The polyether polymer is a polyether polymer composed of units derived from alkylene glycol, and the alkylene group may include a branched structure.

As the polyalkylene glycol, alkylene glycols having 2 to 3 carbon atoms such as ethylene glycol and propylene glycol are preferred. Further, the polyalkylene glycol may be a homopolymer of a single alkylene glycol, or a random copolymer or block copolymer of two types of alkylene glycols.

As the polyalkylene glycol, specifically, for example, polyethylene glycol and polypropylene glycol are preferable. The polyalkylene glycol compound used in the present invention is characterized in that at least one end thereof is capped with an alkyl group, as shown in the following formula [1] or [2]. The alkyl group preferably has 10 to 18 carbon atoms, more preferably 12 to 18 carbon atoms, and is preferably free of unsaturated carbon bonds unlike alkyl groups.

(In the formula, m is an integer of 10 to 18, and n is an integer of 5 to 40.)

(In the formula, m is an integer from 12 to 18, and n is an integer from 4 to 50.)
A polyalkylene glycol compound having an alkyl group at at least one end can be obtained by addition polymerizing an alkylene oxide to an alcohol having an alkyl group. Addition polymerization of alkylene oxide is known and is generally carried out under an alkali catalyst such as sodium hydroxide or potassium hydroxide, although it is not particularly limited.

Etherification methods are known and are not particularly limited, but generally include a method in which polyalkylene glycol is reacted with alcohol in the presence of sodium metal, sodium hydride, sodium hydroxide, or the like.

The number average molecular weight of the polyether polymer whose at least one end is capped with an alkyl group is in the range of 300 to 3,500, preferably 500 to 3,000, more preferably 800 to 2, 500, and if it exceeds the above range, the moisture and heat resistance will be poor and the effect of increasing light guiding properties will be reduced. If it is below the above range, the effect of increasing fluidity will be small and there will be adverse effects such as thermal decomposition of the polycarbonate resin. It begins to affect people. The number average molecular weight of the polyether polymer is the number average molecular weight calculated based on the hydroxyl value measured in accordance with JIS K1577.

Further, as shown in the following formula [3], the polyoxyalkylene bisphenol A ether preferably has polyethylene oxide or polypropylene oxide as the oxygen atoms at both ends of the bisphenol A structure. As for the polyoxyalkylene structure, the number n in the following formula [3] is preferably an integer of 3 to 20, more preferably an integer of 5 to 18, and still more preferably an integer of 8 to 16.

(In the formula, OR' represents ethylene oxide or propylene oxide, and n is an integer from 3 to 20.)

The number average gold molecular weight of the polyoxyalkylene bisphenol A ether is in the range of 300 to 2,000, preferably in the range of 500 to 1,800, more preferably in the range of 1,000 to 1,600. If it exceeds the above range, the heat and humidity resistance will be poor and the effect of increasing light guiding properties will be reduced, and if it is below the above range, the effect of increasing fluidity will be reduced. The number average molecular weight of polyoxyalkylene bisphenol A ether is the number average molecular weight calculated based on the hydroxyl value measured in accordance with JIS K1577.

The specific polyether polymer and/or polyoxyalkylene bisphenol A ether used as component B of the present invention improves the light guiding performance of polycarbonate resin, while impairing mechanical properties, hue, and molding stability. do not have. The content of the specific polyether polymer and/or polyoxyalkylene bisphenol A ether is 0.2 to 1.5 parts by weight based on 100 parts by weight of the polycarbonate resin (component A). The amount is preferably 0.4 to 1.3 parts by weight, more preferably 0.5 to 1.2 parts by weight. If the content is less than the above range, the improvement in transparency and fluidity will not be sufficient, and if it exceeds the above range, the resin will become colored, impairing the transparency of the polycarbonate, and having a negative effect on heat resistance and mechanical strength. It becomes like this.

<Component C: Phosphorus compound having a phenyl group>
The phosphorus compound preferably used as component C in the present invention is preferably a phosphorus compound having a phenyl group. Among these, phosphorus compounds having three phenyl groups are preferred, and triphenylphosphine represented by the following formula [4] is particularly preferred.

By using a phosphorus compound having a phenyl group, it not only provides high fluidity but also functions as an antioxidant. The content of the phosphorus compound having a phenyl group (component C) is preferably 0.01 to 0.1 part by weight based on 100 parts by weight of the polycarbonate resin (component A). More preferably, it is 0.02 to 0.08 parts by weight. When the content is within the above range, fluidity is improved, transparency is sufficiently improved as an antioxidant, and there is an effect that the heat resistance and mechanical strength of the polycarbonate resin are not adversely affected.

<Other ingredients>
The polycarbonate resin composition of the present invention may contain other resins and fillers as long as they do not impair transparency, light guiding properties, etc. However, many of the other resins and fillers are transparent. Therefore, this point should be taken into consideration when selecting the type and amount.

In the polycarbonate resin composition of the present invention, in order to improve its thermal stability, designability, etc., additives used for these improvements are advantageously used, taking the above points into consideration. These additives will be specifically explained below.

(I) Heat stabilizer Various known heat stabilizers can be blended into the polycarbonate resin composition of the present invention. Specifically, phosphorus-based antioxidants, phenol-based antioxidants, etc. other than component C may be used.

Specific examples of such phosphorus-based antioxidants include phosphorous acid (phosphite), phosphonite, phosphinite, phosphine, phosphoric acid (phosphate), phosphonate, phosphinate, phosphine oxide, etc. Among them, phosphite, phosphonite, phosphine, etc. , phosphonates and phosphates are preferably used. Specifically, examples of phosphite compounds include trimethyl phosphite, triethyl phosphite, tripropyl phosphite, triisopropyl phosphite, tributyl phosphite, triphenyl phosphite, tris(nonylphenyl) phosphite, and tridecyl phosphite. Phite, trioctyl phosphite, triotadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2 , 2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, tris(diethylphenyl) phosphite, tris(di-iso-propylphenyl) phosphite, tris(di-n-butylphenyl) phosphite Examples include tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-di-tert-butylphenyl) phosphite, and the like. Furthermore, as other phosphite compounds, those having a cyclic structure that react with dihydric phenols 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'-ethylidenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, and the like.

Examples of phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, Phosphonite, Tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, Tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite , Tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, Tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, Bis (2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, -n-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, etc., tetrakis(di-tert-butylphenyl)-biphenylene diphosphonite, bis(di-tert-butylphenyl)-phenyl-phenylphosphonite are preferred, and tetrakis(2, More preferred are 4-di-tert-butylphenyl)-biphenylene diphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite. Such a phosphonite compound can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

Examples of phosphine compounds other than triphenylphosphine, which is component C, include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, tri- Examples include p-tolylphosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred phosphine compound is triphenylphosphine.

Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

Phosphate compounds 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, Examples include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferred.

Specific examples of phenolic antioxidants include vitamin E, n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butylfer) propionate, and 2-tert-butyl-6-( 3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenylacrylate, 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-hexane Diol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, bis[2-tert-butyl-4-methyl 6-(3-tert-butyl-5-methyl-2-hydroxy) benzyl)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-butylphenol), 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-tris 2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, tetrakis[methylene-3-(3',5'-di-tert-butyl) -4-hydroxyphenyl)propionate]methane and the like can be used preferably.

Among them, n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butylfer)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl- 2'-Hydroxybenzyl)-4-methylphenylacrylate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1,-dimethyl ethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, and tetrakis[methylene-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate]methane. Preferred is n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butylfer) propionate.

The above-mentioned phosphorus antioxidants and phenolic antioxidants can be used alone or in combination of two or more. The content of these phosphorus antioxidants or phenolic antioxidants is preferably 0.0001 to 1 part by weight per 100 parts by weight of component A. The amount is more preferably 0.0005 to 0.5 parts by weight, and even more preferably 0.001 to 0.2 parts by weight.

The amount of phosphorus-based antioxidants, especially phosphite-based antioxidants, is preferably less than 0.02 parts by weight, and is preferably less than 0.015 parts by weight, since the moisture and heat resistance of the polycarbonate resin decreases when the amount is increased. parts by weight or less, more preferably 0.01 parts by weight or less, particularly preferably 0.005 parts by weight or less, most preferably 0.001 parts by weight or less. Moreover, it is preferable not to substantially incorporate it.

(II) Mold release agent A mold release agent may be added to the polycarbonate resin composition of the present invention, if necessary. As such a mold release agent, those known per se can be used. For example, saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes (polyethylene waxes or 1-alkene polymers may be mentioned. Those modified with functional group-containing compounds such as acid modification can also be used), silicone compounds , fluorine compounds, paraffin wax, beeswax, etc. Among these, saturated fatty acid esters, linear or cyclic polydimethylsiloxane oil, polymethylphenyl silicone oil and fluorine oil are preferred. Particularly preferred mold release agents include saturated fatty acid esters, such as monoglycerides such as stearic acid monoglyceride, polyglycerin fatty acid esters such as decaglycerin decastearate and decaglycerin tetrastearate, and lower fatty acids such as stearic acid stearate. Esters, higher fatty acid esters such as sebacate behenate, and erythritol esters such as pentaerythritol tetrastearate are used. The content of the mold release agent is preferably 0.01 to 1 part by weight per 100 parts by weight of component A.

(III) Ultraviolet absorber The polycarbonate resin composition of the present invention may contain an ultraviolet absorber if necessary. Examples of such ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxybenzophenone. Hydroxy-4-benzyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2, 2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis Examples include benzophenone ultraviolet absorbers typified by (5-benzoyl-4-hydroxy-2-methoxyphenyl)methane.

Examples of ultraviolet absorbers include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy -5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'- di-tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-3'-dodecyl-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-bis(α, α'-dimethylbenzyl)phenylbenzotriazole, 2-[2'-hydroxy-3'-(3'',4'',5'',6''-tetraphthalimidomethyl)-5'-methylphenyl]benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5- Chlorobenzotriazole, 2,2'methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], methyl-3-[3-tert- Examples include benzotriazole ultraviolet absorbers typified by a condensate of butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenylpropionate and polyethylene glycol.

Furthermore, examples of ultraviolet absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxy-phenol, 2-(4,6-bis-(2,4 - Clariant Japan Co., Ltd., which produces hydroxyphenyltriazine compounds such as dimethylphenyl-1,3,5-triazin-2-yl)-5-hexyloxy-phenol and 2-(1-arylalkylidene)malonic acid esters. Examples include malonic acid ester compounds represented by Hostavin PR-25 manufactured by Clariant Japan Co., Ltd. and Hostavin B-CAP manufactured by Clariant Japan.

The content of the ultraviolet absorber is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 1 part by weight per 100 parts by weight of component A.

(IV) Light stabilizer A light stabilizer can be added to the polycarbonate resin composition of the present invention, if necessary. Examples of such light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1 , 2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2n-butylmalonate, 1,2,3,4-butane Condensate of carboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and tridecyl alcohol, 1,2,3,4-butanedicarboxylic acid and 1,2,2,6,6-pentamethyl- Condensate of 4-piperidinol and tridecyl alcohol, Tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, Tetrakis(1,2,2 ,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, poly{[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5 -triazine-2,4-diyl][(2,2,6,6-tetramethylpiperidyl)imino]hexamethylene[(2,2,6,6-tetramethylpiperidyl)imino]}, poly{[6- Morpholino-s-triazine-2,4-diyl][(2,2,6,6-tetramethylpiperidyl)imino]hexamethylene[(2,2,6,6-tetramethylpiperidyl)imino]}, 1, 2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and β,β,β',β'-tetramethyl-3,9-(2,4,8, condensate with 10-tetraoxaspiro[5,5]undecane) diethanol, N,N'-bis(3-aminopropyl)ethylenediamine and 2,4-bis[N-butyl-N-(1,2,2 ,6,6-pentamethyl-4-piperidyl)amino]-chloro-1,3,5-triazine condensate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6 - Condensate of pentamethyl-4-piperidinol and β,β,β',β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5]undecane)diethanol, poly Examples include hindered amines represented by methylpropyl 3-oxy-[4-(2,2,6,6-tetramethyl)piperidinyl]siloxane. The content of the light stabilizer is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 1 part by weight per 100 parts by weight of component A.

(V) Bluing agent A bluing agent can be blended into the polycarbonate resin composition of the present invention in order to cancel out the yellowing caused by ultraviolet absorbers and the like. Any bluing agent that is normally used for polycarbonate resins can be used without any particular problem. Generally, anthraquinone dyes are preferred because they are easily available. As a specific bluing agent, for example, the common name Solvent Violet 13 [CA. No (color index No.) 60725; Trade name "Macrolex Violet B" manufactured by Bayer, "Diaresin Blue G" manufactured by Mitsubishi Chemical, "Sumiplast Violet B" manufactured by Sumitomo Chemical], Generic name Solvent Violet 31 [CA ．． No. 68210; Trade name: Mitsubishi Chemical Corporation "Diaresin Violet D"], Generic name: Solvent Violet 33 [CA. No.60725; Trade name: "Diaresin Blue J" manufactured by Mitsubishi Chemical Corporation], Generic name: Solvent Blue94 [CA. No. 61500; Trade name: "Dia Resin Blue N" manufactured by Mitsubishi Chemical Corporation], Generic name: Solvent Violet 36 [CA. No. 68210; Trade name "Macrolex Violet 3R" manufactured by Bayer AG], generic name Solvent Blue 97 [trade name "Macro Rex Blue RR" manufactured by Bayer AG], and generic name Solvent Blue 45 [CA. No. 61110; trade name "Terazol Blue RLS" manufactured by Sandoz Co., Ltd.], and Macrolex Blue RR, Macrolex Violet B, and Terrasol Blue RLS are particularly preferred. The content of the bluing agent is preferably 0.000005 to 0.001 parts by weight, more preferably 0.00001 to 0.0001 parts by weight per 100 parts by weight of component A.

(VI) Fluorescent brightener In the polycarbonate resin composition of the present invention, the optical brightener is not particularly limited as long as it is used to improve the color tone of the resin to white or bluish-white, such as stilbene-based, Examples include benzimidazole-based, benzoxazole-based, naphthalimide-based, rhodamine-based, coumarin-based, and oxazine-based compounds. Specific examples include CI Fluorescent Brightener 219:1, EASTOBRITE OB-1 manufactured by Eastman Chemical Company, and "Hakkor PSR" manufactured by Hakkol Chemical Company. The fluorescent whitening agent has the function of absorbing energy in the ultraviolet region of light and emitting this energy to the visible region. The content of the optical brightener is preferably 0.001 to 0.1 part by weight, more preferably 0.001 to 0.05 part by weight, based on 100 parts by weight of component A.

(VII) Epoxy compound The polycarbonate resin composition of the present invention may contain an epoxy compound as necessary. Such epoxy compounds are blended for the purpose of suppressing mold corrosion, and basically any compound having an epoxy functional group can be used. Specific examples of preferred epoxy compounds include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 1,2-epoxy-4- of 2,2-bis(hydroxymethyl)-1-butanol; Examples include (2-oxiranyl)cyclohexane adducts, copolymers of methyl methacrylate and glycidyl methacrylate, and copolymers of styrene and glycidyl methacrylate. 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, and even more preferably 0.005 parts by weight, based on 100 parts by weight of component A. ~0.1 part by weight.

(VIII) Organometallic Salt The polycarbonate resin composition of the present invention may contain an organometallic salt compound. Such organic metal salts are blended for the purpose of imparting flame retardancy, and are preferably alkali (earth) metal salts of organic acids having 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms. Preferably, organic sulfonic acid alkali (earth) metal salts are more preferable. The organic sulfonic acid alkali (earth) metal salts include fluorine-substituted alkyl sulfones such as metal salts of perfluoroalkyl sulfonic acids having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and alkali metals or alkaline earth metals. Included are metal salts of acids and metal salts of aromatic sulfonic acids having from 7 to 50 carbon atoms, preferably from 7 to 40 carbon atoms, with alkali metals or alkaline earth metals. Alkali metals constituting the metal salt include lithium, sodium, potassium, rubidium, and cesium, and alkaline earth metals include beryllium, magnesium, calcium, strontium, and barium. More preferred are alkali metals. Among such alkali metals, rubidium and cesium, which have larger ionic radii, are preferred when transparency is required, but they are not widely used and are difficult to purify, resulting in lower costs. 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. The alkali metal in the alkali metal sulfonate can be selected depending on these considerations, but potassium sulfonate is the most suitable because it has excellent balance of properties in all respects. Such a potassium salt and an alkali metal sulfonic acid salt consisting of another alkali metal can also be used in combination.

Specific examples of alkali metal perfluoroalkylsulfonates include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, and perfluorobutanesulfonate. Sodium butanesulfonate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, perfluorooctanesulfonic acid Examples include cesium, cesium perfluorohexanesulfonate, rubidium perfluorobutanesulfonate, and rubidium perfluorohexanesulfonate, and these can be used alone or in combination of two or more. The number of carbon atoms in 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. Among these, potassium perfluorobutanesulfonate is particularly preferred. A considerable amount of fluoride ions are usually mixed into the alkali (earth) metal salt of perfluoroalkylsulfonic acid made of an alkali metal. Since the presence of such fluoride ions can be a factor in reducing flame retardancy, it is preferable to reduce them as much as possible. The proportion of such fluoride ions can be measured by ion chromatography. The content of fluoride ions is preferably 100 ppm or less, more preferably 40 ppm or less, particularly preferably 10 ppm or less. Further, in terms of manufacturing efficiency, it is preferable that the content is 0.2 ppm or more. Such an alkali (earth) metal salt of perfluoroalkylsulfonic acid with a reduced amount of fluoride ions can be produced by using a known production method and contained in the raw materials for producing the fluorine-containing organic metal salt. Methods for reducing the amount of fluoride ions, methods for removing hydrogen fluoride etc. obtained by the reaction by using gas generated during the reaction or heating, and purification methods such as recrystallization and reprecipitation for producing fluorine-containing organometallic salts. It can be manufactured by a method of reducing the amount of fluoride ions using fluoride ions. In particular, organic metal salt flame retardants are relatively easily soluble in water, so use ion-exchanged water, especially water that satisfies an electrical resistance value of 18 MΩ·cm or more, that is, an electrical conductivity of about 0.55 μS/cm or less. , and is preferably manufactured by a process of dissolving and washing at a temperature higher than room temperature, and then cooling and recrystallizing. Specific examples of aromatic sulfonic acid alkali (earth) metal salts include, for example, disodium diphenylsulfide-4,4'-disulfonate, dipotassium diphenylsulfide-4,4'-disulfonate, potassium 5-sulfoisophthalate, Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecyl phenyl ether disulfonate, polysodium poly(2,6-dimethylphenylene oxide) polysulfonate , polysodium poly(1,3-phenylene oxide) polysulfonate, polysodium poly(1,4-phenylene oxide) polysulfonate, polypotassium poly(2,6-diphenylphenylene oxide) polysulfonate, 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 diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, dipotassium diphenylsulfone-3,3'-disulfonate, diphenylsulfone-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, Examples include calcium thiophene-2,5-disulfonate, sodium benzothiophenesulfonate, potassium diphenylsulfoxide-4-sulfonate, formalin condensate of sodium naphthalenesulfonate, and formalin condensate of sodium anthracene sulfonate. can. Among these alkali (earth) metal salts of aromatic sulfonic acids, potassium salts are particularly preferred. Among these alkali (earth) metal salts of aromatic sulfonates, potassium diphenylsulfone-3-sulfonate and dipotassium diphenylsulfone-3,3'-disulfonate are preferred, and in particular mixtures thereof (the former and the latter) are preferred. The weight ratio of 15/85 to 30/70) is suitable.

Preferred examples of organic metal salts other than alkali (earth) metal sulfonates include alkali (earth) metal salts of sulfuric esters and alkali (earth) metal salts of aromatic sulfonamides. As alkali (earth) metal salts of sulfuric esters, mention may be made in particular of alkali (earth) metal salts of sulfuric esters of monohydric and/or polyhydric alcohols; Examples of sulfuric esters include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkyl phenyl ether sulfate, pentaerythritol mono-, di-, tri-, and tetra-sulfate ester, and lauric acid monoglyceride sulfate. Examples include esters, sulfuric esters of palmitic acid monoglyceride, and sulfuric esters of stearic acid monoglyceride. Preferred examples of the alkali (earth) metal salts of these sulfuric esters include alkali (earth) metal salts of lauryl sulfate. Alkali (earth) metal salts of aromatic sulfonamides include, for example, saccharin, N-(p-tolylsulfonyl)-p-toluenesulfimide, N-(N'-benzylaminocarbonyl)sulfanylimide, and N-( Examples include alkali (earth) metal salts of phenylcarboxyl) sulfanylimide. The content of the organic metal salt is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, and even more preferably 0.01 to 0.3 part by weight per 100 parts by weight of component A. parts, particularly preferably 0.03 to 0.15 parts by weight.

(IX) Others In addition to the above, the resin composition of the present invention may contain additives known per se in order to impart various functions and improve properties of the molded product, as long as the purpose of the present invention is not impaired. can do. Such additives include reinforcing fillers, sliding agents (e.g. PTFE particles), colorants, fluorescent dyes, inorganic phosphors (e.g. phosphors whose parent crystal is aluminate), antistatic agents, and crystal nucleating agents. , inorganic and organic antibacterial agents, photocatalytic antifouling agents (e.g. particulate titanium oxide, particulate zinc oxide), light diffusing agents, flow modifiers, radical generators, infrared absorbers (heat ray absorbers), photochromic agents, etc. can be mentioned.

<About manufacturing polycarbonate resin composition>
Any method can be used to produce the polycarbonate resin composition of the present invention. For example, after thoroughly mixing component A, component B, and optionally other components using a premixing means such as a V-type blender, Henschel mixer, mechanochemical device, or extrusion mixer, if necessary, use an extrusion granulator. Examples of methods include granulation using a briquetting machine or the like, followed by melt-kneading using a melt-kneading machine typified by a vent-type twin-screw ruder, and pelletizing using a device such as a pelletizer. Alternatively, component A, component B, and optionally other components may be fed independently into a melt kneader, such as a vented twin-screw ruder, or a portion of component A and other components may be premixed. Component B is then diluted and mixed with water or an organic solvent and then supplied to a melt kneader, or such a diluted mixture is premixed with other components and then melted. Another example is a method of feeding it to a kneader. In addition, when there is a liquid component in the blended components, a so-called liquid injection device or liquid addition device can be used to supply the components to the melt-kneading machine.

<Manufacture of molded products>
Any method can be used to produce a molded article made of the polycarbonate resin composition of the present invention. For example, the polycarbonate resin composition can be kneaded using an extruder, a Banbury mixer, a roll, or the like, and then molded by a conventionally known method such as injection molding, extrusion molding, or compression molding to obtain a molded article. Further, a light source can be provided on at least one side of a molded plate obtained by molding into a plate shape, and a reflective plate can be installed on one side of the molded plate to form a surface light source body. As a light source for such a molded plate and a surface light source, in addition to a fluorescent lamp, a self-luminous body such as a cold cathode tube, an LED, a laser diode, an organic EL, etc. can be used. The molded plates and surface light sources of molded products obtained by the present invention are used for mobile phones, mobile terminals, cameras, watches, notebook computers, displays, lighting, traffic lights, automobile lamps, and display parts for home appliances and optical equipment. be done.
Furthermore, it is extremely useful for various industrial applications such as the OA equipment field, the electrical and electronic equipment field, and the automobile field.

Specifically, our products include lighting covers, display diffusers, glass substitutes, optical discs and other related components, battery housings and other molded housings, lens barrels, memory cards, speaker cones, disc cartridges, Examples include surface light emitters, mechanical parts for micromachines, molded products with hinges or molded products for hinges, light-transmitting/light-guiding buttons, and touch panel parts.

The mode of the present invention that the present inventor considers to be the best at present is a combination of the preferable ranges of each of the above-mentioned requirements, and representative examples thereof are described in the following examples. Of course, the present invention is not limited to these forms.

The present invention will be further described below with reference to Examples, but the present invention is not limited to these Examples. The details of each component used and the evaluation are as follows.
(A component)
A: Bisphenol A type aromatic polycarbonate resin (manufactured by Teijin: CM-1000, viscosity average molecular weight 15,400)

(B component)
B-1: Polyether having an alkyl group having 12 carbon atoms at one end, polyethylene glycol and/or polypropylene glycol structure ("Pelletex PC-2421" manufactured by Miyoshi Oil & Fats, number average molecular weight approximately 490)
B-2: Polyether with an alkyl group having 16 or 18 carbon atoms at one end and a polyethylene glycol structure ("Pelletex 2828" manufactured by Miyoshi Oil & Fats, number average molecular weight approximately 830)
B-3: Polyether with an alkyl group having 12 or 14 carbon atoms at one end and a polyethylene glycol structure ("Pelletex 2465" manufactured by Miyoshi Oil & Fats, number average molecular weight approximately 1,960)
B-4: Polyether with an alkyl group having 12 carbon atoms at one end, polyethylene glycol and/or polypropylene glycol structure ("Pelletex PC-2465" manufactured by Miyoshi Oil and Fat, polyether with a number average molecular weight of about 2,740)
B-5 (comparative example): A polyether with a polyethylene glycol structure and a hydrocarbon group having 18 carbon atoms at one end and an unsaturated bond ("Pelletex 2917H" manufactured by Miyoshi Oil & Fats, with a number average molecular weight of approximately 360) polyether)
All of the above components B-1 to B-5 are treated to remove alkali metals derived from the metal catalyst remaining as impurities so as not to impair heat resistance and transmittance.
B-6: Polyoxyalkylene bisphenol A ether with 18 ethylene oxides (“Bisol 18EN” manufactured by Toho Chemical Industry, number average molecular weight approximately 1,010)
B-7: Polyoxyalkylene bisphenol A ether with 30 ethylene oxides (“Bisol 30EN” manufactured by Toho Chemical Industry, number average molecular weight approximately 1,600)

(C component)
C: Triphenylphosphine (manufactured by Johoku Kagaku Kogyo Co., Ltd.: JC-263)
(Other ingredients)
(Release agent)
D: Glycerin monostearate (manufactured by Riken Vitamin Co., Ltd.: Rikemar S-100A)
(Evaluation method)
(1) Spectral light transmittance Pellets obtained from each composition of Examples were dried at 120°C for 5 hours in a hot air circulation dryer, and then molded using an injection molding machine [J85-ELIII manufactured by Japan Steel Works, Ltd.]. A molded plate with a width of 50 mm, a length of 90 mm, and a thickness of 2 mm was molded at a molding temperature of 270° C. and a mold temperature of 80° C. The spectral light transmittance of this 2 mm thick molded plate was measured at 1 nm intervals in the wavelength range of 200 nm to 800 nm using a spectrophotometer [Cary 5000 manufactured by Agilent Corporation]. The average spectral light transmittance in the wavelength range of 340 nm to 420 nm was calculated from the obtained spectral light transmittance.
The higher the value of the spectral light transmittance, the less attenuation of light and the better the light guide performance. When the spectral light transmittance was 87.0% or more, it was marked as ○, and when it was less than 87.0%, it was marked as ×.

(2) Molded plate hue The pellets obtained from each composition of the examples were dried at 120°C for 5 hours in a hot air circulation dryer, and using an injection molding machine [J85-ELIII manufactured by Japan Steel Works, Ltd.], A molded plate having a width of 50 mm, a length of 90 mm, and a thickness of 2 mm was molded at a molding temperature of 270° C. and a mold temperature of 80° C. This molded plate with a thickness of 2 mm was measured in accordance with JIS-K7105 using an integrating sphere spectrophotometer [CE-7000A manufactured by X-Rite] under the conditions of light source D65, viewing angle 10 degrees, and transmission method. *, b*) were measured.
The higher the b* value of this molded plate, the more easily the molded plate discolors to yellow. If the b* value was 0.4 or less, it was marked as ○, and if it exceeded 0.4, it was marked as ×.

(3) Moisture and heat resistance Pellets obtained from each composition of Examples were dried at 120°C for 5 hours in a hot air circulation dryer, and molded using an injection molding machine [J85-ELIII manufactured by Japan Steel Works, Ltd.]. A molded plate having a width of 50 mm, a length of 90 mm, and a thickness of 2 mm was molded at a temperature of 270° C. and a mold temperature of 80° C. This molded plate was subjected to moist heat treatment (temperature 120°C, 24 hours) using a steam sterilizer [SN-510 manufactured by Yamato Scientific Co., Ltd.], and the haze and viscosity average molecular weight (Mv) before and after the moist heat treatment were measured. . The haze of the molded plate was measured according to JIS-K7361-1, and the viscosity average molecular weight (Mv) was measured by the method below.

Measurement of viscosity average molecular weight (Mv) The specific viscosity (η _SP ) calculated by the following formula is determined from a solution of polycarbonate resin dissolved in 100 ml of methylene chloride at 20°C using an Ostwald viscometer, and the determined specific viscosity ( The viscosity average molecular weight Mv was calculated from η _SP ) using the following formula.
Specific viscosity (η _SP )=(t−t ₀ )/t ₀
[ _t0 is the number of seconds that methylene chloride falls, t is the number of seconds that the sample solution falls]
η _SP /c=[η]+0.45×[η] ² c (however, [η] is the limiting viscosity)
[η]=1.23×10 ⁻⁴ Mv ^0.83
c=0.7

The higher the Haze after the moist heat treatment, the lower the transparency of the molded plate, and the greater the decrease in the viscosity average molecular weight after the moist heat treatment, the easier it is to hydrolyze the resin. The increase in Haze before and after the moist heat treatment was expressed as ΔHaze, and those with ΔHaze of 8.0 or less were marked with ○, and those with ΔHaze of more than 8.0 were marked with ×. In addition, the decrease in Mv before and after moist heat treatment is expressed as ΔMv, and those with Mv after treatment of 14,000 or more or ΔMv of 2,000 or less are ○, and those with Mv after treatment are less than 14,000 and Those whose ΔMv exceeded 2,000 were marked as ×.

(4) Melt volume flow rate (MVR)
The pellets obtained from each composition of the examples were dried at 120°C for 4 hours in a hot air circulation dryer, and the melt volume flow rate ( MVR) was measured. Melt volume flow rate of 80 cm ³ /10 minutes or more was marked ◎, 60 cm ³ /10 minutes or more but less than 80 cm ³ /10 minutes was marked ○, and less than 60 cm ³ /10 minutes was marked ×.

[Examples 1 to 9 and Comparative Examples 1 to 4]
Component A, B component, C component, and other components were mixed in a blender in the amounts listed in Table 1, and then melt-kneaded using a vented twin-screw extruder to obtain pellets. The vented twin-screw extruder used was TEX30α manufactured by Japan Steel Works (fully meshed, rotating in the same direction, double threaded screws). The extrusion conditions were a discharge rate of 30 kg/h, a screw rotation speed of 270 rpm, a vent vacuum degree of 1 kPa, and an extrusion temperature of 260°C. The evaluation results are shown in Table 1.

Examples 1 to 9 all have high transparency, no yellowing, heat and humidity resistance, and excellent fluidity. On the other hand, those that do not contain component B, such as Comparative Examples 1 and 2, are inferior in transparency and fluidity compared to those that contain component B. In addition, when the B component is excessive as in Comparative Example 3, transparency is impaired and yellowing and deterioration of heat and humidity resistance are observed. Even when it is a base, transparency is impaired and yellowing and deterioration of heat and humidity resistance are observed.

The polycarbonate resin composition of the present invention has excellent light guiding properties, little yellowing during molding or deterioration in a moist heat environment, and excellent fluidity, so molded products obtained from the polycarbonate resin composition It is extremely useful for various industrial applications such as LED lighting and other lighting fields, OA equipment fields, electrical and electronic equipment fields, and automobile fields.

Claims (6)

(A) For 100 parts by weight of polycarbonate resin (component A), (B) a polyether polymer having an alkyl group at at least one terminal and/or a number average molecular weight of 300 to 3,500. A polycarbonate resin composition having light guiding performance, characterized in that it contains 0.2 to 1.5 parts by weight of polyoxyalkylene bisphenol A ether (component B) having a molecular weight of 300 to 2,000. A claim that component B is at least one polyether polymer selected from the group consisting of polyethers having an alkyl group at at least one end represented by the following formula [1] and/or the following formula [2] Item 2. A polycarbonate resin composition having the light guiding performance according to item 1.
(In the formula, m is an integer of 10 to 18, and n is an integer of 5 to 40.)
(In the formula, m is an integer from 12 to 18, and n is an integer from 4 to 50.) The polycarbonate resin composition having light guiding performance according to claim 1, wherein component B is a polyoxyalkylene bisphenol A ether represented by the following formula [3].
(In the formula, OR' represents ethylene oxide or propylene oxide, and n is an integer from 3 to 20.) The light guide according to claim 1, which contains (C) 0.01 to 0.1 parts by weight of a phosphorus compound having a phenyl group (component C) based on 100 parts by weight of the polycarbonate resin (component A). Polycarbonate resin composition with performance. The polycarbonate resin composition having light guiding performance according to claim 4, wherein component C is a phosphorus compound having three phenyl groups represented by the following formula [4].
A molded article made of a polycarbonate resin composition having the light guiding performance according to claim 1.