JP6918536B2 - Polycarbonate resin composition - Google Patents

Description

The present invention relates to a polycarbonate resin composition. More specifically, the present invention relates to a polycarbonate resin composition in which light reflection characteristics, dimensional stability and thermal stability are improved by using a polycarbonate-polydiorganosiloxane copolymer resin, a titanium dioxide pigment and a specific inorganic filler in combination.

Polycarbonate resin is widely used in electrical, mechanical, automobile, medical applications, etc. because it has excellent transparency, heat resistance, mechanical strength, and the like. Further, there is a resin composition which is highly filled with a white pigment typified by a titanium dioxide pigment and has excellent light reflectivity. Molded products made of the resin composition are used in reflectors for backlights of liquid crystal displays, reflectors for illuminated push switches and photoelectric switches, display internal frames of vending machines, strobe reflectors, and the like.

In such a resin composition, not only performance such as high brightness and high white hue, but also strict molding conditions (for example, high injection speed and high molding temperature) are required to cope with thinning and miniaturization of molded products. Etc.) are also required to have thermal stability that can withstand. That is, it is required that yellowing due to thermal deterioration during molding, appearance defects such as silver streaks, and reduction in the molecular weight of the polycarbonate resin do not occur even under such severe molding conditions. Such yellowing lowers the light reflection characteristics, and it is assumed that silver streaks do not exist in the molded product in the first place, and a decrease in the molecular weight of the polycarbonate resin causes a decrease in mechanical properties and heat resistance. In addition, from the viewpoint of energy saving in recent years, high light reflectivity is required so that the reflection efficiency can be improved, and even in thin-walled and miniaturized molded products, high light-shielding property is required so that the amount of reflected light is not lost due to light transmission. There is. In such a requirement, a large amount of titanium dioxide pigment may be added. As a result, yellowing due to thermal deterioration of the resin during molding, appearance defects such as silver streaks, and a decrease in the molecular weight of the polycarbonate resin are more likely to occur. Therefore, higher thermal stability is required in the polycarbonate resin composition containing the titanium dioxide pigment.

It is known that aluminum oxide and organosiloxane are used as surface treatment agents as a heat-stabilizing formulation of titanium dioxide pigments (see Patent Document 1). Further, it is known that silver streak can be reduced by using a titanium dioxide pigment having an aluminum oxide content of 0.1 to 2% by weight as a surface treatment agent for an engineering plastic such as a polyphenylene ether resin. Yes (see Patent Document 2). Further, it is known that polyorganohydrogensiloxane is used in the titanium dioxide-containing polycarbonate resin composition (see Patent Document 3). Furthermore, dimensional stability may be required for materials such as reflectors and their peripheral members used for backlights of liquid crystal displays such as computers and televisions, such as reflective frames, and polycarbonate resins, titanium dioxide, and organic metal salts. A composition containing an inorganic filler has been proposed for the purpose of improving the dimensional accuracy of the resin composition containing the above. (See Patent Document 4). However, it cannot be said that this composition has sufficiently improved the decrease in the molecular weight of the polycarbonate resin due to the blending of the inorganic filler and the accompanying decrease in the mechanical properties and heat resistance.

Special Publication No. 60-3430 Japanese Unexamined Patent Publication No. 11-60743 Special Publication No. 63-26140 Japanese Unexamined Patent Publication No. 2003-15657

An object of the present invention is to provide a polycarbonate resin composition having improved light reflection characteristics, dimensional stability and thermal stability.

As a result of diligent studies to solve the above problems, the present inventors have added a titanium dioxide pigment and a specific inorganic filler to a resin component composed of a polycarbonate-polydiorganosiloxane copolymer resin and an aromatic polycarbonate resin. It has been found that a polycarbonate resin composition having improved light reflection characteristics, dimensional stability and thermal stability can be obtained. That is, the above problem is 100 parts by weight of a resin component composed of (A) polycarbonate-polydiorganosiloxane copolymer resin (component A) 10 to 100% by weight and (B) aromatic polycarbonate resin (component B) 0 to 90% by weight. On the other hand, at least one kind of inorganic material selected from the group consisting of (C) titanium dioxide pigment (C component) by 10 to 40 parts by weight, (D) needle-like inorganic filler, fibrous inorganic filler and plate-like inorganic filler. It contains 10 to 40 parts by weight of the filler (D component) and 0.01 to 1 part by weight of the (E) phosphate stabilizer (E component), and has a linear expansion coefficient of 0.5 × in the parallel direction at 23 to 55 ° C. It is achieved by a polycarbonate resin composition which is 10 ^{-4 / ° C or less.}

Hereinafter, details of each component of the present invention will be described.
(Component A: Polycarbonate-polydiorganosiloxane copolymer resin)
The polycarbonate-polydiorganosiloxane copolymer resin used as the component A 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 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. They may be different, where a and b are integers 1 to 4, respectively, 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 of, and if there are more than one, they may be the same or different, c is an integer of 1-10 and d is an integer of 4-7.)]

（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 carbon atoms 1 to 10. 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. More preferably, 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 1.0% by weight to 10.% by weight based on the total weight of the polycarbonate resin composition. 0% by weight is preferable, more preferably 2.0% by weight to 10.0% by weight, further preferably 2.0% by weight to 8.0% by weight, and most preferably 3.0% by weight to 8% by weight. It is 0.0% by weight. If the content of the polydiorganosiloxane component is less than 1.0% by weight, the low temperature impact resistance and thermal stability are not sufficient, and if it exceeds 10.0% by weight, the appearance may be poor during molding and the heat resistant temperature may be lowered. It is not preferable because it exists. 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.)

The polycarbonate-polydiorganosiloxane copolymer resin used as the component A of the present invention is a polycarbonate-polydiorganosiloxane copolymer resin in which a polydiorganosiloxane domain having an average size of 5 to 18 nm is present in the matrix of the polycarbonate polymer. Is preferable. The average size of the polydiorganosiloxane domain is more preferably 5 to 15 nm, even more preferably 5 to 12 nm, and most preferably 8 to 12 nm. If the average size is less than 5 nm, the low temperature impact resistance is not sufficient, and if it exceeds 18 nm, the appearance may be poor during molding, which is not preferable.

The average size of this polydiorganosiloxane domain is evaluated by the Small Angle X-ray Scattering (SAXS) method. The small-angle X-ray scattering method is a method for measuring diffuse scattering / diffraction that occurs in a small-angle region where the scattering angle (2θ) is less than 10 °. In this small-angle X-ray scattering method, when a substance has regions having different electron densities and having a size of about 1 to 100 nm, diffuse scattering of X-rays is measured by the difference in electron densities. The particle size of the object to be measured is determined based on the scattering angle and the scattering intensity. When the polydiorganosiloxane domain is dispersed in the matrix of the polycarbonate-polydiorganosiloxane copolymer used as the component A of the present invention, the X-rays are diffusely scattered due to the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domain. Occurs. The scattering intensity I at each scattering angle (2θ) in the range where the scattering angle (2θ) is less than 10 ° is measured, the small angle X-ray scattering profile is measured, the polydiorganosiloxane domain is a spherical domain, and the particle size distribution varies. From the tentative particle size and the tentative particle size distribution model, a simulation is performed using commercially available analysis software to obtain the average size of the polydiorganosiloxane domain. According to the small-angle X-ray scattering method, the average size of polydiorganosiloxane domains dispersed in a matrix of polycarbonate polymers, which cannot be accurately measured by observation with a transmission electron microscope, can be measured accurately, easily, and with good reproducibility. Can be done.

Next, a method for producing the above-mentioned preferable polycarbonate-polydiorganosiloxane copolymer resin will be described below. By reacting 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 for producing a 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 component A 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 that induces the carbonate structural unit represented by the general formula [2] while stirring the mixed solution is added to the mixed solution. By adding at a rate of 0.01 mol / min or less per 1 mol of the amount of dihydric phenol (I) charged in the preparation, and interfacial polycondensation of the dihydroxyaryl-terminated polydiorganosiloxane and the chlorohomate compound. , Polycarbonate-polydiorganosiloxane copolymer resin is obtained.

The polycarbonate-polydiorganosiloxane copolymer resin used as the component A 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 component A of the present invention is preferably in the range of 13,000 to 25,000, more preferably 13,000 to 21,000, and 16,000 to 21, The range of 000 is more preferable, and the range of 16,000 to 20,000 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 component A 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 component A is 10 to 100% by weight, preferably 30 to 100% by weight, and more preferably 50 to 100% by weight in 100% by weight of the resin component. If the content of the component A is less than 10% by weight, the thermal stability is not sufficient, and the decrease in molecular weight during extrusion or molding becomes large.

(B component: polycarbonate resin)
The polycarbonate resin used as the B component of the present invention is usually obtained by reacting a dihydroxy compound and a carbonate precursor by an interfacial transesterification method or a melt transesterification method, or a carbonate prepolymer by a solid phase transesterification 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) cyclohexa , 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-dimethyladamantan 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 B component 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, dibutyl carbonate and the like. 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 B component 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 B component of the present invention is preferably in the range of 13,000 to 25,000, more preferably 13,000 to 21,000, and preferably in the range of 16,000 to 21,000. Even more preferable, the range of 16,000 to 20,000 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 Mv.

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 Mv ^0.83
c = 0.7

The total amount of Cl (chlorine) in the polycarbonate resin used as the component B 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 will deteriorate, which is not preferable.

(C component: titanium dioxide pigment)
The C component of the present invention is a titanium dioxide pigment. As such titanium dioxide pigments, those usually used for various coloring applications can be used, and are widely known by themselves. There is also a titanium dioxide pigment consisting of 100% by weight of TiO ₂ (in the present invention, the titanium dioxide component of the titanium dioxide pigment _{is referred to as "TiO 2} ", and the entire pigment including the surface treatment agent is referred to as "titanium dioxide pigment". write). However, surface treatment is usually performed with oxides of various metals such as aluminum, silicon, titanium, zirconium, antimony, tin and zinc. Also in the present invention, the preferred titanium dioxide pigment is one that has been surface-treated with other metal oxides. The metal oxide component for these surface treatments may be in a mode in which a _{part of the metal oxide component is present inside the TiO 2 particles.}

Further, it is more preferable that the titanium dioxide pigment of the C component is surface-treated with an organic compound. As such a surface treatment agent, various treatment agents such as polyol-based, amine-based, and silicone-based can be used. Examples of the polyol-based surface treatment agent include pentaerythritol, trimethylolethane, and trimethylolpropane, and examples of the amine-based surface treatment agent include an acetate of triethanolamine and an acetate of trimethylolamine. Examples of the silicone-based surface treatment agent include halogen-substituted organosilicon compounds and organosilicon compounds containing an alkoxy group and / or Si—H group, and the latter organosilicon compound is particularly preferable. Alkoxychlorosilane is exemplified as the halogen-substituted organosilicon compound, and alkylalkoxysilane, alkylalkoxysiloxane, alkylhydrogensiloxane and the like are exemplified as the organosilicon compound containing an alkoxy group and / or Si—H group.

In such a silane compound and a siloxane compound, a part of the alkyl group may be substituted with a phenyl group, but it is more preferable that none of them is substituted with a phenyl group. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group.

The alkylalkoxysilane compound may contain any of 1 to 3 alkoxy groups, or may be a mixture thereof, but 2 to 3 alkoxy groups are preferable, and 3 alkoxy groups are particularly preferable. .. Specific examples of the alkylalkoxysilane compound include methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, isoptyltrimethoxysilane, methyloctyldimethoxysilane, decyltrimethoxysilane, and octadecyltrimethoxysilane. Illustrated.

The content ratio of the alkoxy group and the Si—H group in the siloxane compound 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. A range of 6 mol / 100 g is more preferred. Such a ratio can be obtained by measuring the amount of hydrogen or alcohol generated per unit weight of the siloxane compound by the alkaline decomposition method.

Generally, the structure of a siloxane 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 ) Bifunctional siloxane unit such as 2SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ = CH) SiO, (C ₆ H _{5) 2SiO} , 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 ) SiO _3/2 Etc., trifunctional siloxane unit, Q unit: a tetrafunctional siloxane unit represented by SiO ₂ . Specifically, the structure of the above-mentioned siloxane compound has, as a demonstrative formula, D _n , T _p , M _m D _n , M _m T _p , M _m Q _q , M _m D _n T _p , M _m D _n Q _q. , M _m T _p Q _q , M _m D _n T _p Q _q , D _n T _p , D _n Q _q , D _n T _p Q _q . Among these, the preferred structures of the silicone compounds are M _m D _n , M _m T _p , M _m D _n T _p , M _m D _n Q _q , and more preferable structures are M _m D _n or M _m D _n. It is T _p. Here, the coefficients m, n, p, and q in the demonstrative formulas are integers of 1 or more representing the degree of polymerization of each siloxane unit, and the total of the coefficients in each siloxane formula is the average degree of polymerization of the siloxane compound. .. This average degree of polymerization is preferably in the range of 2 to 150, more preferably in the range of 3 to 80. When any of m, n, p, and q has a numerical value of 2 or more, it can be a siloxane unit of 2 or more types having different hydrogen atoms and organic residues to be bonded.

The amount of the organic compound to be surface-treated is preferably 1% by weight or less, more preferably 0.6% by weight or less per 100% by weight of the C component. On the other hand, the lower limit is 0.05% by weight or more. Titanium dioxide pigments surface-treated with an organosilicon compound containing an alkoxy group and / or a Si—H group provide better light reflectivity to the resin composition of the present invention.

Preferable embodiments of the titanium dioxide pigment of the present invention include (i) weight loss from 23 ° C. to 100 ° C. according to its thermal weight analysis (TGA), (a) weight loss from 23 ° C. to 300 ° C., and (b) weight loss from 23 ° C. to 300 ° C. ) When the weight is%, 0.05 ≦ (b) − (a) ≦ 0.6 is satisfied, and (ii) the concentration ratios derived from the Ti element, the Al element, and the Si element in the fluorescent X-ray measurement are taken. When (c), (d) and (e) are set, 0.001 ≦ (d) / (c) ≦ 0.01 is satisfied, and 0.001 ≦ (e) / (c) ≦ 0.02. It meets.

The lower limit of the values (b)-(a) is more preferably 0.15, and the upper limit of such values is more preferably 0.3. The lower limit of (d) / (c) is more preferably 0.003, and the upper limit thereof is more preferably 0.01. The lower limit of (e) / (c) is more preferably 0.005, and the upper limit thereof is more preferably 0.015.

When the above (b)-(a) is 0.6 or less, (d) / (c) is 0.01 or less, and (e) / (c) is 0.02 or less, the effect of thermal stability becomes more effective. Remarkably demonstrated. When (b)-(a) is 0.05 or more, and (d) / (c) and (e) / (c) are 0.001 or more, a good hue is obtained, especially at the time of high filling. Excellent light reflection characteristics can be obtained. The thermogravimetric analysis (TGA) measurement under the above condition (i) is performed under the measurement conditions in which the temperature is raised from 23 ° C. to 20 ° C./min in a nitrogen gas atmosphere to 900 ° C. in a TGA measuring device. .. The fluorescent X-ray measurement under the above condition (ii) is performed by the basic parameter method.

_{The crystal form of TiO 2} in the C component may be either anatase type or rutile type, and they can be mixed and used as necessary. The rutile type is more preferable in terms of initial mechanical properties and long-term weather resistance. Anatase-type crystals may be contained in the rutile-type crystals. Further, as _{the method for producing TiO 2} , a product produced by a sulfuric acid method, a chlorine method, or various other methods can be used, but the chlorine method is more preferable. Further, the titanium dioxide pigment of the present invention is not particularly limited in its shape, but a particulate pigment is more preferable. The average particle size of the titanium dioxide pigment is preferably 0.01 to 0.4 μm, more preferably 0.1 to 0.3 μm, and even more preferably 0.1 to 0.25 μm. Such an average particle size is calculated by measuring each single particle size from electron microscope observation and averaging the numbers.

The TiO ₂ surface can be coated with various metal oxides by various commonly used methods. For example, it is manufactured from the following steps 1) to 8). That is, 1) untreated TiO ₂ after dry pulverization is used as an aqueous slurry, 2) the slurry is wet pulverized to be atomized, 3) fine particle slurry is collected, and 4) the fine particle slurry is water-soluble with a metal salt. Add compound, 5) Neutralize and _{coat TiO 2} surface with metal hydroxide, 6) Remove by-products, adjust slurry pH, filter, and clean with pure water, 7) Cleaned Examples thereof include drying the cake and 8) crushing the dried product with a jet mill or the like. In addition to such a method, for example, a method of reacting an active metal compound with _{TiO 2 particles in a gas phase can be mentioned.} Further _{, in coating the TiO 2} surface with the metal oxide surface treatment agent, firing is performed after the surface treatment, surface treatment is performed again after the surface treatment, and firing is performed after the surface treatment and the surface treatment is performed again. It is possible. Further, as the surface treatment with metal oxide, either a high-density treatment or a low-density (porous) treatment can be selected.

The above conditions (i) and (ii) can be adjusted by adjusting the metal oxide for the surface treatment and the conditions of the firing treatment thereof. The titanium dioxide pigment of the present invention is surface-treated with aluminum oxide and silicon oxide as is clear from such conditions. These may be surface-treated as a mixture in any order, but are preferably treated with aluminum oxide followed by silicon oxide. More preferably, it is a titanium dioxide pigment surface-treated with an organosilicon compound containing an alkoxy group and / or a Si—H group after being treated with the metal oxide as described above.

The content of the C component is 10 to 40 parts by weight, preferably 20 to 35 parts by weight, and more preferably 25 to 35 parts by weight with respect to 100 parts by weight of the resin component. If the content of the C component is less than 10 parts by weight, the reflectance is inferior, and if it exceeds 40 parts by weight, the thermal stability is deteriorated.

(D component: inorganic filler)
The inorganic filler used as the D component of the present invention has any of needle-like, fibrous and plate-like shapes. When an inorganic filler having no needle-like, fibrous, or plate-like shape is used, the reinforcing effect of the inorganic filler is small, so that the linear expansion integer becomes large and the dimensional stability deteriorates. The needle-shaped inorganic filler is an inorganic filler having a whisker-like shape, a columnar shape, or the like, and is selected from wallastonite, boehmite, and the like. The fibrous inorganic filler refers to a thin and long fibrous inorganic filler, and is selected from glass fiber, metal fiber, ceramic fiber and the like. The plate-shaped inorganic filler is an inorganic filler having a shape such as flaky or scaly, and is selected from talc, mica, glass flakes and the like. Among the above-mentioned inorganic fillers, glass, talc, mica and wallastnite are particularly suitable. The D component of the present invention preferably has a high aspect ratio represented by length / diameter or major axis / thickness.

(Glass)
The glass fiber is not particularly limited in the glass composition of A glass, C glass, E glass and the like, and may _{contain components such as TiO 2} , SO ₃ and P ₂ O ₅ depending on the case. However, E glass (non-alkali glass) is more preferable. The glass fiber is formed by stretching molten glass by various methods and quenching it into a predetermined fibrous form. The quenching and stretching conditions in such a case are not particularly limited. Further, the cross-sectional shape may be a shape other than a perfect circle, such as an ellipse, a cocoon, or a trefoil, in addition to a perfect circle. Further, a perfect circular glass fiber and a glass fiber having a shape other than the perfect circle may be mixed.

The fiber diameter of the glass fiber is preferably 1 to 25 μm, more preferably 3 to 17 μm. If the fiber diameter is too small, the fiber tends to break and the rigidity tends to decrease. In addition, since the surface area is large, a relatively large amount of coating material is required, and when flame retardancy is required, it tends to have an adverse effect. If the fiber diameter is too large, the appearance of the molded product tends to deteriorate.

The fiber length of the glass fiber is preferably 50 to 500 μm, more preferably 100 to 400 μm, still more preferably 120 to 300 μm as the number average fiber length in the pellet or molded product made of the thermoplastic resin composition of the present invention. Is. The number average fiber length is a value calculated by an image analyzer from the residue of the glass fiber collected after dissolving the molded product in a solvent or decomposing the resin with a basic compound by observing with an optical microscope or the like. .. Further, when calculating such a value, a value having a fiber diameter of 10 μm or less is a value obtained by a method that does not count.

Examples of the plate-shaped glass filler include metal-coated glass flakes, glass flakes containing metal oxide-coated glass flakes, and the like. The glass flakes used as the base of the plate-shaped glass filler are plate-shaped glass fillers produced by a method such as a cylindrical blow method or a sol-gel method. Various sizes of raw materials for such glass flakes can be selected depending on the degree of pulverization and classification. The average particle size of the glass flakes used as the raw material is preferably 10 to 1000 μm, more preferably 20 to 500 μm, and even more preferably 30 to 300 μm. This is because those in the above range are excellent in both handleability and molding processability. Normally, a plate-shaped glass filler is cracked by melt-kneading with a resin, and its average particle size is reduced. The number average particle size of the plate-shaped glass filler in the resin composition is preferably 10 to 200 μm, more preferably 15 to 100 μm, still more preferably 20 to 80 μm. The number average particle diameter is calculated by an image analyzer from an image obtained by observing a plate-shaped glass filler collected by treatments such as high-temperature ashing of a molded product, dissolution with a solvent, and decomposition with a chemical. Is the value to be. Further, when calculating such a value, a value having a length shorter than that of the flake thickness as a guide is not counted. The thickness is preferably 0.5 to 10 μm, more preferably 1 to 8 μm, and even more preferably 1.5 to 6 μm. The plate-shaped glass filler having the above number average particle size and thickness achieves good mechanical strength, appearance, and moldability.

The glass composition of the fibrous glass filler and the plate-shaped glass filler is not particularly limited as various glass compositions typified by A glass, C glass, E glass and the like are applied. Such a glass filler may contain components such as _{TiO 2} , SO ₃ and P ₂ O _{5, if necessary.} Among these, E glass (non-alkali glass) is more preferable. Further, as the glass filler, those which have been surface-treated with a well-known surface treatment agent such as a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent are preferable from the viewpoint of improving mechanical strength. In addition, glass fibers (including those coated with metal or metal oxide) and glass flakes (including those coated with metal or metal oxide) are olefin resins, styrene resins, acrylic resins, Those that have been focused with a polyester resin, an epoxy resin, a urethane resin, or the like are preferably used. The amount of the sizing agent adhered to the focusing-treated filler is preferably 0.5 to 8% by weight, more preferably 1 to 4% by weight, based on 100% by weight of the filler.

Further, the fibrous glass filler and the plate glass filler of the present invention include those in which different materials are surface-coated. Metals and metal oxides are preferably exemplified as such dissimilar materials. Examples of the metal include silver, copper, nickel, and aluminum. Examples of the metal oxide include cerium oxide, zirconium oxide, iron oxide, aluminum oxide, and silicon oxide. The surface coating method for such 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, CVD method, etc. (For example, thermal CVD, MOCVD, plasma CVD, etc.), PVD method, sputtering method and the like can be mentioned.

(talc)
Talc and the in the present invention, the chemical compositional a hydrated magnesium silicate, is generally represented by the chemical formula _{4SiO 2 · 3MgO · 2H 2 O} , a scaly particles having a regular layered structure, also the composition thereof include a SiO ₂ 56 to 65 wt%, the MgO 28 to 35 wt%, and a _{H 2} O about 5 wt%. Other small amounts of components include Fe ₂ O ₃ 0.03 to 1.2% by weight, Al ₂ O ₃ 0.05 to 1.5% by weight, Ca O 0.05 to 1.2% by weight, and K _{2 O.} Contains 0.2% by weight or less, Na ₂ O contains 0.2% by weight or less, and the like. The particle size of talc has an average particle size of 0.1 to 15 μm (more preferably 0.2 to 12 μm, still more preferably 0.3 to 10 μm, particularly preferably 0.5 to 5 μm) measured by the sedimentation method. It is preferably in the range. Further, it is particularly preferable to use talc having a bulk density of 0.5 (g / cm ^{3) or more as a raw material.} _{The average particle size of talc refers to D 50} (median diameter of particle size distribution) measured by the X-ray transmission method, which is one of the liquid phase precipitation methods. Specific examples of the device for performing such measurement include Sedigrap 5100 manufactured by Micromeritix.

There are no particular restrictions on the manufacturing method for crushing talc from rough stones, and axial flow milling methods, annular milling methods, roll milling methods, ball milling methods, jet milling methods, container rotary compression shear milling methods, etc. are used. can do. Further, the talc after crushing is preferably classified by various classifiers and has a uniform particle size distribution. There are no particular restrictions on the classifier, including impactor-type inertial force classifiers (variable impactors, etc.), Coanda effect-based inertial force classifiers (elbow jets, etc.), and centrifugal field classifiers (multi-stage cyclone, microplex, dispersion separator, etc.). , AccuCut, Turbo Classifier, Turboplex, Micron Separator, and Super Separator, etc.).

Further, the talc is preferably in an aggregated state in terms of its handleability and the like, and as such a production method, there are a method by degassing compression, a method of compressing using a sizing agent and the like. In particular, the degassing compression method is preferable because it is simple and does not mix unnecessary sizing agent resin components into the resin composition of the present invention.

(Mica)
As the mica, those having an average particle size of 10 to 100 μm measured by the microtrack laser diffraction method can be preferably used. More preferably, the average particle size is 20 to 50 μm. If the average particle size of mica is less than 10 μm, the effect of improving the rigidity is not sufficient, and if it exceeds 100 μm, the rigidity is not sufficiently improved, and the mechanical strength such as impact characteristics may be significantly reduced, which is not preferable. As the mica, those having a thickness of 0.01 to 1 μm actually measured by observation with an electron microscope can be preferably used. More preferably, the thickness is 0.03 to 0.3 μm. As the aspect ratio, preferably 5 to 200, more preferably 10 to 100 can be used. The mica used is preferably muscovite mica, and its Mohs hardness is about 3. Muscovite mica can achieve higher rigidity and higher strength than other mica such as florobite, and solves the problem of the present invention at a better level. Further, the mica may be pulverized by either a dry pulverization method or a wet pulverization method. The dry pulverization method is generally lower in cost, while the wet pulverization method is effective for pulverizing mica thinner and finer, and as a result, the effect of improving the rigidity of the resin composition is higher.

(Wallast Night)
The fiber diameter of wallastonite is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, and even more preferably 0.1 to 3 μm. The aspect ratio (average fiber length / average fiber diameter) is preferably 3 or more. The upper limit of the aspect ratio is 30 or less. Here, the fiber diameter is determined by observing the reinforcing filler with an electron microscope, determining the individual fiber diameters, and calculating the number average fiber diameter from the measured values. An electron microscope is used because it is difficult for an optical microscope to accurately measure the size of a target level. For the fiber diameter, the filler to be measured is randomly extracted from the image obtained by observation with an electron microscope, the fiber diameter is measured near the center, and the number average fiber is obtained from the obtained measured value. Calculate the diameter. The observation magnification is about 1000 times, and the number of measurements is 500 or more (600 or less is suitable for work). On the other hand, in the measurement of the average fiber length, the filler is observed with an optical microscope, the individual lengths are obtained, and the number average fiber length is calculated from the measured values. Observation with a light microscope begins with preparing a sample that is dispersed so that the fillers do not overlap very much. The observation is performed under the condition of 20 times the objective lens, and the observed image is captured as image data in a CCD camera having about 250,000 pixels. The fiber length is calculated by using an image analysis device for the obtained image data and using a program for obtaining the maximum distance between two points of the image data. Under such conditions, the size per pixel corresponds to a length of 1.25 μm, and the number of measurements is 500 or more (600 or less is suitable for work).

In order to sufficiently reflect the inherent whiteness of the wallastnite of the present invention in the resin composition, the iron content mixed in the raw material ore and the iron content mixed in due to the wear of the equipment when the raw material ore is crushed are separated by a magnetic separator. It is preferable to remove as much as possible. By such magnetic separator treatment, the iron content in wallastnite is preferably 0.5% by weight or less in terms of _{Fe 2} O _3.

The content of the D component is 10 to 40 parts by weight, preferably 20 to 40 parts by weight, and more preferably 25 to 35 parts by weight with respect to 100 parts by weight of the resin component. If the content of the D component is less than 10 parts by weight, sufficient dimensional stability cannot be obtained, and if it exceeds 40 parts by weight, the thermal stability deteriorates and the decrease in molecular weight during extrusion or molding becomes large.

(E component: phosphate stabilizer)
The phosphate-based stabilizer used as the E component of the present invention is used for the purpose of improving thermal stability during manufacturing or molding, and improving mechanical properties, hue, and molding stability. Phenyl tranquilizers include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl. Examples thereof include phosphate and diisopropyl phosphate, with preference given to triphenyl phosphate and trimethyl phosphate. The content of the E component is 0.01 to 1 part by weight, preferably 0.03 to 0.8 parts by weight, and more preferably 0.05 to 0.5 parts by weight with respect to 100 parts by weight of the resin component. be. If the content of the E component is less than 0.01 parts by weight, sufficient thermal stability cannot be obtained, and if it exceeds 1 part by weight, the hydrolysis resistance deteriorates.

(F component: UV absorber)
In the resin composition of the present invention, an ultraviolet absorber can be blended for the purpose of imparting light resistance. Specific examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2-hydroxy-4-benzyloxy. Benzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4 , 4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy- Examples thereof include 4-n-dodecyloxybenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. Specific examples of the ultraviolet absorber include 2- (2-hydroxy-5-methylphenyl) benzotriazol and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazol in the benzotriazole system. , 2- (2-Hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'- Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) ) Bentotriazol, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazol, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazo- Le, 2- (2-Hydroxy-5-tert-octylphenyl) benzotriazol, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazol, 2- (2-hydroxy-4-octoxyphenyl) ) Bentriazol, 2,2'-methylenebis (4-cumyl-6-benzotriazolphenyl), 2,2'-p-phenylenebis (1,3-benzoxazine-4-one), and 2- [2 -Hydroxy-3- (3,4,5,6-tetrahydrophthalimidemethyl) -5-methylphenyl] benzotriazol, and 2- (2'-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole Copolymerization of a vinyl-based monomer copolymerizable with the monomer or 2- (2'-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and a vinyl-based monomer copolymerizable with the monomer Examples thereof include a polymer having a 2-hydroxyphenyl-2H-benzotriazole skeleton such as a polymer. Specifically, the ultraviolet absorber is, in the hydroxyphenyltriazine system, for example, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-hexyloxyphenol, 2- (4, 6-Diphenyl-1,3,5-triazine-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-ethyloxyphenol , 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazine-2-yl) ) -5-Butyloxyphenol and the like are exemplified. Further, the phenyl group of the above-exemplified compound such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. A compound that has become a phenyl group is exemplified. Specific examples of the ultraviolet absorber are cyclic iminoesters, for example, 2,2'-p-phenylenebis (3,1-benzoxazine-4-one) and 2,2'-m-phenylenebis (3,1). -Benzooxazine-4-one), and 2,2'-p, p'-diphenylenebis (3,1-benzoxazine-4-one) and the like are exemplified. As the ultraviolet absorber, specifically, in the case of a cyanoacrylate type, for example, 1,3-bis-[(2'-cyano-3', 3'-diphenylacryloyl) oxy] -2,2-bis [(2-2-bis]. Examples thereof include cyano-3,3-diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene. Further, the above-mentioned ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that such an ultraviolet-absorbing monomer and / or a photostable monomer and a single amount of an alkyl (meth) acrylate or the like are used. It may be a polymer-type ultraviolet absorber copolymerized with the body. As the ultraviolet absorbing monomer, a compound containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of the (meth) acrylic acid ester is preferably exemplified. NS. Among the above, benzotriazole-based and hydroxyphenyltriazine-based are preferable in terms of ultraviolet absorption ability, and cyclic iminoester-based and cyanoacrylate-based are preferable in terms of heat resistance and hue. Specifically, for example, ChemiPro Kasei Co., Ltd. "Chemisorb 79" and the like can be mentioned. The UV absorber may be used alone or in a mixture of two or more. The blending amount of the ultraviolet absorber is preferably 0.01 to 1 part by weight, more preferably 0.05 to 0.8 part by weight, and further preferably 0.1 to 0.5 part by weight with respect to 100 parts by weight of the resin component. It is a department.

(Other additives)
In order to improve the thermal stability, hue, and releasability 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 other than the component E can be added to 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 other than the E component to the extent that hydrolyzability is not promoted. Examples of phosphorus-based stabilizers other than the E component include phosphorous 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.

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.

(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 above The resin composition of the present invention may contain other heat stabilizers other than the phosphorus-based stabilizers and hindered phenol-based stabilizers. 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) 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.

(III) Release Agent It is preferable to further add a mold release agent to the polycarbonate resin composition of the present invention for the purpose of improving productivity at the time of molding and reducing distortion of the molded product. As such a mold release agent, a known one can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, acid-modified and other functional group-containing compounds can also be used), silicone compound, fluorine compound (poly). Fluorooil such as fluoroalkyl ether), paraffin wax, beeswax and the like can be mentioned. Among them, a fatty acid ester is mentioned as a preferable release agent. Such fatty acid esters are esters of fatty alcohols and aliphatic carboxylic acids. Such an aliphatic alcohol may be a monohydric alcohol or a divalent or higher polyhydric alcohol. The carbon number of the alcohol is in the range of 3 to 32, more preferably in the range of 5 to 30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, and triacanthanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. In the fatty acid ester of the present invention, a polyhydric alcohol is more preferable. On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, bechenic acid, and the like. Saturated aliphatic carboxylic acids such as icosanoic acid and docosanoic acid, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and sethalic acid can be mentioned. .. Among the above, the aliphatic carboxylic acid preferably has 14 to 20 carbon atoms. Of these, saturated aliphatic carboxylic acids are preferable. Particularly stearic acid and palmitic acid are preferred. The above-mentioned aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from animal fats and oils such as beef tallow and lard and natural fats and oils such as palm oil and sunflower oil. Therefore, these aliphatic carboxylic acids are usually mixtures containing other carboxylic acid components having different carbon atom numbers. Therefore, also in the production of the fatty acid ester of the present invention, an aliphatic carboxylic acid produced from such natural fats and oils and in the form of a mixture containing other carboxylic acid components, particularly stearic acid and palmitic acid are preferably used. The fatty acid ester of the present invention may be either a partial ester or a total ester (full ester). However, a partial ester usually has a high hydroxyl value and easily induces decomposition of the resin at a high temperature, so that it is more preferably a full ester. The acid value of the fatty acid ester of the present invention is preferably 20 or less, more preferably 4 to 20, and even more preferably 4 to 12 from the viewpoint of thermal stability. The acid value can be substantially 0. The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1 to 30. Further, the iodine value is preferably 10 or less. The iodine value can be substantially 0. These characteristics can be determined by the method specified in JIS K 0070. Examples of the polyolefin wax include microcrystalline wax, Fischer-Tropsch wax, and α-olefin polymer. Those containing an acidic group are preferable in order to suppress the breakage and cracking of the D component and further to further improve the thermal stability of the resin composition. Examples of the acidic group include a carboxyl group, a carboxylic acid anhydride group, a sulfonic acid group, a sulfinic acid group, a phosphonic acid group and a phosphinic acid group. A suitable acidic group is at least one of a carboxyl group, a carboxylic acid anhydride group, a sulfonic acid group, a sulfinic acid group, a phosphonic acid group and a phosphinic acid group. In particular, a polyolefin-based wax having at least one acidic group selected from a carboxyl group, a carboxylic acid anhydride group and a phosphonic acid group is preferable, and a polyolefin-based wax having a carboxyl group and / or a carboxylic acid anhydride group is particularly preferable. In the acidic group-containing polyolefin wax, the concentration of the acidic group is preferably in the range of 0.05 to 10 meq / g, more preferably in the range of 0.1 to 6 meq / g, and further preferably in the range of 0.5 to 4 meq / g. The range. Further, the molecular weight of the olefin wax is preferably 1,000 to 10,000. The molecular weight is a weight average molecular weight calculated based on a calibration curve obtained from standard polystyrene in GPC (gel permeation chromatography). Further, a copolymer of α-olefin and maleic anhydride satisfying the conditions of such concentration and molecular weight is suitable. Such a copolymer can be produced by a melt polymerization method or a bulk polymerization method in the presence of a radical catalyst according to a conventional method. Here, as the α-olefin, those having an average carbon number of 10 to 60 can be preferably mentioned. More preferably, the α-olefin has an average carbon number of 16 to 60, and more preferably 25 to 55. The content of the release agent is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, still more preferably 0.05, based on 100 parts by weight of the total of the A component and the B component. ~ 0.5 parts by weight. In such a range, the polycarbonate resin composition has good releasability and roll releasability. In particular, such an amount of fatty acid ester provides a polycarbonate resin composition having good releasability and releasability without impairing good hue.

(Light reflection characteristics)
High reflectance is required for reflectors for backlights of liquid crystal displays, reflectors for illuminated push switches and photoelectric switches, display internal frames for vending machines, and light reflectors such as strobe reflectors. The reflectance of the resin composition in the present invention is preferably 90% or more, more preferably 91% or more, still more preferably 95% or more. If the reflectance is less than 90%, sufficient light reflection characteristics cannot be obtained, and the brightness may decrease when used as a light reflector.

(Dimensional stability)
Dimensional stability is required for materials such as reflectors and peripheral members used for backlights of liquid crystal displays such as computers and televisions, such as reflective frames. The smaller the coefficient of linear expansion of the resin composition, the better the dimensional stability. The coefficient of linear expansion in the parallel direction of the resin composition in the present invention at 23 to 55 ° C. is 0.5 × 10 ^-4 / ° C. or less, more preferably ^{0.4 × 10 -4} / ° C. or less, and 0.3 × 10 -4 / ° C. It ^{is more preferably 10 -4} / ° C or lower. If the coefficient of linear expansion is ^{greater than 0.5 × 10 -4} / ° C, dimensional stability deteriorates.

(Manufacturing of thermoplastic resin composition)
Any method is adopted for producing the thermoplastic resin composition of the present invention. For example, components A to E and optionally other additives 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 extruded granulation as necessary. Examples thereof include a method in which the premix is granulated by a vessel or a briquetting machine, then melt-kneaded by a melt-kneader typified by a bent twin-screw extruder, and then pelletized by a pelletizer.

In addition, each component is independently supplied to a melt kneader represented by a bent twin-screw extruder, or a part of each component is premixed and then supplied to the melt kneader independently of the remaining components. There is also a way to do it. As a method of premixing a part of each component, for example, a method of premixing components other than the component A and the component B in advance and then mixing the thermoplastic resin of the component A and the component B or directly supplying the component to the extruder can be mentioned. Be done.

As a method of premixing, for example, when the A component and the B component include those having a powder form, a master batch of the additive diluted with the powder is produced by blending a part of the powder and the additive to be blended. However, there is a method of using such a masterbatch. Further, there is also a method of independently supplying one component from the middle of the melt extruder. If some of the components to be blended are in liquid form, a so-called liquid injection device or liquid addition device can be used to supply the melt extruder.

As the extruder, one having a vent capable of degassing the moisture in the raw material and the volatile gas generated from the melt-kneaded resin can be preferably used. A vacuum pump is preferably installed from the vent to efficiently discharge the generated water and volatile gas to the outside of the extruder. It is also possible to install a screen for removing foreign substances and the like mixed in the extruded raw material in the zone in front of the die portion of the extruder to remove the foreign substances from the resin composition. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (disc filter, etc.) and the like.

Examples of the melt kneader include a Banbury mixer, a kneading roll, a single-screw extruder, and a multi-screw extruder having three or more shafts, in addition to the twin-screw extruder.

The resin extruded as described above is directly cut and pelletized, or the strands are cut with a pelletizer after forming the strands and pelletized. When it is necessary to reduce the influence of external dust and the like during pelletization, it is preferable to clean the atmosphere around the extruder. Furthermore, in the production of such pellets, various methods already proposed for polycarbonate resins for optical discs are used to narrow the shape distribution of pellets, reduce miscuts, and reduce fine powder generated during transportation or transportation. , And bubbles (vacuum bubbles) generated inside the strands and pellets can be appropriately reduced. With these formulations, it is possible to increase the cycle of molding and reduce the rate of defects such as silver. The shape of the pellet can be a general shape such as a cylinder, a prism, and a sphere, but more preferably a cylinder. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, still more preferably 2.5 to 3.5 mm.

(About a molded product made of the resin composition of the present invention)
In the resin composition of the present invention, various products can be produced by injection molding pellets obtained by the above-mentioned method. In such injection molding, not only ordinary molding methods, but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including injection of supercritical fluid), insert molding, and insert molding, depending on the intended purpose. Molded products can be obtained using injection molding methods such as in-mold coating molding, heat insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. The advantages of these various molding methods are already widely known. Further, either a cold runner method or a hot runner method can be selected for molding.

Further, the resin composition in 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.

Specific examples of the molded product in which the resin composition of the present invention is used include a reflector for a backlight of a liquid crystal display device. Examples of the light source of such a backlight include a cold cathode fluorescent lamp and a light emitting diode (LED, particularly a white LED), and are particularly suitable for an array of white LEDs.

Since the polycarbonate resin composition of the present invention has excellent light reflection characteristics, dimensional stability and thermal stability, it is suitably used for various light reflection materials. More specifically, various lamp reflectors can be mentioned, for example, reflectors for lighting such as fluorescent lamps, reflectors / reflectors for backlights of various display devices such as liquid crystal displays, reflectors for switches, and LED arrays. Examples thereof include a reflector of the above and a reflector in which these functions are combined. That is, the polycarbonate resin composition of the present invention is useful for various uses such as various electronic / electrical equipment, OA equipment, vehicle parts, mechanical parts, other agricultural materials, transport containers, play equipment, and miscellaneous goods, and is industrially effective. The effect is exceptional.

The embodiment of the present inventor is a collection of preferable ranges of each of the above 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.

The present invention will be further described below with reference to examples. The evaluation was based on the following method.
(1) Linear Expansion Coefficient After annealing treatment (drying at 120 ° C. × 1 h) from a strip-shaped molded product having a thickness of 40 mm obtained by injection molding, a 5 mm square test piece was cut out. The linear expansion coefficient of the test piece at 23 ° C to 55 ° C at a heating rate of 2 ° C / min using the linear expansion coefficient measuring device "TMA4000SE" manufactured by NETZSCH as the direction for measuring the resin flow direction during injection molding. Was measured.
(2) Reflectance A flat plate with a thickness of 2 mm obtained by injection molding is measured at 45 ° incident total light relative reflectance using a haze / transmittance / reflector HR-100 manufactured by Murakami Color Technology Research Institute Co., Ltd. did.
(3) Thermal stability The viscosity average molecular weight of the pellets obtained by melt-kneading was measured by the method described in the text. On the other hand, the viscosity average molecular weight of the polycarbonate powder before melt-kneading was also measured in the same manner. The value obtained by subtracting the molecular weight after the melt-kneading from the molecular weight before the melt-kneading was evaluated as ΔMv. It can be said that the smaller the ΔMv, the better the thermal stability.

[Examples 1 to 8 and Comparative Examples 1 to 7]
After mixing the components A to E excluding the component D and various additives in the respective blending amounts shown in the table with a blender, the obtained mixture was charged from the first supply port at the rearmost part of the extruder. For each of the various additives other than the D component, a premix with the polycarbonate resin was prepared in advance with a concentration of 10 to 100 times the blending amount as a guide, and then the whole mixture was mixed with a blender. On the other hand, the D component was charged from the second supply port in the middle of the cylinder using a side feeder. Each input amount was precisely measured by a measuring instrument [CWF manufactured by Kubota Co., Ltd.]. As the extruder, a vent type twin-screw extruder (TEX30XSST, Japan Steel Works, Ltd.) having a diameter of 30 mmφ was used. In the screw configuration, the kneading zone of the first stage was provided before the position of the side feeder, and the kneading zone of the second stage was provided after the position of the side feeder. Strands were extruded under the conditions of a cylinder-temperature and a die temperature of 300 ° C. and a vent suction degree of 3 kPa, cooled in a water bath, and then strand-cut with a pelletizer to pelletize. The pellets obtained above are dried at 120 ° C. for 5 hours using a hot air dryer, and then by an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 300 ° C. and a mold temperature of 80 ° C. Each evaluation test piece was prepared and each of the above evaluations was carried out. The results are shown in Table 1.

The details of each component used are as follows.
(Component A)
PC-1: Polycarbonate-polydiorganosiloxane copolymer resin powder having a viscosity average molecular weight of 19,400 obtained by the following production method [Production 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. The average number of repetitions in the formula p = about 37) In a solution prepared by dissolving 430 parts in 1600 parts of methylene chloride, the dihydroxyaryl-terminated polydiorganosiloxane becomes 0.0008 mol / min per 1 mol of the amount of divalent phenol (I). After adding at a rate to make it emulsified, 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. (Polydiorganosiloxane component content 8.2%, average size of polydiorganosiloxane domain 9 nm, viscosity average molecular weight 19,400)

(B component)
PC-2: Polycarbonate resin powder having a viscosity average molecular weight of 19,700 obtained by the following production 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 phosgene 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.

(C component)
C-1: Titanium dioxide pigment (manufactured by Regino Color Industry Co., Ltd .: white DCF-T-17007, crystal system = rutile, manufacturing method = chlorine method)
(D component)
D-1: Glass filler (chopped strand) (manufactured by Nitto Boseki Co., Ltd .: CS-3PE-455FB)
D-2: Talc (manufactured by Katsumitsuyama Mining Co., Ltd .: Victory Light TK-RC)
D-3: Mica (manufactured by Kinsei Matek Co., Ltd .: KDM200)
D-4: Wallast Night (manufactured by Kinsei Matek Co., Ltd .: SH-1250)
D-5: Powdered glass filler (component E)
E-1: Phosphate stabilizer (Daihachi Chemical Industry Co., Ltd. trimethyl phosphate (TMP))
(F component)
F-1: UV absorber (BASF: TINUVIN 234 (trade name))
(Other ingredients)
Release agent: Acid-modified olefin wax, which is a copolymer of maleic anhydride and α-olefin (manufactured by Mitsubishi Chemical Corporation: Diacarna PA30M)

As is clear from the above table, the compositions of Examples 1 to 8 have a reflectance of 90% or more, a linear expansion coefficient of 0.5 × 10 ^-4 / ° C. or less, a small ΔMv, and excellent light reflection. It can be seen that it has properties, dimensional stability and thermal stability. That is, it can be seen that the resin composition has properties suitable for a light reflecting material. On the other hand, Comparative Examples 1 and 2 containing no A component have a large ΔMv and are inferior in thermal stability. In Comparative Example 3 using the D component which is not in the shape of a needle, a fiber, or a plate, the linear expansion integer is large and the dimensional stability is inferior. In Comparative Example 4 which does not contain the C component, the reflectance is low and the light reflection characteristics are inferior, and in Comparative Example 5 which contains an excessive amount of the C component, ΔMv is large and the thermal stability is inferior. In Comparative Example 6 which does not contain the D component, the linear expansion integer is large and the dimensional stability is inferior, and in Comparative Example 7 which contains the D component excessively, ΔMv is large and the thermal stability is inferior.

The present invention provides a polycarbonate resin composition suitable for a light reflecting material. However, in addition to this, it is also possible to utilize the semiconductor property of the titanium dioxide pigment as a dielectric material, a heat storage material, or the like.

Claims (3)

Resin consisting of (A) polycarbonate-polydiorganosiloxane copolymer resin (component A) 10 to 100% by weight and (B) aromatic polycarbonate resin (component B) 0 to 90% by weight excluding polycarbonate-polydiorganosiloxane copolymer resin. At least selected from the group consisting of (C) 10 to 40 parts by weight of titanium dioxide pigment (C component), (D) needle-like, fibrous or plate-like glass, mica and wallastnite with respect to 100 parts by weight of the component. It contains 10 to 40 parts by weight of a kind of inorganic filler (D component) and 0.01 to 1 part by weight of (E) phosphate-based stabilizer (E component), and has a linear expansion coefficient of 0 in the parallel direction at 23 to 55 ° C. .5 × 10 ^-4 / ° C. or lower polycarbonate resin composition. The polycarbonate resin composition according to claim 1, which contains 0.01 to 1 part by weight of the (F) ultraviolet absorber (F component) with respect to 100 parts by weight of the resin component. The polycarbonate resin composition according to claim 1 or 2, which has a reflectance of 90% or more.