JP2016113563A - Polycarbonate resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition having improved color tone and color difference by outdoor exposure and a molded article thereof.SOLUTION: Color tone and color difference by outdoor exposure are improved in a polycarbonate resin composition containing 100 pts.mass of a polycarbonate resin containing a constitutional unit derived from a dihydroxy compound having a cyclic ether structure, 0.01 pts.wt. to 30 pts.wt. of titanium oxide and 0.01 pts.wt. to 1 pts.wt. of phosphoric ester metal slat and a molded article thereof.SELECTED DRAWING: None

Description

  The present invention relates to a polycarbonate resin composition and a molded article having improved hue and color difference in outdoor exposure.

  Polycarbonate is generally produced using raw materials derived from petroleum resources. However, in recent years, there is a concern about the exhaustion of petroleum resources, and provision of polycarbonate using raw materials obtained from biomass resources such as plants is required. In addition, since there is concern that global warming due to an increase and accumulation of carbon dioxide emissions will lead to climate change, etc., carbon neutral plant-derived monomers are used as raw materials even after disposal after use. Development of polycarbonate resin is required. In addition, the polycarbonate resin composition using various additives, fillers, and the like has been studied with the aim of applying the polycarbonate resin to various uses.

On the other hand, in the field of engineering plastics including polycarbonate resin, titanium oxide has been conventionally used for light reflecting members. Patent Document 1 describes a polycarbonate resin composition in which an aromatic polycarbonate resin is blended with titanium oxide and a fluorescent brightening agent.
In polycarbonates obtained by transesterification of isosorbide and diphenyl carbonate, polycarbonate resin compositions to which titanium oxide is added are proposed in Patent Documents 2 and 3 as being intended for use as light reflecting members.

JP 2008-195818 A JP 2009-191227 A JP 2012-214796 A

  However, according to the study of the present inventor, Patent Document 1 describes that the light resistance of a polycarbonate resin composition is improved by adding a fluorescent whitening agent, There was a need to improve the color difference. Also in Patent Documents 2 and 3, although various physical properties such as light resistance have been improved, there is room for improvement in hue and color difference in outdoor exposure because the colored components are decolored by exposure to sunlight. It was.

  An object of the present invention is to provide a polycarbonate resin composition having improved hue and color difference in outdoor exposure, and a molded article thereof.

As a result of intensive studies to solve the above problems, the present inventor has improved the hue and the color difference in outdoor exposure when the polycarbonate resin containing a specific structure polycarbonate resin, titanium oxide, and phosphate metal salt is used. As a result, the present invention has been reached. That is, the gist of the present invention is as follows.
[1] 0.01 parts by weight or more and 30 parts by weight or less of titanium oxide with respect to 100 parts by weight of the polycarbonate resin containing the structural unit (a) derived from the dihydroxy compound (α) having a cyclic ether structure; A polycarbonate resin composition comprising 0.01 to 1 part by weight of an acid ester metal salt.
[2] The polycarbonate resin in the resin composition is produced using at least one metal compound selected from the group consisting of a lithium compound and a metal compound of Group 2 of the long-period periodic table as a transesterification reaction catalyst. The polycarbonate resin composition according to [1].
[3] The polycarbonate resin composition according to [1] or [2], wherein the phosphate metal salt is a salt of a Group 12 metal element.
[4] The polycarbonate resin composition according to any one of [1] to [3], which contains an antioxidant.
[5] The polycarbonate resin composition according to any one of [1] to [4], which contains a light stabilizer.
[6] The polycarbonate resin composition according to any one of [1] to [5], which contains a release agent.
[7] The polycarbonate resin composition according to any one of [1] to [6], wherein the dihydroxy compound (α) having a cyclic ether structure is a dihydroxy compound having a structure represented by the following formula (1): object.

[8] The polycarbonate resin composition according to any one of [1] to [7], wherein the polycarbonate resin includes a structural unit derived from an aliphatic hydrocarbon dihydroxy compound.
[9] A polycarbonate resin molded product obtained by molding the polycarbonate resin composition according to any one of [1] to [8].
[10] The polycarbonate resin molded product according to [9], wherein the polycarbonate resin molded product is obtained by molding by an injection molding method.

  According to the present invention, it is possible to provide a polycarbonate resin composition having improved hue and color difference in outdoor exposure, and a molded product thereof.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention. It is not limited to the contents of. In the present invention, “to” is used as an expression including numerical values or physical quantities before and after. In addition, when the expression “substituent” is used in the present invention, the type of the substituent is not limited unless otherwise specified, and means up to a molecular weight of 200.

[Polycarbonate resin composition]
The polycarbonate resin composition of the present invention is 0.01 parts by weight or more and 30 parts by weight of titanium oxide with respect to 100 parts by weight of the polycarbonate resin containing the structural unit (a) derived from the dihydroxy compound (α) having a cyclic ether structure. And a polycarbonate resin composition containing 0.01 to 1 part by weight of a phosphate ester metal salt.

The polycarbonate resin composition is a polycarbonate having improved hue and color difference when exposed outdoors. This is because the coloring component in the polycarbonate resin composition is decolored by heat, so that when exposed outdoors, the resin composition is decolorized by the heat of sunlight. In contrast, the polycarbonate resin composition of the present invention contains a phosphoric acid ester metal salt, so that the phosphoric acid ester metal salt solves the problem of decolorization of the colorant due to the heat of sunlight. It is now possible to provide a polycarbonate resin composition with improved color difference and a molded product thereof.
The components used in the polycarbonate resin composition of the present invention are described in detail below.

[Polycarbonate resin]
The polycarbonate resin used in the polycarbonate resin composition of the present invention is a polycarbonate resin containing a structural unit derived from a dihydroxy compound having a cyclic ether structure (hereinafter sometimes referred to as “structural unit (a)”). Such a polycarbonate resin is obtained by polycondensation by a transesterification reaction using a dihydroxy compound having a cyclic ether structure (hereinafter sometimes referred to as “dihydroxy compound (α)”) and a carbonic acid diester as raw materials.

  The polycarbonate resin used in the present invention is less than 145 ° C, preferably less than 135 ° C, more preferably less than 125 ° C from the viewpoint of improving the impact resistance of the polycarbonate resin composition. Further, from the viewpoint of improving heat resistance, the glass transition temperature Tg is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, and further preferably 100 ° C. or higher. The glass transition temperature Tg of the polycarbonate resin can be controlled by appropriately selecting and introducing the structural unit (b) described later in addition to the structural unit derived from the dihydroxy compound having the cyclic ether structure.

  In the present invention, the glass transition temperature is a value measured by the following method. First, using a differential scanning calorimeter (“DSC220” manufactured by SII Nanotechnology Inc.), about 10 mg of polycarbonate resin is heated at a rate of temperature increase of 10 ° C./min, and a DSC curve is measured. Next, in accordance with JIS-K7121 (1987), a straight line obtained by extending the base line on the low temperature side to the high temperature side, and a tangent line drawn at a point where the gradient of the curve at the stepped change portion of the glass transition is maximized. The extrapolated glass transition start temperature, which is the temperature of the intersection point with, is obtained, and this is set as the glass transition temperature Tg.

<Raw material>
(Dihydroxy compound)
Specific examples of the dihydroxy compound having a cyclic ether structure (dihydroxy compound (α)) include compounds having a cyclic ether structure in the molecule represented by the following formulas (1), (2) and (3). It is done.

  Among these, viewpoints such as ease of availability, ease of handling, high reactivity during polymerization, and the hue of the obtained polycarbonate resin and the polycarbonate resin composition using the same are improved. Therefore, oxyalkylene glycols such as diethylene glycol and triethylene glycol are preferable. Among dihydroxy compounds having a cyclic structure in the molecule, those having a plurality of ether bonds in the molecule are preferred. In addition, the dihydroxy compound having a cyclic ether structure in the molecule may be monocyclic or polycyclic, but preferably has a plurality of cyclic ether structures, and further includes two cyclic ether structures. It is preferable that the two cyclic ether structures have the same structure. Moreover, from the viewpoint of heat resistance, among the dihydroxy compounds having a cyclic ether structure in the molecule, anhydrous sugar alcohols typified by the dihydroxy compound represented by the formula (1) are preferable.

Examples of the dihydroxy compound represented by the formula (1) include isosorbide, isomannide, and isoide which are in a stereoisomeric relationship. These may be used alone or in combination of two or more.
Of these dihydroxy compounds (α), it is preferable to use a dihydroxy compound having no aromatic ring structure from the viewpoint of the light resistance of the polycarbonate resin. Among them, there are a variety of easily available resources that are abundant as plant-derived resources. Isosorbide obtained by dehydrating condensation of sorbitol produced from starch is most preferable from the viewpoints of availability and production, light resistance, optical properties, moldability, heat resistance, and carbon neutral.

The ratio of the structural unit (a) derived from the dihydroxy compound having a cyclic ether structure to the structural unit derived from all dihydroxy compounds in the polycarbonate resin is preferably 10 mol% or more, more preferably 20 mol% or more. 30 mol% or more is more preferable. By setting the structural unit derived from the dihydroxy compound (α) to the above lower limit value or more, the color tone, light resistance and the like of the polycarbonate resin tend to be excellent. On the other hand, the upper limit of the ratio of the structural unit (a) to the structural unit derived from all dihydroxy compounds is 100 mol%, but various physical properties can be improved by introducing the structural unit (b) and other structural units described below. The effect of can be obtained. For this reason, what is necessary is just to determine the upper limit of the ratio of a structural unit (a) suitably according to a desired physical property.

  In the polycarbonate resin used in the present invention, in addition to the structural unit (a), a structural unit (b) derived from an aliphatic hydrocarbon dihydroxy compound (hereinafter sometimes referred to as “dihydroxy compound (β)”). It is preferable that both are included. When the polycarbonate resin used in the present invention has the structural unit (b), the glass transition temperature tends to be low, and as a result, it becomes easy to obtain a polycarbonate resin having high impact resistance. From this viewpoint, the proportion of the structural unit (b) in the polycarbonate resin used in the present invention is preferably 10 mol% or more, more preferably 20 mol% or more with respect to the total of the structural unit (a) and the structural unit (b). More preferably, it is more preferably 30 mol% or more, and particularly preferably more than 40 mol%. On the other hand, from the viewpoint of hue and light resistance, the proportion of the structural unit (b) is 90 mol% or less, more preferably 80 mol% or less, still more preferably, based on the total of the structural unit (a) and the structural unit (b). It is 70 mol% or less.

Examples of the aliphatic hydrocarbon dihydroxy compound (dihydroxy compound (β)) include a linear aliphatic hydrocarbon dihydroxy compound, a linear branched aliphatic hydrocarbon dihydroxy compound, an alicyclic hydrocarbon dihydroxy compound, and the like. Of these, alicyclic hydrocarbon dihydroxy compounds are preferred.
Examples of the linear aliphatic hydrocarbon dihydroxy compound include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, Examples include 1,5-heptanediol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol, and the like. Examples of the dihydroxy compound of the linear branched aliphatic hydrocarbon include neopentyl glycol and hexylene glycol.

  The alicyclic hydrocarbon dihydroxy compound is a compound having a cyclic structure hydrocarbon skeleton and two hydroxy groups, and the hydroxy group may be directly bonded to the cyclic structure or may be bonded to the cyclic structure via a substituent. May be combined. The cyclic structure may be monocyclic or polycyclic. Specific examples of the alicyclic hydrocarbon dihydroxy compound include cyclohexanediols such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 2-methyl-1,4-cyclohexanediol. Cyclohexenediols such as 4-cyclohexene-1,2-diol, cyclohexanedimethanols such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, Cyclohexene dimethanol such as 4-cyclohexene-1,2-diol, norbornane dimethanol such as 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 1, - adamantane-diol, 2,2-adamantane diol. Of these, cyclohexanedimethanols such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol are preferred. Of the cyclohexanedimethanols, 1,4-cyclohexanedimethanol is particularly preferred.

The polycarbonate resin used in the present invention may contain a structural unit derived from a dihydroxy compound other than the dihydroxy compound (α) and the dihydroxy compound (β) (hereinafter sometimes referred to as “other dihydroxy compound”). Good. More specifically, as other dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A], 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane,
2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy- (3,5-diphenyl) phenyl) propane, 2,2-bis (4-hydroxy-) 3,5-dibromophenyl) propane, 2,2-bis (4-hydroxyphenyl) pentane, 2,4′-dihydroxy-diphenylmethane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-5-nitrophenyl) ) Methane, 1,1-bis (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfone 2,4′-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 4,4′-dihydride Fragrances such as xydiphenyl ether, 4,4′-dihydroxy-3,3′-dichlorodiphenyl ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-2-methylphenyl) fluorene Group bisphenols.

  When including structural units derived from other dihydroxy compounds, the amount of structural units derived from other dihydroxy compounds relative to all structural units derived from dihydroxy compounds is preferably relative to all structural units derived from dihydroxy compounds. It is 20 mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less, and particularly preferably 5 mol% or less. However, other dihydroxy compounds having an aromatic ring preferably have no aromatic ring structure in the molecular structure of the polycarbonate resin from the viewpoint of light resistance.

  The dihydroxy compound used in the present invention may contain a stabilizer such as a reducing agent, antioxidant, oxygen scavenger, light stabilizer, antacid, pH stabilizer, heat stabilizer, etc. Since the dihydroxy compound used in the invention is easily altered, it is preferable to include a basic stabilizer. Basic stabilizers include group 1 or group 2 metal hydroxides, carbonates, phosphates, phosphites, hypophosphorous acid in the long-period periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005). Salts, borates, fatty acid salts, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium Basic ammonium compounds such as um hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, butyltriphenylammonium hydroxide, 4-aminopyridine, 2-aminopyridine, N, N -Dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole And amine compounds such as aminoquinoline. Among these, sodium or potassium phosphates and phosphites are preferable because of their effects and ease of distillation removal described later, and disodium hydrogen phosphate and disodium hydrogen phosphite are particularly preferable.

  Although there is no restriction | limiting in particular in content in the dihydroxy compound used for this invention of these basic stabilizers, if there is too little, there exists a possibility that the effect which prevents the quality change of the dihydroxy compound used for this invention may not be acquired, and too much. Since it may cause modification of the dihydroxy compound used in the present invention, it is usually 0.0001% by weight to 1% by weight, preferably 0.001% by weight to 0.1% by weight, based on the dihydroxy compound used in the present invention. It is.

Further, when the dihydroxy compound used in the present invention containing these basic stabilizers is used as a raw material for producing polycarbonate resin, the basic stabilizer itself becomes a polymerization catalyst, and it becomes difficult to control the polymerization rate and quality. It is preferable to remove the basic stabilizer by ion exchange resin or distillation before using it as a raw material for the production of polycarbonate resin, since it may deteriorate the initial hue and consequently deteriorate the light resistance of the molded product. .

  When the dihydroxy compound used in the present invention has a cyclic ether structure such as isosorbide, it is gradually oxidized by oxygen, so that it is prevented from being decomposed by oxygen by preventing moisture from being mixed during storage and production. It is important to use an oxygen scavenger or handle under a nitrogen atmosphere. When isosorbide is oxidized, decomposition products such as formic acid may be generated. For example, when isosorbide containing these decomposition products is used as a polycarbonate resin production raw material, the resulting polycarbonate resin may be colored, and not only the physical properties may be significantly degraded, but also the polymerization reaction may be affected. In some cases, a high molecular weight polymer cannot be obtained.

  In order to obtain the dihydroxy compound used in the present invention which does not contain the above oxidative decomposition product, and in order to remove the aforementioned basic stabilizer, it is preferable to carry out distillation purification. The distillation in this case may be simple distillation or continuous distillation, and is not particularly limited. As distillation conditions, it is preferable to carry out distillation under reduced pressure in an inert gas atmosphere such as argon or nitrogen. In order to suppress thermal denaturation, it is 250 ° C. or lower, preferably 200 ° C. or lower, particularly 180 °. It is preferable to carry out under the conditions of ℃ or less.

  By such distillation purification, the dihydroxy compound used in the present invention is made to have a formic acid content in the dihydroxy compound used in the present invention of 20 ppm by weight or less, preferably 10 ppm by weight or less, particularly preferably 5 ppm by weight or less. When a dihydroxy compound containing is used as a polycarbonate resin production raw material, a polycarbonate resin excellent in hue and thermal stability can be produced without impairing polymerization reactivity. The formic acid content is measured by ion chromatography.

(Carbonated diester)
The polycarbonate resin used in the present invention can be obtained by polycondensation by a transesterification reaction using the dihydroxy compound containing the dihydroxy compound used in the present invention and the carbonic acid diester as raw materials. As a carbonic acid diester used, what is normally represented by following formula (4) is mentioned. These carbonic acid diesters may be used alone or in combination of two or more.

In the above formula (4), A ¹ and A ² are each independently a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group. is there. A ¹ and A ² are preferably a substituted or unsubstituted aromatic hydrocarbon group, and more preferably an unsubstituted aromatic hydrocarbon group.
Examples of the carbonic acid diester represented by the formula (4) include substituted diaryls such as diphenyl carbonate and ditolyl carbonate, and substituted dialkyls such as dimethyl carbonate, diethyl carbonate and di-t-butyl carbonate. Is a substituted diaryl, and among the substituted diaryls, diphenyl carbonate is preferred. Carbonic acid diesters may contain impurities such as chloride ions, which may hinder the polymerization reaction or worsen the hue of the resulting polycarbonate resin. It is preferable to use what was done.

<Transesterification reaction catalyst>
The polycarbonate resin used in the present invention is usually produced by transesterifying the dihydroxy compound containing the dihydroxy compound used in the present invention with the carbonic acid diester represented by the formula (4) as described above. More specifically, it can be obtained by transesterification and removing by-product monohydroxy compounds and the like out of the system. In this case, polycondensation is usually carried out by transesterification in the presence of a transesterification catalyst.

The transesterification reaction catalyst (hereinafter sometimes simply referred to as a catalyst or a polymerization catalyst) that can be used in the production of the polycarbonate resin used in the present invention can particularly affect transparency and hue.
The catalyst to be used is not particularly limited as long as it does not cause a significant decrease in physical properties. However, as a catalyst that can be normally used, the group 1 or 2 in the long-period periodic table (hereinafter simply referred to as “Group 1”, “2”) A basic compound such as a metal compound, a basic boron compound, a basic phosphorus compound, a basic ammonium compound, an amine compound, and the like. Among these, a group 1 metal compound and / or a group 2 metal compound are preferable, and a group 2 metal compound is particularly preferably used from the viewpoint of transparency, light resistance, and hue.

  It is possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound in combination with the Group 1 metal compound and / or the Group 2 metal compound. It is particularly preferred to use only Group 1 metal compounds and / or Group 2 metal compounds. In addition, the group 1 metal compound and / or the group 2 metal compound are usually used in the form of a hydroxide or a salt such as a carbonate, a carboxylate, or a phenol salt. From the viewpoint of easiness, a hydroxide, carbonate, and acetate are preferable, and acetate is preferable from the viewpoint of hue and polymerization activity.

  Examples of the Group 1 metal compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, Cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride , Sodium phenyl borohydride, potassium phenyl borohydride, lithium phenyl borohydride, cesium phenyl borohydride, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, dinatrate hydrogen phosphate , Dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenyl phosphate, dipotassium phenyl phosphate, dilithium phenyl phosphate, dicesium phenyl phosphate, sodium, potassium, lithium, Examples include cesium alcoholate, phenolate, and disodium salt, dipotassium salt, dilithium salt, and dicesium salt of bisphenol A. Of these, lithium compounds are preferred.

Examples of the Group 2 metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, Strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, etc. Among these, magnesium compounds, calcium compounds, barium compounds are preferred, polymerization activity From the viewpoint of the hue of the polycarbonate resin obtained, a magnesium compound and / or a calcium compound is more preferable, and most preferably a calcium compound. That.

  Examples of the basic boron compound include tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethylbenzyl boron, trimethylphenyl boron, triethylmethyl boron, triethylbenzyl boron, triethylphenyl boron, tributylbenzyl. Examples include sodium, potassium, lithium, calcium, barium, magnesium, or strontium salts such as boron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, butyltriphenylboron, etc. It is done.

Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.
Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide Sid, butyl triphenyl ammonium hydroxide, and the like.

  Examples of the amine compound include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2 -Dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and the like.

  In particular, the use of at least one metal compound selected from the group consisting of a lithium compound and a metal compound of Group 2 of the long-period periodic table as a catalyst can improve the transparency, hue, and light resistance of the polycarbonate resin. It is preferable to make various physical properties such as the above excellent. Furthermore, in order to make the polycarbonate resin used in the present invention particularly excellent in transparency, hue and light resistance, it is possible to use at least one metal compound selected from the group consisting of magnesium compounds and calcium compounds as a catalyst. preferable.

  The amount of the polymerization catalyst used is preferably 0.1 μmol to 300 μmol, more preferably 0.5 μmol to 100 μmol per 1 mol of all dihydroxy compounds used in the polymerization, among which lithium and two groups in the long-period periodic table are included. When using a compound containing at least one metal selected from the group, particularly when using a magnesium compound and / or a calcium compound, the amount of metal is preferably 0.1 μmol or more per 1 mol of the total dihydroxy compound, More preferably 0.5 μmol or more, particularly preferably 0.7 μmol or more. The upper limit is preferably 20 μmol, more preferably 10 μmol, particularly preferably 3 μmol, and most preferably 1.5 μmol.

If the amount of the catalyst is too small, the polymerization rate is slowed down. As a result, when trying to obtain a polycarbonate resin having a desired molecular weight, the polymerization temperature has to be increased, and the hue and light resistance of the obtained polycarbonate resin are deteriorated. Or the unreacted raw material volatilizes during the polymerization, and the molar ratio of the dihydroxy compound containing the dihydroxy compound used in the present invention to the carbonic acid diester represented by the formula (4) may collapse, and the desired molecular weight may not be reached. There is. On the other hand, when there is too much usage-amount of a polymerization catalyst, the hue of the polycarbonate resin obtained will be deteriorated and the light resistance of a polycarbonate resin may deteriorate.

  Furthermore, when using the substituted diphenyl carbonate such as diphenyl carbonate and ditolyl carbonate as the carbonic acid diester represented by the formula (4) to produce the polycarbonate resin used in the present invention, phenol and substituted phenol are by-produced, Although it is unavoidable that it remains in the polycarbonate resin, phenol and substituted phenol also have an aromatic ring, which absorbs ultraviolet rays and may cause deterioration of light resistance, as well as causing odor during molding. There is a case. The polycarbonate resin contains an aromatic monohydroxy compound having an aromatic ring such as by-product phenol of 1000 ppm by weight or more after a normal batch reaction, but from the viewpoint of light resistance and odor reduction, it is removed. It is preferably 700 ppm by weight or less, more preferably 500 ppm by weight or less, and particularly preferably 300 ppm by weight or less using a horizontal reactor having excellent volatility or an extruder with a vacuum vent. However, it is difficult to remove completely industrially, and the lower limit of the content of the aromatic monohydroxy compound is usually 1 ppm by weight. Note that these aromatic monohydroxy compounds may naturally have a substituent depending on the raw material used, and may have, for example, an alkyl group having 5 or less carbon atoms.

Further, Group 1 metals, especially sodium, potassium, and cesium, especially lithium, sodium, potassium, and cesium, may be mixed not only from the catalyst used but also from raw materials and reactors. If the resin is contained in a large amount, the hue may be adversely affected. Therefore, the total amount of these compounds in the polycarbonate resin is preferably small, and the amount of metal is usually 1 ppm by weight or less, preferably 0.8. Weight ppm or less, More preferably, it is 0.7 weight ppm or less.
The amount of metal in the polycarbonate resin can be measured by various conventionally known methods. After recovering the metal in the polycarbonate resin by a method such as wet ashing, atomic emission, atomic absorption, Inductively Coupled Plasma (ICP) It can measure using the method of these.

<Production method of polycarbonate resin>
The polycarbonate resin used in the present invention is obtained by polycondensation of the dihydroxy compound containing the dihydroxy compound used in the present invention and the carbonic acid diester of the above formula (5) by a transesterification reaction. The raw material dihydroxy compound and carbonic acid diester Is preferably mixed uniformly before the transesterification reaction.

  The mixing temperature is usually 80 ° C. or higher, preferably 90 ° C. or higher, and the upper limit is usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower. Among these, 95 ° C. or higher and 120 ° C. or lower is preferable. If the mixing temperature is too low, the dissolution rate may be slow or the solubility may be insufficient, often resulting in problems such as solidification. If the mixing temperature is too high, the dihydroxy compound may be thermally deteriorated, resulting in a deterioration of the hue of the polycarbonate resin thus obtained, which may adversely affect light resistance.

  The operation of mixing the dihydroxy compound containing the dihydroxy compound used in the present invention, which is a raw material of the polycarbonate resin used in the present invention, and the carbonic acid diester represented by the above formula (4) is performed with an oxygen concentration of 10% by volume or less, and further preferably 0.8. It is preferable from the viewpoint of preventing the deterioration of the hue to be performed in an atmosphere of 0001 vol% to 10 vol%, particularly 0.0001 vol% to 5 vol%, particularly 0.0001 vol% to 1 vol%.

In order to obtain the polycarbonate resin used in the present invention, the carbonic acid diester represented by the formula (4) is 0.90 to 1.20 relative to the dihydroxy compound including the dihydroxy compound used in the present invention used for the reaction. The molar ratio is preferably used, and more preferably 0.95 to 1.10. When this molar ratio is reduced, the terminal hydroxyl group of the produced polycarbonate resin is increased, the thermal stability of the polymer is deteriorated, coloring occurs during molding, the rate of transesterification reaction is reduced, and the desired high molecular weight. The body may not be obtained. On the other hand, when the molar ratio increases, the rate of transesterification may decrease. The decrease in the transesterification reaction rate may increase the heat history during the polymerization reaction, and may deteriorate the hue and light resistance of the resulting polycarbonate resin. Furthermore, when the molar ratio of the carbonic acid diester represented by the formula (4) is increased with respect to the dihydroxy compound including the dihydroxy compound used in the present invention, the amount of residual carbonic acid diester in the obtained polycarbonate resin is increased. May absorb ultraviolet rays and deteriorate the light resistance of the polycarbonate resin.

The concentration of the carbonic acid diester remaining in the polycarbonate resin used in the present invention is preferably 200 ppm by weight or less, more preferably 100 ppm by weight or less, particularly preferably 60 ppm by weight or less, and particularly preferably 30 ppm by weight or less. Actually, the polycarbonate resin may contain unreacted carbonic acid diester, and the lower limit of the concentration is usually 1 ppm by weight.
In the present invention, the method of polycondensing a dihydroxy compound and a carbonic acid diester is usually carried out in multiple stages using a plurality of reactors in the presence of the above-mentioned catalyst. The type of reaction may be any of batch type, continuous type, or a combination of batch type and continuous type.

  In the initial stage of polymerization, it is preferable to obtain a prepolymer at a relatively low temperature and low vacuum, and in the latter stage of polymerization, it is preferable to increase the molecular weight to a predetermined value at a relatively high temperature and high vacuum, but the jacket temperature at each molecular weight stage. Appropriate selection of the internal temperature and pressure in the reaction system is important from the viewpoints of hue and light resistance. For example, if either the temperature or the pressure is changed too quickly before the polymerization reaction reaches a predetermined value, the unreacted monomer will be distilled, causing the molar ratio of the dihydroxy compound and the carbonic acid diester to change, resulting in a decrease in the polymerization rate. May be invited.

  Furthermore, it is effective to use a reflux condenser for the polymerization reactor in order to suppress the amount of the monomer to be distilled off, and the effect is particularly great in a reactor at the initial stage of polymerization where there are many unreacted monomer components. The temperature of the refrigerant introduced into the reflux cooler can be appropriately selected according to the monomer used. Usually, the temperature of the refrigerant introduced into the reflux cooler is 45 ° C. to 180 ° C. at the inlet of the reflux cooler. Preferably, it is 80 degreeC-150 degreeC, Most preferably, it is 100 degreeC-130 degreeC. If the temperature of the refrigerant introduced into the reflux condenser is too high, the reflux amount is reduced and the effect is reduced. If it is too low, the distillation efficiency of the monohydroxy compound to be originally distilled tends to be reduced. As the refrigerant, hot water, steam, heat medium oil or the like is used, and steam or heat medium oil is preferable.

In order to maintain the polymerization rate appropriately and suppress the distillation of the monomer, while keeping the hue, thermal stability, light resistance, etc. of the finally obtained polycarbonate resin, The selection of the quantity is important.
The polycarbonate resin used in the present invention is preferably produced by polymerizing in a plurality of stages using a plurality of reactors using a catalyst, but the reason for carrying out the polymerization in a plurality of reactors is the initial stage of the polymerization reaction. In order to shift the equilibrium to the polymerization side in the later stage of the polymerization reaction, it is important to suppress the volatilization of the monomer while maintaining the necessary polymerization rate because there are many monomers contained in the reaction solution. This is because it is important to sufficiently distill off the by-produced monohydroxy compound. Thus, in order to set different polymerization reaction conditions, it is preferable from the viewpoint of production efficiency to use a plurality of polymerization reactors arranged in series.

As described above, the number of reactors used in the method of the present invention may be at least two or more, but from the viewpoint of production efficiency, etc., three or more, preferably 3 to 5, particularly preferably 4 One. In the present invention, if there are two or more reactors, a plurality of reaction stages having different conditions may be provided in the reactor, or the temperature and pressure may be continuously changed.
In the present invention, the polymerization catalyst can be added to the raw material preparation tank, the raw material storage tank, or can be added directly to the polymerization tank. From the viewpoint of supply stability and polymerization control, the polymerization catalyst is supplied to the polymerization tank. A catalyst supply line is installed in the middle of the raw material line before being fed, and preferably supplied as an aqueous solution.

If the temperature of the polymerization reaction is too low, the productivity is lowered and the thermal history of the product is increased. If it is too high, not only the monomer is volatilized but also decomposition and coloring of the polycarbonate resin may be promoted.
Specifically, the reaction in the first stage is performed at 140 to 270 ° C., preferably 180 to 240 ° C., more preferably 200 to 230 ° C. as the maximum internal temperature of the polymerization reactor. 110 kPa to 10 kPa, preferably 70 kPa to 5 kPa, more preferably 30 kPa to 1 kPa, reaction time is 0.1 to 10 hours, preferably 0.5 to 3 hours, while distilling out the generated monohydroxy compound out of the reaction system To be implemented. In the second and subsequent stages, the pressure in the reaction system is gradually reduced from the pressure in the first stage, and the monohydroxy compound that is subsequently generated is removed from the reaction system. 200 Pa or less, maximum internal temperature of 210 ° C. to 270 ° C., preferably 220 ° C. to 250 ° C., usually 0.1 hour to 10 hours, preferably 1 hour to 6 hours, particularly preferably 0.5 hour. Perform for ~ 3 hours.

  In particular, in order to suppress the coloring and thermal deterioration of the polycarbonate resin and obtain a polycarbonate resin having a good hue and light resistance, the maximum internal temperature in all reaction stages is less than 250 ° C., particularly 225 ° C. to 245 ° C. preferable. In order to suppress the decrease in the polymerization rate in the latter half of the polymerization reaction and minimize degradation due to thermal history, it is necessary to use a horizontal reactor with excellent plug flow and interface renewability at the final stage of polymerization. preferable.

In order to obtain a polycarbonate resin having a predetermined molecular weight, if the polymerization temperature is high and the polymerization time is too long, transparency and hue tend to deteriorate.
The monohydroxy compound produced as a by-product is preferably reused as a raw material for diphenyl carbonate, bisphenol A, etc. after purification as necessary from the viewpoint of effective utilization of resources.
The polycarbonate resin used in the present invention is usually cooled and solidified after polycondensation as described above, and pelletized with a rotary cutter or the like. The method of pelletization is not limited, but it is extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of a strand and pelletized, or uniaxial or biaxial extrusion in the molten state from the final polymerization reactor. The resin is supplied to the machine, melt-extruded, cooled and solidified into pellets, or extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of strands, once pelletized, and then uniaxially again Or after supplying resin to a twin-screw extruder, melt-extruding, cooling and solidifying and pelletizing, etc. are mentioned.

  At that time, in the extruder, the residual monomer under reduced pressure devolatilization, and generally known heat stabilizers, neutralizers, UV absorbers, mold release agents, colorants, antistatic agents, lubricants, lubricants, A plasticizer, a compatibilizer, a flame retardant, etc. can be added and kneaded. The melt kneading temperature in the extruder depends on the glass transition temperature and molecular weight of the polycarbonate resin, but is usually 150 ° C to 300 ° C, preferably 200 ° C to 270 ° C, more preferably 230 ° C to 260 ° C. When the melt-kneading temperature is lower than 150 ° C., the melt viscosity of the polycarbonate resin is high, the load on the extruder is increased, and the productivity is lowered. When the temperature is higher than 300 ° C., the polycarbonate resin is severely deteriorated by heat and may cause a decrease in mechanical strength due to a decrease in molecular weight, coloring, and gas generation.

  When the polycarbonate resin used in the present invention is produced, it is desirable to install a filter in order to prevent foreign substances from entering. The filter installation position is preferably on the downstream side of the extruder, and the foreign matter removal size (opening) of the filter is preferably 100 μm or less as the filtration accuracy for 99% removal. In particular, in the case of disagreeing with the entry of minute foreign matters for film use etc., it is preferably 40 μm or less, more preferably 10 μm or less.

Extrusion of the polycarbonate resin used in the present invention is preferably performed in a class 7 defined in JIS B 9920 (2002), more preferably in a clean room having a higher cleanliness than class 6 in order to prevent foreign matter from being mixed after extrusion. It is desirable to implement.
Moreover, when cooling the extruded polycarbonate resin into chips, it is preferable to use a cooling method such as air cooling or water cooling. As the air used for air cooling, it is desirable to use air from which foreign substances in the air have been removed in advance with a hepa filter or the like to prevent reattachment of foreign substances in the air. When water cooling is used, it is desirable to use water from which metal in water has been removed with an ion exchange resin or the like, and foreign matter in water has been removed with a filter. The opening of the filter to be used is preferably 10 μm to 0.45 μm as 99% removal filtration accuracy.

<Physical properties of polycarbonate resin>
The molecular weight of the polycarbonate resin used in the present invention thus obtained can be represented by a reduced viscosity, and the reduced viscosity is usually 0.30 dL / g or more, preferably 0.35 dL / g or more, usually 1 .20 dL / g or less, preferably 1.00 dL / g or less, and more preferably 0.80 dL / g or less.

  If the reduced viscosity of the polycarbonate resin is too low, the mechanical strength of the molded product tends to decrease. If it is too large, the fluidity at the time of molding tends to decrease, and the productivity and moldability tend to decrease. The reduced viscosity is measured using a Ubbelohde viscometer at a temperature of 20.0 ° C. ± 0.1 ° C., precisely prepared at a polycarbonate concentration of 0.6 g / dL using methylene chloride as a solvent.

  In addition, the polycarbonate resin used in the present invention may be a heat stabilizer, a neutralizing agent, an ultraviolet absorber, a release agent, a colorant, an antistatic agent, a lubricant, or a lubricant before performing various moldings, if necessary. Additives such as plasticizers, compatibilizers, and flame retardants can also be mixed with a tumbler, super mixer, floater, V-type blender, nauter mixer, Banbury mixer, extruder, and the like.

[Titanium oxide]
The polycarbonate resin composition of the present invention contains 0.01 to 30 parts by weight of titanium oxide with respect to 100 parts by weight of the polycarbonate resin. By blending titanium oxide with the polycarbonate resin, light reflectance, impact resistance and the like are improved.
The content of titanium oxide (including the amount of “surface treatment agent” described later) in the present invention is 0.01 part by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the polycarbonate resin. 1 part by weight or more, more preferably 0.5 part by weight or more, further preferably 1 part by weight or more, while preferably 30 parts by weight or less, more preferably 10 parts by weight or less, still more preferably 5 parts by weight. It is as follows. If the content of titanium oxide is too small, the effect of improving light reflectivity and impact resistance due to the blending of titanium oxide cannot be obtained sufficiently. On the other hand, if the content is too large, impact resistance is deteriorated and the appearance is poor.

  As the titanium oxide used in the present invention, any conventionally known titanium oxide can be used, and the surface thereof may be surface-treated with an organic surface treatment agent or an inorganic surface treatment agent. For example, commercially available titanium oxide is often surface-treated with a hydrous oxide such as silica, alumina, zirconia, etc. from the viewpoint of improving weather resistance, dispersibility, and handling properties. However, since silica has high water absorption and is easily influenced by moisture, the inorganic surface treatment agent is preferably alumina or zirconia.

The amount of these inorganic surface treatment agents for titanium oxide may be selected and determined as appropriate. However, for example, when the content of the surface treatment agent in titanium oxide or the like is too much relative to titanium oxide or the like,
In a polycarbonate resin molded product in which an inorganic treatment layer is formed on a metal surface and a polycarbonate resin composition containing the inorganic treatment layer is molded by the adsorbed water, there are cases where appearance defects and dripping during combustion increase. On the other hand, if the amount is too small, the improvement effect may be insufficient, such as insufficient dispersibility. From these viewpoints, the amount of the surface treatment agent is preferably 0.1 to 5% by weight with respect to titanium oxide.

  Moreover, in order to avoid the problem by the adsorbed water mentioned above, it is preferable to use an organic surface treating agent as the surface treating agent for titanium oxide. Examples of such a surface treatment agent include an organosilane compound and an organosilicon compound having an alkoxy group, an epoxy group, an amino group, or a Si—H bond. Among them, hydrogen polysiloxane (a silicon compound having a Si—H bond) is preferable, and the treatment amount with the organic surface treatment agent is preferably 0.5 to 5% by weight with respect to titanium oxide, and 1 to 3% by weight. % Is more preferable.

  The average particle diameter of the titanium oxide used in the present invention is arbitrary, and may be appropriately selected and determined according to the use of the polycarbonate resin composition containing the titanium oxide. When this average particle diameter is too small, the light shielding property and light reflectivity in the polycarbonate resin composition of the present invention may be insufficient. On the other hand, if the average particle size is too large, the light shielding properties and light reflectivity are inferior, and the surface of the resin molded body may be roughened or the impact resistance may be lowered. Therefore, the average particle diameter of titanium oxide is preferably 0.05 μm or more, more preferably 0.1 μm or more, further preferably 0.15 μm or more, and on the other hand, 0.5 μm or less. Is preferably 0.35 μm or less.

As a method for producing titanium oxide used in the present invention, those obtained by any conventionally known production method such as a hydrochloric acid method or a sulfuric acid method can be used, and any of them can be suitably used. In particular, titanium oxide produced by the chlorine method is preferable because of its excellent whiteness.
Moreover, there is no restriction | limiting in particular also about the crystal form of a titanium oxide, Any can be used, such as a rutile type and an anatase type. In particular, rutile-type titanium oxide is preferable because it is excellent in terms of whiteness, light reflectivity, and light resistance.
Titanium oxide can be obtained as a commercial product. Examples of commercially available products include DuPont's Taipure (registered trademark) series, DuPont's Thai Select (registered trademark) series, Ishihara Sangyo's Taipaque (registered trademark), and the like.

[Phosphate metal salt]
The polycarbonate resin composition of the present invention contains 0.01 part by weight or more and 1 part by weight or less of a phosphate ester metal salt with respect to 100 parts by weight of the polycarbonate resin. By blending a phosphoric acid ester metal salt with the polycarbonate resin and titanium oxide, the color difference of the polycarbonate resin composition when exposed outdoors is improved.

  The content of the phosphoric acid ester metal salt in the present invention is 0.01 part by weight or more and 1 part by weight or less with respect to 100 parts by weight of the polycarbonate resin, preferably 0.02 part by weight or more, more preferably 0.03 part. It is preferably not less than 0.05 parts by weight, more preferably not more than 1 part by weight, more preferably not more than 0.8 parts by weight, still more preferably not more than 0.5 parts by weight. If the content of the phosphoric acid ester metal salt is too small, the effect of improving the color difference of the polycarbonate resin composition when exposed to the outdoors cannot be obtained sufficiently. On the other hand, if the content is too large, the mechanical properties are poor.

As the carbon number of the phosphoric acid ester of the phosphoric acid ester metal salt in the present invention, the color difference in the outdoor exposure of the polycarbonate resin composition is easy to improve, so the upper limit of the carbon number is preferably 10 or more, carbon The number is more preferably 12 or more, and more preferably 14 or more. Further, the lower limit is preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less.

  The phosphoric acid ester metal salt in the present invention is preferably a Group 2, 12 or 13 metal salt from the effect of preventing discoloration at high temperatures, and among these, a Group 12 metal is more preferable. Specific examples of Group 2, Group 12, and Group 13 metals include zinc, magnesium, and calcium. Among these, Group 12 zinc is particularly preferable because of less deterioration in hue when added.

The phosphate metal salt in the present invention is specifically the following phosphate ester metal salt.
Examples thereof include monostearyl acid phosphate zinc salt, distearyl acid phosphate zinc salt, and mixtures thereof. Among these, a mixture of monostearyl acid phosphate zinc salt and distearyl acid phosphate zinc salt is particularly preferable because of the effect of preventing discoloration and its durability.
Moreover, a phosphoric acid ester metal salt can be obtained as a commercial item. Examples of commercially available products include “ADEKA STAB” (registered trademark) SP-2011 (registered trademark) manufactured by ADEKA, JP-518Zn series manufactured by Johoku Chemical Industry Co., Ltd., and LBT-1830 manufactured by Sakai Chemical Industry Co., Ltd.

[Antioxidant]
The polycarbonate resin composition of the present invention preferably further contains an antioxidant. When the antioxidant is used, the blending amount is preferably 0.001 part by weight or more, more preferably 0.05 part by weight or more, further preferably 0.01 part by weight with respect to 100 parts by weight of the polycarbonate resin. On the other hand, it is preferably 1 part by weight or less, more preferably 0.5 part by weight or less, and further preferably 0.3 part by weight or less. It is preferable that the content of the antioxidant is not less than the above lower limit value because the coloration suppressing effect during molding tends to be good. On the other hand, if the content of the antioxidant is not more than the above upper limit value, the amount of deposits on the mold during injection molding decreases, or the amount of deposits on the roll decreases when a film is formed by extrusion molding. This is preferable because the surface appearance of the product tends to be better.

As antioxidant, a phenolic antioxidant, phosphorus antioxidant, sulfur type antioxidant, etc. are mentioned as a preferable thing, and all may be used alone or in combination of two or more. In particular, a sulfur-based antioxidant is preferable from the viewpoint of improving light resistance.
Examples of the phenolic antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate, triethylene glycol-bis [ 3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] , Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1 , 3,5-trimethyl-2 4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4′-biphenylenediphosphinic acid tetrakis ( 2,4-di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane and the like. Among these compounds, an aromatic monohydroxy compound substituted with one or more alkyl groups having 5 or more carbon atoms is preferable. Specifically, octadecyl-3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate, pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol-bis [3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and the like, preferably pentaerythris Lithyl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate is more preferred.

  Examples of phosphorus antioxidants include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, tri Octadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert -Butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol Diphosphite, bis (2,4--tert- butylphenyl) pentaerythritol phosphite, distearyl pentaerythritol diphosphite and the like. Among these, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is preferred, and tris (2,4-di-tert-butylphenyl) phosphite is more preferred.

  Examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, diester Stearyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), bis [2-methyl-4- (3 -Laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1′-thiobis (2-naphthol) and the like. Among the above, pentaerythritol tetrakis (3-lauryl thiopropionate) is preferable.

[Release agent]
The polycarbonate resin composition of the present invention preferably contains a release agent. When using a mold release agent, the content thereof is preferably 0.001 part by weight or more, more preferably 0.01 part by weight or more, further preferably 0.1 part by weight with respect to 100 parts by weight of the polycarbonate resin. On the other hand, it is preferably 2 parts by weight or less, more preferably 1 part by weight or less, still more preferably 0.5 parts by weight or less. It is preferable for the content of the release agent to be equal to or more than the above lower limit because there is an advantage that the molded product can be easily released from the mold during molding and the molded product can be easily obtained. On the other hand, if the content of the release agent is less than or equal to the above upper limit value, mold deposits tend to decrease at the time of molding, and the mold maintenance labor is reduced when molding is carried out in large quantities. In addition, the molded product is preferable because the appearance tends to be good.

Although it does not specifically limit as a mold release agent, A higher fatty acid, a stearic acid ester, etc. are mentioned. From the viewpoint of releasability and transparency, stearates are preferred as release agents. Any type of release agent may be used alone, or two or more types may be used in combination.
As the stearic acid ester, a partial or total ester of a substituted or unsubstituted monovalent or polyhydric alcohol having 1 to 20 carbon atoms and stearic acid is preferable. Such partial esters or total esters of monohydric or polyhydric alcohols and stearic acid include ethylene glycol distearate, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, stearyl stearate, pentaerythritol. More preferred are monostearate, pentaerythritol tetrastearate, propylene glycol monostearate, stearyl stearate, butyl stearate, sorbitan monostearate, 2-ethylhexyl stearate and the like. Of these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate and stearyl stearate are more preferred, and ethylene glycol distearate and stearic acid monoglyceride are particularly preferred.

  As the higher fatty acid, a substituted or unsubstituted saturated fatty acid having 10 to 30 carbon atoms is preferable. A saturated fatty acid having 10 to 30 carbon atoms is more preferable, and examples of such higher fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, and behenic acid. Further, saturated fatty acids having 16 to 18 carbon atoms are more preferred, and examples of such saturated fatty acids include palmitic acid and stearic acid, with stearic acid being particularly preferred.

  In the present invention, the addition timing and addition method of the release agent are not particularly limited. For example, when the polycarbonate resin is produced by the transesterification method, when the polymerization reaction is completed; regardless of the polymerization method, the polycarbonate resin in the middle of kneading the polycarbonate resin with another compounding agent is melted. A case where it is blended and kneaded with a solid polycarbonate resin such as pellets or powder using an extruder or the like. As an addition method, a release agent may be directly mixed or kneaded with a polycarbonate resin; a high-concentration master batch prepared using a release agent with a small amount of a polycarbonate resin or other resin may be added.

[Other ingredients]
The component which can be mix | blended with the polycarbonate resin composition of this invention below is mentioned. These components can be used within a range that does not significantly impair the effects of the present invention, and unless otherwise specified, “parts by weight” of each component means a blending amount with respect to 100 parts by weight of the polycarbonate resin. . However, the components listed below do not include those corresponding to the above-mentioned polycarbonate resin, titanium oxide, antioxidant and mold release agent.

  In the polycarbonate resin composition of the present invention, a resin other than the polycarbonate resin (hereinafter sometimes simply referred to as “other resin”) is used for the purpose of further improving and adjusting the molding processability and various physical properties. You can also. Specific examples of other resins include resins such as polyester resins, polyethers, polyamides, polyolefins, polymethylmethacrylates, and rubber-like modified resins such as core-shell type, graft type or linear random and block copolymers. A quality agent etc. are mentioned.

As the blending amount of other resins, it is usually blended in a proportion of 0 to 30 parts by weight and preferably in a proportion of 20 parts by weight or less with respect to the entire polycarbonate resin composition used in the present invention. More preferably, it is blended at a ratio of 10 parts by weight or less.
Further, in the polycarbonate resin composition of the present invention, a stilbene benzoxazole derivative, a fluorescent brightening agent, a filler, a flame retardant, a flame retardant aid, an acidic compound, an ultraviolet light absorption aid, as long as the object of the present invention is not impaired. A heat stabilizer, a light stabilizer, an antistatic agent and the like can be appropriately blended. However, the components listed below are representative examples of those that can be used, and in the present invention, blending of components other than those listed below is not precluded.

  In the polycarbonate resin composition of the present invention, a stilbene benzoxazole derivative such as 4,4′-bis (5-methylbenzoxazol-2-yl) stilbene is added to the polycarbonate resin composition for the purpose of enhancing light reflectance and light resistance. It can contain 1-1000 ppm. When this content exceeds 1000 ppm, not only the improvement of the effect commensurate with the increase in content cannot be expected, but the residence heat stability and appearance may be deteriorated. In addition, 4,4′-bis (5-methylbenzoxazol-2-yl) stilbene is a conventionally known arbitrary method, for example, a method described in JP-B No. 41-20225, JP-T No. 2002-535393, or the like. Can be obtained.

  In the present invention, any conventionally known optical brightener other than 4,4′-bis (5-methylbenzoxazol-2-yl) stilbene may be used as long as the effects of the present invention are not impaired. . Examples of the fluorescent whitening agent include coumarin, naphthotriazolyl stilbene, benzoxazole, benzimidazole, and diaminostilbene-disulfonate fluorescent whitening agents.

  In the present invention, 4,4′-bis (5-methylbenzoxazol-2-yl) stilbene and an optical brightener other than 4,4′-bis (5-methylbenzoxazol-2-yl) stilbene are used in combination. In this case, the content of 4,4′-bis (5-methylbenzoxazol-2-yl) stilbene in the entire optical brightener is preferably 20% by weight or more. In particular, it is preferably 30% by weight or more, more preferably 40% by weight or more, and particularly preferably 50% by weight or more. If the content of 4,4′-bis (5-methylbenzoxazol-2-yl) stilbene is too low, improvement in light reflectivity, light resistance, hue, etc. in the obtained polycarbonate resin composition and resin molded product is not good. May be sufficient.

A filler can be blended in the polycarbonate resin composition of the present invention as long as the object of the present invention is not impaired. Examples of the filler that can be blended in the polycarbonate resin composition of the present invention include inorganic fillers and organic fillers.
The blending amount of the filler is 0 to 100 parts by weight. The blending amount of the filler is preferably 50 parts by weight or less, more preferably 40 parts by weight or less, and still more preferably 35 parts by weight or less. Although the reinforcing effect of the polycarbonate resin composition can be obtained by blending the filler, the appearance tends to be deteriorated when blending more than 100 parts by weight.

  Examples of the inorganic filler (in the present invention, excluding titanium oxide from the “inorganic filler”) include, for example, glass fiber, glass milled fiber, glass flake, glass bead, silica, alumina, gypsum, and gypsum whisker. , Talc, mica; carbon black, graphite, iron powder, copper powder, silicon carbide, silicon carbide fiber, silicon nitride, silicon nitride fiber, brass fiber, stainless steel fiber, whisker and the like. Among these, glass fiber filler, glass powder filler, glass flake filler; various whiskers, mica and talc are preferable. More preferably, glass fiber, glass flake, glass milled fiber, mica and talc are mentioned. Particularly preferred is at least one selected from glass fiber and talc. Although the inorganic filler mentioned above can also be used only by 1 type, it can also be used in combination of 2 or more type.

Among inorganic fillers, any glass fiber or glass milled fiber may be used as long as it is used in thermoplastic resins. In particular, alkali-free glass (E glass) is preferable. The diameter of glass fiber becomes like this. Preferably they are 6 micrometers-20 micrometers, More preferably, they are 9 micrometers-14 micrometers. If the diameter of the glass fiber is too small, the reinforcing effect tends to be insufficient. On the other hand, if it is excessively large, the product appearance is liable to be adversely affected. The glass fiber is preferably chopped strands cut to a length of 1 mm to 6 mm; preferably glass milled fibers that are commercially available after being pulverized to a length of 0.01 mm to 0.5 mm. These may be used alone or in combination. When glass fiber is used in the present invention, acrylic resin or urethane is used to improve surface treatment with a silane coupling agent such as aminosilane or epoxysilane, or to improve handleability, in order to improve adhesion with a polycarbonate resin. It may be used after being subjected to a focusing treatment with a resin or the like.

Any glass beads can be used as long as they are used in thermoplastic resins. Among these, alkali-free glass (E glass) is preferable. The shape of the glass beads is preferably spherical with a particle size of 10 μm to 50 μm.
As glass flakes, scaly glass flakes can be mentioned. The maximum diameter of the glass flake after blending the polycarbonate resin is generally 1000 μm or less, preferably 1 μm to 500 μm, and the aspect ratio (the ratio of the maximum diameter to the thickness) is 5 or more, preferably 10 or more, Preferably it is 30 or more.

Examples of organic fillers include powdered organic fillers such as wood powder, bamboo powder, coconut starch, cork powder, and pulp powder; balun-like and spherical shapes such as crosslinked polyester, polystyrene, styrene / acrylic copolymer, urea resin, and the like. Organic fillers: Fibrous organic fillers such as carbon fibers, synthetic fibers, and natural fibers can be used.
The carbon fiber is not particularly limited, and is produced by firing using, for example, acrylic fiber, petroleum or carbon-based special pitch, cellulose fiber, lignin or the like as a raw material. There are various types. The average of the aspect ratio (fiber length / fiber diameter) of the carbon fibers is preferably 10 or more, more preferably 50 or more. If the average aspect ratio is too small, the conductivity, strength, and rigidity of the polycarbonate resin composition tend to be reduced. The diameter of the carbon fiber is 3 μm to 15 μm, and any shape such as chopped strand, roving strand, milled fiber, etc. can be used to adjust the aspect ratio. Carbon fiber can be used 1 type or in mixture of 2 or more types.

As long as the properties of the polycarbonate resin composition of the present invention are not impaired, the carbon fiber may be subjected to surface treatment such as epoxy treatment, urethane treatment, oxidation treatment, etc., in order to increase the affinity with the polycarbonate resin.
The polycarbonate resin composition of the present invention may further contain an acidic compound. When the acidic compound is used, the compounding amount of the acidic compound is usually 0.00001 part by weight or more and 0.1 part by weight or less, preferably 0.0001 part by weight or more and 0.01 part by weight or less, More preferably, they are 0.0002 weight part or more and 0.001 weight part or less. When the compounding amount of the acidic compound is 0.00001 parts by weight or more, it is preferable in terms of coloration suppression when the residence time in the injection molding machine of the polycarbonate resin composition becomes long during injection molding. If the blending amount is more than 0.1 parts by weight, the hydrolysis resistance of the polycarbonate resin composition may be lowered.

  Examples of acidic compounds include hydrochloric acid, nitric acid, boric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, adipic acid, ascorbic acid, aspartic acid, azelaic acid, adenosine phosphoric acid, benzoic acid Acid, formic acid, valeric acid, citric acid, glycolic acid, glutamic acid, glutaric acid, cinnamic acid, succinic acid, acetic acid, tartaric acid, oxalic acid, p-toluenesulfinic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, nicotinic acid , Bronsted acids such as picric acid, picolinic acid, phthalic acid, terephthalic acid, propionic acid, benzenesulfinic acid, benzenesulfonic acid, malonic acid, maleic acid, and esters thereof. Among these acidic compounds or derivatives thereof, sulfonic acids or esters thereof are preferable, and p-toluenesulfonic acid, methyl p-toluenesulfonate, and butyl p-toluenesulfonate are particularly preferable.

These acidic compounds can be added in the manufacturing process of a polycarbonate resin composition as a compound which neutralizes the basic transesterification catalyst used in the polycondensation reaction of the polycarbonate resin mentioned above.
The polycarbonate resin composition of the present invention can be blended with an ultraviolet absorber as long as the object of the present invention is not impaired. The blending amount of the UV absorber can be appropriately selected according to the type of the UV absorber, but in the present invention, the UV absorber is 0 to 5 parts by weight with respect to the entire polycarbonate resin composition. is there.

Here, the ultraviolet absorber is not particularly limited as long as it is a compound having ultraviolet absorbing ability. Examples of the compound having ultraviolet absorbing ability include organic compounds and inorganic compounds. Of these, organic compounds are preferred because they are easy to ensure affinity with the polycarbonate resin and are easily dispersed uniformly.
The molecular weight of the organic compound having ultraviolet absorbing ability is not particularly limited, but is usually 200 or more, preferably 250 or more. Also. Usually, it is 600 or less, preferably 450 or less, more preferably 400 or less. If the molecular weight is too small, there is a possibility of causing a decrease in UV resistance performance after long-term use. When the molecular weight is excessively large, there is a possibility that the transparency of the resin composition is lowered after long-term use.

  Preferred ultraviolet absorbers include benzotriazole compounds, benzophenone compounds, triazine compounds, benzoate compounds, salicylic acid phenyl ester compounds, cyanoacrylate compounds, malonic acid ester compounds, oxalic acid anilide compounds, and the like. . Of these, benzotriazole compounds, hydroxybenzophenone compounds, and malonic ester compounds are preferably used. These may be used alone or in combination of two or more.

  More specific examples of the benzotriazole compounds include 2- (2′-hydroxy-3′-methyl-5′-hexylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl- 5'-hexylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-methyl-5'-t -Octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-dodecylphenyl) benzotriazole, 2- (2'-hydroxy-3'-methyl-5'-t-dodecylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, methyl-3- (3- (2H-benzotriazol-2-yl ) -5-t-butyl-4-hydroxyphenyl) propionate and the like.

Examples of hydroxybenzophenone compounds include 2,2′-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and the like.
Examples of the malonic ester compounds include 2- (1-arylalkylidene) malonic esters, tetraethyl-2,2 ′-(1,4-phenylene-dimethylidene) -bismalonate, and the like.

  Examples of the triazine compound include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3. 5-triazine, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-isooctyloxyphenyl) -s-triazine, 2- (4,6-diphenyl-1,3, 5-triazin-2-yl) -5-[(hexyl) oxy] -phenol (manufactured by Ciba Geigy, Tinuvin 1577FF) and the like.

Examples of the cyanoacrylate compound include ethyl-2-cyano-3,3-diphenyl acrylate, 2′-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and the like.
Examples of the oxalic acid anilide compound include 2-ethyl-2′-ethoxy-oxalanilide (manufactured by Clariant, Sanduvor VSU).

Moreover, a light stabilizer can be mix | blended in order to further improve the light resistance of the polycarbonate resin composition and polycarbonate resin molded product of the present invention. Examples of such a light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis- (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, poly [[ 6- (1,1,3
3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6 , 6-tetramethyl-4-piperidyl) imino]], N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6). -Pentamethyl-4-piperidylamino) -6-chloro-1,3,5-triazine condensate, dibutylamine, 1,3,5-triazine, N, N'-bis (2,2,6,6)- And a polycondensate of tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine. Of these, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis- (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate are preferred.

  The light stabilizer can be blended at a ratio of 0 part by weight or more and 2 parts by weight or less, but in order to obtain the blending effect of the light stabilizer, 0.005 part by weight or more and 0.5 part by weight. It is preferable to mix | blend in the ratio of the part below, More preferably, it mix | blends in the ratio of 0.01 weight part or more and 0.2 weight part or less. By blending the light stabilizer in such a range, the molded product obtained by molding the polycarbonate resin composition of the present invention without causing bleeding of the light stabilizer on the surface of the polycarbonate resin composition and deterioration of mechanical properties of various molded products. Light resistance can be improved.

Furthermore, the polycarbonate resin composition of the present invention can contain an antistatic agent within a range that does not impair the object of the present invention. The antistatic agent is usually used in an amount of 0 to 2 parts by weight with respect to 100 parts by weight of the polycarbonate resin.
In the present embodiment, the timing of addition and the addition method of components such as fluorescent whitening agent, filler, acidic compound, ultraviolet absorption aid, thermal stabilizer, light stabilizer, antistatic agent, etc. to be blended in the polycarbonate resin composition are as follows: There is no particular limitation. For example, when the polycarbonate resin is produced by the transesterification method, when the polymerization reaction is completed; the polycarbonate resin or the polycarbonate resin composition in the middle of kneading with the polycarbonate resin or other compounding agent, regardless of the polymerization method. Examples include a state where the product is melted, and a case where blending and kneading with a polycarbonate resin composition in a solid state such as pellets or powder using an extruder or the like. Examples of the addition method include a method in which various components are directly mixed or kneaded with a polycarbonate resin, a method in which a small concentration of a polycarbonate resin composition or other resin, etc. and a high concentration master batch prepared using various components are added. .

[Polycarbonate resin molded product]
A polycarbonate resin molded product can be obtained by molding the polycarbonate resin composition of the present invention. As a method for obtaining a polycarbonate resin molded article, a method of directly mixing raw materials such as polycarbonate resin, titanium oxide, and other resins and additives as necessary, and then molding the raw material into an extruder or an injection molding machine, the raw material And the like are melt-mixed using a twin screw extruder, extruded into a strand shape to produce pellets, and then the pellets are put into an extruder or an injection molding machine to be molded. The molding method of the polycarbonate resin molded product is not particularly limited, and a molding method such as an injection molding method, an extrusion molding method, or a compression molding method can be used, but the injection molding method is preferable from the viewpoint of the degree of freedom of the shape of the molded product. .

(Light reflecting member)
Since the polycarbonate resin composition of the present invention is excellent in hue, light reflectance, impact resistance and the like, a molded product thereof can be suitably used as a light reflecting member. Further, the polycarbonate resin composition of the present invention is advantageous as a light reflecting member from the viewpoint that it is excellent in light resistance and hardly deteriorates by light irradiation. The light reflecting member of the present invention not only has an excellent hue, but also maintains the impact resistance, light resistance, hue, heat resistance, dimensional stability, thermal stability, appearance, etc. inherent to the polycarbonate resin. Therefore, a light reflecting plate for a backlight of a liquid crystal display device, a light reflecting frame or a light reflecting sheet, and a light reflecting component such as a lighting device such as an electric / electronic device or an advertisement light, or an automotive device such as an automotive meter panel Or it is useful in the light reflection part agent use of a wide range, such as a light reflection sheet. In addition, the use of the polycarbonate resin composition of the present invention is not limited to the use of the light reflecting agent, and can be appropriately applied as long as it does not depart from the gist of the present invention.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by a following example, unless the summary is exceeded.
In the following, the physical properties or characteristics of the polycarbonate resin, the polycarbonate resin composition, and the molded product were evaluated by the following methods.

(1) Preparation method of test piece The pellet of the polycarbonate resin composition was dried at 90 ° C. for 6 hours using a hot air dryer. Next, the pellets of the dried polycarbonate resin composition are supplied to an injection molding machine (J75EII type manufactured by Nippon Steel Co., Ltd.), and the injection molded plate is subjected to a resin temperature of 240 ° C., a mold temperature of 60 ° C. and a molding cycle of 40 seconds. (Width 100 mm × length 100 mm × thickness 2 mm) was molded.

(2) Hue measurement According to JIS K7105 (1981), the spectrocolor difference meter (SE2000 manufactured by Nippon Denshoku Industries Co., Ltd.) is used for the injection-molded plate obtained in (1), and the D65 light source reflection method is used. The L ^* , a ^* , and b ^* values of the test piece were measured.

(3) Outdoor exposure The injection-molded plate obtained in (2) above was subjected to outdoor exposure treatment 24 hours a day and night in fine weather. The L ^* , a ^* , and b ^* values of the test pieces after exposure were measured. The values before processing were L ₀ ^* , a ₀ ^* , b ₀ ^* , and the values after processing were L ^* , a ^* , b ^*, and the color difference ΔE ^* was determined by the following equation. The smaller the color difference value, the smaller the change in color tone due to deterioration after the outdoor exposure test.

ΔL ^* = | L ^* −L ₀ ^* |
Δa ^* = | a ^* −a ₀ ^* |
Δb ^* = | b ^* −b ₀ ^* |
ΔE ^* = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2

  Moreover, the symbol of the compound used by the following example and the comparative example is as follows.

ISB: Isosorbide (Rocket Fleure, trade name POLYSORB)
CHDM: 1,4-cyclohexanedimethanol (Eastman)
DPC: Diphenyl carbonate (Mitsubishi Chemical Corporation)
<Titanium oxide>
Taipure R103 (DuPont, product name “Ti-Pure” R103)
Taipei PC-3 (product name "TIPAQUE" PC-3, manufactured by Ishihara Sangyo Co., Ltd.)
<Heat resistance improver>
SP-2011: Stearyl acid phosphate zinc salt (manufactured by ADEKA, product name “ADK STAB” (registered trademark) SP-2011)
AX-71: Phosphate ester (manufactured by ADEKA, product name “ADK STAB” (registered trademark) AX-71)

Other additives are as follows.
<Antioxidant>
2112: Phosphite antioxidant (manufactured by ADEKA, product name “ADK STAB” (registered trademark) 2112)
1010: Phenolic antioxidant (manufactured by BASF Japan, product name “IRGANOX” (registered trademark) 1010)
AO-412S: Phosphorous antioxidant (manufactured by ADEKA, product name “ADK STAB” (registered trademark) AO-412S)
<Release agent>
E-275: Glycol distearate (manufactured by NOF Corporation, product name “Unistar” E-275)
<Light resistance stabilizer>
TINUVIN 329: Benzotriazole UVA (manufactured by BASF, product name “TINUVIN” (registered trademark) 329)
TINUVIN770DF: HALS (manufactured by BASF, product name “TINUVIN” (registered trademark) 770DF)

[Example 1]
In a polymerization reactor equipped with a stirring blade and a reflux condenser controlled at 100 ° C., ISB and CHDM, DPC and calcium acetate monohydrate having a chloride ion concentration of 10 ppb or less by purification by distillation, a molar ratio In ISB / CHDM / DPC / calcium acetate monohydrate = 0.70 / 0.30 / 1.00 / 1.3 × 10 ⁻⁶ and sufficiently purged with nitrogen (oxygen concentration 0.0005) ~ 0.001 vol%).

  Subsequently, heating was performed with a heating medium, and stirring was started when the internal temperature reached 100 ° C., and the contents were melted and made uniform while controlling the internal temperature to be 100 ° C. After that, temperature increase was started, the internal temperature was adjusted to 210 ° C. in 40 minutes, and when the internal temperature reached 210 ° C., control was performed so as to maintain this temperature, and at the same time, pressure reduction was started and the temperature reached 210 ° C. After 90 minutes, the pressure was changed to 13.3 kPa (absolute pressure, the same applies hereinafter), and the pressure was maintained for another 60 minutes.

The phenol vapor produced as a by-product with the polymerization reaction is led to a reflux condenser using a steam controlled at 100 ° C. as the inlet temperature to the reflux condenser, and a monomer component contained in the phenol vapor in a slight amount is introduced into the polymerization reactor. Then, the phenol vapor that did not condense was recovered by guiding it to a condenser using 45 ° C. warm water as a refrigerant.
After the contents thus oligomerized are once restored to atmospheric pressure, they are transferred to another polymerization reaction apparatus equipped with a stirring blade and a reflux condenser controlled in the same manner as described above. The internal temperature was set to 220 ° C. and the pressure was set to 200 Pa in 60 minutes. Thereafter, the internal temperature was set to 230 ° C. and the pressure was set to 133 Pa or less over 20 minutes. When the predetermined stirring power was reached, the pressure was restored, the contents were extracted in the form of strands, and pelletized (polycarbonate resin 1) with a rotary cutter.

  Next, the pellets of the polycarbonate resin 1 obtained, and Taipure R103 as titanium oxide, Adekastab SP-2011 as phosphate esters, and Unistar E-275 as a release agent so as to have the composition shown in Table 1 below. Irganox 1010 and ADK STAB 2112 as antioxidants, and TINUVIN 329 and TINUVIN 770DF as light-resistant stabilizers were used as a twin screw extruder (LABOTEX 30HSS-32) manufactured by Nippon Steel Works, Ltd. The resin was extruded in a strand shape so that the resin temperature was 250 ° C., cooled and solidified with water, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump, and the pressure at the vent port was controlled to be 500 Pa. The evaluation results of the obtained pellet-like polycarbonate resin composition according to the above method are shown in Table 1 described later.

[Example 2]
Except that Adeka Stab AO-412S was used as an antioxidant and the composition shown in Table 1 below was used, the same procedure as in Example 1 was carried out to produce and evaluate a polycarbonate resin composition. It is shown in Table 1.

[Comparative Example 1]
A polycarbonate resin composition was produced and evaluated in the same manner as in Example 1 except that Adeka Stub SP-2011 was not used and the composition shown in Table 1 below was used. The results are shown in Table 1. It was.

[Comparative Example 2]
A polycarbonate resin composition was produced and evaluated in the same manner as in Example 2 except that Adeka Stub SP-2011 was not used and the composition shown in Table 1 below was used. The results are shown in Table 1. It was.

[Comparative Example 3]
Polycarbonate was used in the same manner as in Example 1 except that Adeka Stub SP-2011 was not used, Adeka Stab AX-71 was used as the phosphate ester, and the addition amount was changed to the composition shown in Table 1 below. The resin composition was produced and evaluated, and the results are shown in Table 1.

[Comparative Example 4]
Using Typeke PC-3 as titanium oxide, except that the amount added was changed to the composition shown in Table 1 below, the same procedure as in Comparative Example 1 was conducted to produce and evaluate a polycarbonate resin composition. The results are shown in Table 1.

Table 1 shows the following.
In the resin compositions of the examples, the change in ΔE ^* was as small as 0.8 or less as compared with the resin compositions of the comparative examples, and almost no change in appearance of the hue was observed.

The polycarbonate resin composition and molded product of the present invention are excellent in light resistance, hue, etc., and can provide materials to a wide range of fields such as injection molding fields such as electric / electronic parts and automotive parts, and extrusion fields such as films and sheets. Is possible. Further, the polycarbonate resin composition of the present invention is particularly useful as a light reflecting member because it is excellent in hue, color difference in outdoor exposure, and the like.

Claims (10)

  It contains 0.01 parts by weight or more and 30 parts by weight or less of titanium oxide with respect to 100 parts by weight of the polycarbonate resin containing the structural unit (a) derived from the dihydroxy compound (α) having a cyclic ether structure, and a phosphate metal A polycarbonate resin composition comprising 0.01 part by weight or more and 1 part by weight or less of a salt.   The polycarbonate resin in the resin composition is produced using at least one metal compound selected from the group consisting of a lithium compound and a metal compound of Group 2 of the long-period periodic table as a transesterification reaction catalyst. Item 5. The polycarbonate resin composition according to Item 1.   The polycarbonate resin composition according to claim 1, wherein the phosphate metal salt is a salt of a Group 12 metal element.   The polycarbonate resin composition according to any one of claims 1 to 3, comprising an antioxidant.   The polycarbonate resin composition according to any one of claims 1 to 4, comprising a light stabilizer.   The polycarbonate resin composition of any one of Claims 1-5 containing a mold release agent. The polycarbonate resin composition according to claim 1, wherein the dihydroxy compound (α) having a cyclic ether structure is a dihydroxy compound having a structure represented by the following formula (1).

  The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin contains a structural unit derived from an aliphatic hydrocarbon dihydroxy compound.   The polycarbonate resin molded product obtained by shape | molding the polycarbonate resin composition of any one of Claims 1-8.   The polycarbonate resin molded product according to claim 9, wherein the polycarbonate resin molded product is obtained by molding by an injection molding method.