JP5635228B2 - Polycarbonate resin composition - Google Patents

Description

  The present invention relates to a novel polycarbonate resin composition. More specifically, the present invention relates to a polycarbonate resin composition containing a portion that can be derived from a carbohydrate that is a biogenic substance, having both good heat resistance and heat stability, and excellent hue, weather resistance, and rigidity.

  The polycarbonate resin is a polymer in which an aromatic or aliphatic dioxy compound is linked by a carbonic acid ester, and among them, a polycarbonate resin obtained from 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A) (hereinafter “PC-”). A ”(sometimes referred to as“ A ”) is used in many applications such as mechanical parts, automobile parts, electrical / electronic parts, and office equipment parts because of its excellent properties such as mechanical strength and transparency. Reinforced polycarbonate resins obtained by adding various reinforcing agents to polycarbonate resins are also used in a wide range of applications due to their excellent mechanical strength and heat resistance.

  Furthermore, there is a resin composition that is highly filled with a white pigment typified by a titanium dioxide pigment and excellent in light reflectivity. Molded articles made of the resin composition are used in backlight reflectors for liquid crystal display devices, reflectors for illuminated push switches and photoelectric switches, display internal frames for vending machines, and strobe reflectors.

  In such a resin composition, not only performance such as high brightness and high white hue, but also severe molding conditions (for example, higher injection speed and higher molding temperature) to cope with thinness and downsizing of molded products. Etc.) is required. That is, it is required that defective phenomena such as yellowing and silver streak due to thermal deterioration during molding do not occur even under such severe molding conditions. Such yellowing reduces light reflection characteristics, and it is assumed that silver streaks are not present in the molded product in the first place. In addition, in recent years, there has been a demand for high light reflectivity so as to increase the reflection efficiency from the point of energy saving, and high light-shielding properties so that there is no loss of the amount of reflected light due to light transmission even in thin and compact molded products. There is a request. In such a demand, a large amount of titanium dioxide pigment may be added. As a result, molding defects such as yellowing and silver streaks due to thermal degradation of the resin during molding are more likely to occur. Therefore, higher thermal stability has been required in the polycarbonate resin composition containing the titanium dioxide pigment.

  It is known that aluminum oxide and organosiloxane are used as surface treatment agents as a heat stabilizing formulation for titanium dioxide pigment (see Patent Document 1). Further, it is known that silver streak can be reduced by using a titanium dioxide pigment having an aluminum oxide content of 0.1 to 2% by weight as a surface treating agent in an engineering plastic such as polyphenylene ether resin. Yes (see Patent Document 2). In addition, it is known to use polyorganohydrogensiloxane in a titanium oxide-containing polycarbonate resin composition (see Patent Document 3).

  Furthermore, a resin composition comprising an aromatic polycarbonate resin, an alkali metal perfluoroalkanesulfonic acid, and a titanium dioxide pigment is known (see Patent Document 4). In addition to this patent document, a resin composition comprising an aromatic polycarbonate resin, an alkali metal perfluoroalkanesulfonic acid, and a titanium dioxide pigment is disclosed and known (see Patent Documents 5 to 8).

  On the other hand, polycarbonate resins such as PC-A are generally manufactured using raw materials obtained from petroleum resources. However, there is a concern about the exhaustion of petroleum resources, and environmentally derived from biogenic materials such as plants. There is a growing demand for materials that use raw materials.

  A typical example of a biomass material that uses biogenic materials as raw materials is polylactic acid. Among biomass plastics, it has relatively high heat resistance and mechanical properties, so its application is expanding to tableware, packaging materials, general merchandise, etc. However, polylactic acid is insufficient in heat resistance when used as a molding material having excellent light reflectivity, and the crystalline polymer has low crystallinity, so that it cannot cope with high injection speed. There's a problem.

  On the other hand, as a polycarbonate resin using a biogenic material as a raw material, an aliphatic polycarbonate resin using a raw material obtained from an ether diol residue that can be produced from a carbohydrate has been studied.

に示したエーテルジオールは、たとえば糖類およびでんぷんなどから容易に作られ、３種の立体異性体が知られているが、具体的には下記式（ｂ）

に示す、１，４：３，６ージアンヒドローＤーソルビトール（本明細書では以下「イソソルビド」と呼称する）、下記式（ｃ）

に示す、１，４：３，６ージアンヒドローＤーマンニトール（本明細書では以下「イソマンニド」と呼称する）、下記式（ｄ）

に示す、１，４：３，６ージアンヒドローＬーイジトール（本明細書では以下「イソイディッド」と呼称する）である。 For example, the following formula (a)

The ether diol shown in Fig. 2 is easily made from, for example, sugars and starch, and three stereoisomers are known. Specifically, the following formula (b)

1,4: 3,6-dianhydro-D-sorbitol (hereinafter referred to as “isosorbide”), represented by the following formula (c)

1,4: 3,6-dianhydro-D-mannitol (hereinafter referred to as “isomannide”), represented by the following formula (d):

1,4: 3,6-dianhydro-L-iditol (hereinafter referred to as “isoidid” in the present specification).

  Isosorbide, isomannide, and isoidide are obtained from D-glucose, D-mannose, and L-idose, respectively. For example, isosorbide can be obtained by hydrogenating D-glucose and then dehydrating it using an acid catalyst.

  So far, among the above-mentioned ether diols, in particular, incorporation into polycarbonate using isosorbide as a monomer has been studied. Among them, isosorbide homopolycarbonate is described in Patent Documents 9 and 10 and Non-Patent Documents 1 and 2. The glass transition temperature of this homopolycarbonate is 166 ° C. in Non-Patent Document 1, and the glass transition temperature by differential calorimetry at a heating rate of 10 ° C./min in Patent Document 10 is 170 ° C. or higher compared with PC-A. Heat resistance is sufficient, and in addition, there is no ultraviolet absorption site such as an aromatic ring, so it is considered that the weather resistance is good. However, ether diols that can be produced from such saccharides were used as raw materials for polymers. In this case, coloring of the polymer is likely to occur during molding, causing a problem in practical use. Further, this polycarbonate is produced in the presence of a tin catalyst, has a thermal decomposition temperature (5% weight loss temperature) of around 300 ° C., and there is room for improvement in thermal stability. Furthermore, there is no report on a resin composition that is highly filled with a white pigment typified by such an aliphatic polycarbonate and a titanium dioxide pigment and excellent in light reflectivity.

Japanese Patent Publication No. 60-003430 Japanese Patent Laid-Open No. 11-060743 Japanese Examined Patent Publication No. 63-026140 JP 2003-183491 A JP 2002-372609 A JP 2003-226805 A JP 2003-213114 A JP 2003-342462 A British Patent Application No. 1079686 International Publication No. 2007/013463 Pamphlet “Journal of Applied Polymer Science”, 2002, Vol. 86, p. 872-880 “Macromolecules”, 1996, Vol. 29, p. 8077-8082

  The present invention solves the above problems, has a high content of biogenic substances, has excellent heat resistance, thermal stability, weather resistance and moldability, and has excellent hue and light reflectivity. The purpose is to provide goods.

で表されるカーボネート構成単位を含有するポリカーボネート樹脂中に含まれる炭素−炭素二重結合成分がポリマーの着色に深く関わりがある事を見出した。そして、ポリマー末端に生成する下記式（２）または（３）で表される炭素−炭素二重結合成分が含まれる割合をある特定の数値以下にしたポリカーボネート樹脂（Ａ成分）と二酸化チタン顔料（Ｂ成分）からなるポリカーボネート樹脂組成物が優れた耐熱性、熱安定性、耐候性および成形性を有し、かつ着色が少ないことを見出し本発明に至った。 As a result of intensive studies to achieve the above object, the present inventor has found that the following formula (1)

It was found that the carbon-carbon double bond component contained in the polycarbonate resin containing the carbonate structural unit represented by the formula is deeply related to the coloring of the polymer. And the polycarbonate resin (A component) which made the ratio in which the carbon-carbon double bond component represented by following formula (2) or (3) produced | generated at a polymer terminal is contained below a certain specific numerical value and a titanium dioxide pigment ( The present inventors have found that a polycarbonate resin composition comprising the component (B) has excellent heat resistance, thermal stability, weather resistance and moldability, and is less colored.

２．上記Ｂ成分は、アルコキシ基および／またはＳｉ−Ｈ基を含有する有機ケイ素化合物で表面処理されている二酸化チタン顔料である前項１記載のポリカーボネート樹脂組成物、
３．上記Ｂ成分は、（ｉ）その熱重量解析(ＴＧＡ)による２３℃〜１００℃における重量減少を（ａ）重量％、および２３℃〜３００℃における重量減少を（ｂ）重量％としたとき、０．０５≦（ｂ）−（ａ）≦０．６を満たし、（ｉｉ）その蛍光Ｘ線測定におけるＴｉ元素、Ａｌ元素、およびＳｉ元素に由来する重量割合をそれぞれ（ｃ）重量％、（ｄ）重量％および（ｅ）重量％としたとき、０．００１≦（ｄ）／（ｃ）≦０．０１を満たし、かつ０．００１≦（ｅ）／（ｃ）≦０．０２を満たす二酸化チタン顔料（Ｂ成分）である前項１または２に記載のポリカーボネート樹脂組成物、および
４．前項１記載のポリカーボネート樹脂組成物から形成された光反射材、
が提供される。 That is, according to the present invention: A polycarbonate resin containing a carbonate constituent unit represented by the following formula (1), wherein the polymer terminal contains a carbon-carbon double bond component represented by the following formula (2) and the following formula (3). Of 0.1 to 80 parts by weight of a titanium dioxide pigment (component B) with respect to 100 parts by weight of a polycarbonate resin (component A) having a total amount of 0.3% or less based on the carbonate constituent unit. Polycarbonate resin composition,

2. The polycarbonate resin composition according to item 1, wherein the component B is a titanium dioxide pigment that is surface-treated with an organosilicon compound containing an alkoxy group and / or a Si-H group.
3. When the above component B is (i) weight loss at 23 ° C. to 100 ° C. by thermogravimetric analysis (TGA) is (a) wt%, and weight loss at 23 ° C. to 300 ° C. is (b) wt%, 0.05 ≦ (b) − (a) ≦ 0.6 is satisfied, and (ii) the weight ratio derived from the Ti element, Al element, and Si element in the fluorescent X-ray measurement is (c) wt%, ( d) When wt% and (e) wt%, 0.001 ≦ (d) / (c) ≦ 0.01 is satisfied, and 0.001 ≦ (e) / (c) ≦ 0.02 is satisfied. 3. The polycarbonate resin composition according to item 1 or 2, which is a titanium dioxide pigment (component B), and A light reflecting material formed from the polycarbonate resin composition according to item 1,
Is provided.

Hereinafter, the present invention will be described in detail.
The polycarbonate resin (component A) used in the present invention is a polycarbonate resin containing a carbonate constituent unit represented by the formula (1), and among all the carbonate constituent units, the constituent unit represented by the formula (1) is 60. It is preferably at least mol%, more preferably at least 70 mol%, further preferably at least 80 mol%, particularly preferably at least 90 mol%. Most preferably, it is a homopolycarbonate resin consisting only of the carbonate structural unit of the formula (1).

The polycarbonate resin (component A) used in the present invention is a polycarbonate resin containing a carbonate constituent unit represented by the above formula (1), and is represented by the above formula (2) and the above formula (3) at the polymer terminal. The total amount of the carbon-carbon double bond component is 0.3% or less, preferably 0.2% or less, particularly preferably 0.15% or less with respect to the carbonate structural unit. The ratio was determined from the integral value of ¹ HNMR of the polycarbonate as follows.

That is, in ¹ HNMR (heavy solvent: CDCl ₃ ) of the polycarbonate resin containing the carbonate structural unit represented by the above formula (1), when the integral intensity of the proton represented by H ^h in FIG. When the integrated intensity of the carbon-carbon double bond component (peak of 6.5 to 6.7 ppm: see FIG. 2) is L, the ratio is represented by the following formula (A).

  The polycarbonate resin (component A) used in the present invention has a solution b value of 5.0 or less, preferably 4.5 or less, when measured at an optical path length of 30 mm in a 15% by weight methylene chloride solution of the polycarbonate resin. 0 or less is particularly preferable. The solution b value was measured using a Nippon Denshoku Co., Ltd. color difference meter 300A with the above solution placed in a sample tube with an optical path length of 30 mm.

In the polycarbonate resin (component A) used in the present invention, the lower limit of the specific viscosity at 20 ° C. of a solution obtained by dissolving 0.7 g of resin in 100 ml of methylene chloride is preferably 0.14 or more, and 0.20 or more. Is more preferably 0.22 or more. The upper limit of the specific viscosity is preferably 0.55 or less, more preferably 0.45 or less, and still more preferably 0.37 or less. When the specific viscosity is lower than 0.14, it becomes difficult to give sufficient mechanical strength to the molded product obtained from the light diffusing polycarbonate resin composition of the present invention. On the other hand, if the specific viscosity is higher than 0.55, the melt fluidity becomes too high, and the melting temperature having the fluidity necessary for molding becomes higher than the decomposition temperature, which is not preferable. Further, the polycarbonate resin (component A) used in the present invention has a melt viscosity measured by a capillary rheometer at 250 ° C. of 0.2 × 10 ^{3 to} 4.0 × 10 ³ Pa · s under the condition of a shear rate of 600 sec ^−1. It is preferably in the range of s, more preferably in the range of 0.4 × 10 ^{3 to} 3.0 × 10 ³ Pa · s, and 0.4 × 10 ^{3 to} 2.4 × 10 ³ Pa · s. More preferably, it is in the range. When the melt viscosity is in this range, the mechanical strength is excellent, and the moldability is good without the occurrence of silver during molding.

  The polycarbonate resin (component A) used in the present invention has a glass transition temperature (Tg) of preferably 120 to 175 ° C, more preferably 145 to 170 ° C, and further preferably 145 to 165 ° C. When Tg is less than 120 ° C, the heat resistance (particularly heat resistance due to moisture absorption) is poor, and when it exceeds 175 ° C, the melt fluidity during molding is poor. Tg is measured by DSC (model DSC2910) manufactured by TA Instruments.

  The polycarbonate resin (component A) used in the present invention has a 5% weight reduction temperature of preferably 320 to 400 ° C, more preferably 330 to 400 ° C. A 5% weight loss temperature within the above range is preferable because there is almost no decomposition of the resin during melt molding. The 5% weight loss temperature is measured by TA Instruments TGA (model TGA2950).

で表されるイソソルビド、イソマンニド、イソイディッドなどが挙げられる。 The polycarbonate resin (component A) used in the present invention can be produced by a melt polymerization method from a diol component containing an ether diol represented by the above formula (a) and a carbonic acid diester. As the ether diol, specifically, the following formulas (b), (c) and (d)

And isosorbide, isomannide, and isoidide represented by the formula:

  These saccharide-derived ether diols are substances obtained from natural biomass and are one of so-called renewable resources. Isosorbide is obtained by hydrogenating D-glucose obtained from starch and then dehydrating it. Other ether diols can be obtained by the same reaction except for the starting materials.

  In particular, a polycarbonate resin in which the carbonate structural unit includes a carbonate structural unit derived from isosorbide (1,4: 3,6-dianhydro-D-sorbitol) is preferable. Isosorbide is an ether diol that can be easily made from starch, and can be obtained in abundant resources, and is superior in all ease of manufacture, properties, and versatility of use compared to isomannide and isoidide. .

  As a manufacturing method of polycarbonate resin (A component) used for this invention, ether diol represented by the said Formula (a) and carbonic acid diester are mixed, and alcohol or phenol produced | generated by transesterification is carried out under high temperature and pressure reduction. A melt polymerization method of distilling is preferably used.

  The reaction temperature is preferably as low as possible in order to suppress decomposition of the ether diol and obtain a highly viscous resin with little coloration, but the polymerization temperature is 180 ° C. to 280 ° C. in order to proceed the polymerization reaction appropriately. It is preferably in the range of ° C, more preferably in the range of 180 ° C to 270 ° C.

In the initial stage of the reaction, ether diol and carbonic acid diester are heated at normal pressure and pre-reacted, and then gradually reduced in pressure, and the system is changed to 1.3 × 10 ^{−3 to} 1.3 × 10 ^{− in the} late stage of the reaction. A method of facilitating the distillation of alcohol or phenol produced by reducing the pressure to about ⁵ MPa is preferred. The reaction time is usually about 0.5 to 4 hours.

  Examples of the carbonic acid diester used for the production of the polycarbonate resin (component A) used in the present invention include esters such as optionally substituted aryl groups having 6 to 20 carbon atoms, aralkyl groups, or alkyl groups having 1 to 18 carbon atoms. It is done. Specific examples include diphenyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (p-butylphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. preferable.

  The carbonic acid diester is preferably mixed so as to have a molar ratio of 1.02 to 0.98 with respect to the total diol compound, more preferably 1.01 to 0.98, still more preferably 1.01 to 0. .99. If the molar ratio of the carbonic acid diester is more than 1.02, the carbonic acid diester residue acts as a terminal block and a sufficient degree of polymerization cannot be obtained, which is not preferable. Even when the molar ratio of carbonic acid diester is less than 0.98, a sufficient degree of polymerization cannot be obtained, which is not preferable.

  A polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, alkali metal compounds such as sodium salt or potassium salt of dihydric phenol, tetramethylammonium hydroxide, tetraethylammonium hydroxide, Examples thereof include nitrogen-containing basic compounds such as tetrabutylammonium hydroxide, trimethylamine, and triethylamine. As a method for obtaining the polycarbonate resin (component A) used in the present invention, it is preferable to use a combination of a nitrogen-containing basic compound and an alkali metal compound. In order to obtain a polycarbonate resin having a good hue, the alkali metal concentration Adjustment is important. In addition to being added as a catalyst, the alkali metal may be contained in the ether diol represented by the above formula (a), which is a raw material (see JP 2005-509667 A), and is therefore contained in the ether diol. It is preferable to adjust the alkali metal concentration in consideration of the alkali metal content.

  In the present invention, the alkali metal concentration when heated and melted at normal pressure is preferably 0.1 to 1.0 ppm, more preferably 0.1 to 0.7 ppm, particularly preferably 0.1 in the molten solution. Adjust to ˜0.5 ppm. When the alkali metal concentration is less than 0.1 ppm, it is not possible to obtain a polycarbonate resin having a sufficiently low polymerization catalyst activity and having a target specific viscosity. This will cause the hue to deteriorate. The molten solution is defined as a molten solution when ether diol and carbonic acid diester are mixed and melted. The concentration (= content) of the alkali metal was the total of the raw materials that were dry ashed, dissolved in nitric acid, fixed in pure water, and quantified by atomic absorption spectrophotometry. The atomic absorption photometer used was Z5000 manufactured by Hitachi, Ltd.

  The amount of the nitrogen-containing basic compound used in combination with the alkali metal compound is such that the ratio of the nitrogen-containing basic compound and the alkali metal is 50/1 to 2000/1 by weight ratio (nitrogen-containing basic compound / alkali metal). It is preferable to mix | blend so that it may become this range. This ratio is more preferably 100/1 to 2000/1, and particularly preferably 100/1 to 1000/1. When the ratio between the nitrogen-containing basic compound and the alkali metal is within this range, a polycarbonate resin (component A) having a good hue can be obtained.

  Further, the reaction system is preferably maintained in an atmosphere of a gas inert to raw materials such as nitrogen, reaction mixture, and reaction product. Examples of inert gases other than nitrogen include argon. Furthermore, an additive such as an antioxidant may be added as necessary, but an organic phosphorus compound represented by the following formula (4) which is an antioxidant is particularly preferable.

In the above formula (4), R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, particularly a hydrogen atom, a methyl group, or an isopropyl group. , An isobutyl group, a tert-butyl group, or a tert-pentyl group is preferable.

R ² is an alkyl group having 4 to 10 carbon atoms, preferably an alkyl group having 4 to 6 carbon atoms, and particularly preferably an isobutyl group, a tert-butyl group, a tert-pentyl group, or a cyclohexyl group.

R ³ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, or a carbon atom. From an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aralkyloxy group having 7 to 20 carbon atoms At least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, particularly a hydrogen atom or 1 to 10 carbon atoms. Are preferred.

  Preferred examples of the above formula (4) include bis (2-tert-butylphenyl) pentaerythritol diphosphite, bis (2-tert-pentylphenyl) pentaerythritol diphosphite, bis (2-cyclohexylphenyl) pentaerythritol diphosphite. Phyto, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphos And bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is preferable. Such an antioxidant may be one kind or a mixture of two or more kinds.

  The blending amount of the antioxidant is preferably 0.02 to 0.3 parts by weight, more preferably 0.05 to 0.3 parts by weight, and 0.05 to 0.25 parts by weight with respect to 100 parts by weight of the polycarbonate resin. Particularly preferred. When the antioxidant is within this range, it is possible to suppress a decrease in molecular weight or a deterioration in hue due to thermal decomposition during the production of the polycarbonate resin (component A).

  A catalyst deactivator can also be added to the polycarbonate resin obtained by the above production method. As the catalyst deactivator, known catalyst deactivators are effectively used. Among them, ammonium salts and phosphonium salts of sulfonic acid are preferable, and further, dodecylbenzenesulfonic acid such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid is preferable. The salts of paratoluenesulfonic acid such as the above-mentioned salts and paratoluenesulfonic acid tetrabutylammonium salt are preferred. As esters of sulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl paratoluenesulfonate, ethyl paratoluenesulfonate, butyl paratoluenesulfonate, para Octyl toluenesulfonate, phenyl p-toluenesulfonate and the like are preferably used, and among them, tetrabutylphosphonium dodecylbenzenesulfonate is most preferably used. These catalyst deactivators are used in an amount of 0.5 to 50 mol, preferably 0.5 to 10 mol, per mol of the polymerization catalyst selected from alkali metal compounds and / or alkaline earth metal compounds. It can be used in a proportion, more preferably in a proportion of 0.8 to 5 mol.

  In addition, the polycarbonate resin used in the present invention may be copolymerized with aliphatic diols and / or aromatic bisphenols within a range that does not impair the properties thereof. The proportion of the aliphatic diols and / or aromatic bisphenols in the total diol component is preferably 40 mol% or less, more preferably 30 mol% or less, further preferably 20 mol% or less, and particularly preferably 10 mol% or less. .

（式中、ｍは１〜２０の整数） As the aliphatic diol, an aliphatic diol represented by the following formula (α) is preferably used.

(Where m is an integer from 1 to 20)

  Specifically, linear diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanediol, cyclohexanedimethanol, etc. Among these, 1,3-propanediol, 1,4-butanediol, hexanediol, and cyclohexanedimethanol are preferable.

  As aromatic bisphenols, 2,2-bis (4-hydroxyphenyl) propane (commonly known as “bisphenol A”), 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4 '-(m-phenylenediisopropylidene) diphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 2,2-bis (4 -Hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) decane, 1,3-bis {2- (4 -Hydroxyphenyl) propyl} benzene and the like.

  In addition to the ether diol represented by the above formula (1), the aliphatic diol represented by the above formula (2) and the aromatic bisphenol, other diol residues can also be contained. Other diols include aromatic diols such as dimethanolbenzene and diethanolbenzene.

  Moreover, the polycarbonate resin (A component) used for this invention can also introduce | transduce an end group in the range which does not impair the characteristic. Such end groups can be introduced by adding the corresponding hydroxy compound during polymerization. The terminal group is preferably a terminal group represented by the following formula (5) or (6).

であり、好ましくは炭素原子数４〜２０のアルキル基、炭素原子数４〜２０のパーフルオロアルキル基、または上記式（７）であり、特に炭素原子数８〜２０のアルキル基、または上記式（７）が好ましい。Ｘは単結合、エーテル結合、チオエーテル結合、エステル結合、アミノ結合およびアミド結合からなる群より選ばれる少なくとも一種の結合が好ましいが、より好ましくは単結合、エーテル結合およびエステル結合からなる群より選ばれる少なくとも一種の結合であり、なかでも単結合、エステル結合が好ましい。ａは１〜５の整数であり、好ましくは１〜３の整数であり、特に１が好ましい。 In the above formulas (5) and (6), R ⁴ represents an alkyl group having 4 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a perfluoroalkyl group having 4 to 30 carbon atoms, or the following formula ( 7)

Preferably an alkyl group having 4 to 20 carbon atoms, a perfluoroalkyl group having 4 to 20 carbon atoms, or the above formula (7), particularly an alkyl group having 8 to 20 carbon atoms, or the above formula. (7) is preferred. X is preferably at least one bond selected from the group consisting of a single bond, ether bond, thioether bond, ester bond, amino bond and amide bond, more preferably selected from the group consisting of a single bond, ether bond and ester bond. It is at least one kind of bond, and among them, a single bond and an ester bond are preferable. a is an integer of 1 to 5, preferably an integer of 1 to 3, and 1 is particularly preferable.

In the above formula (7), R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, It is at least one group selected from the group consisting of an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, preferably each independently a carbon atom. And at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms, particularly at least one group independently selected from the group consisting of a methyl group and a phenyl group. Is preferred. b is an integer of 0 to 3, an integer of 1 to 3 is preferable, and an integer of 2 to 3 is particularly preferable. c is an integer of 4 to 100, preferably an integer of 4 to 50, and particularly preferably an integer of 8 to 50.

  Since the polycarbonate resin (component A) used in the present invention has a carbonate structural unit in the main chain structure using raw materials obtained from renewable resources such as plants, these hydroxy compounds are also derived from renewable resources such as plants. The obtained raw material is preferable. Examples of hydroxy compounds obtained from plants include long-chain alkyl alcohols having 14 or more carbon atoms (cetanol, stearyl alcohol, behenyl alcohol) obtained from vegetable oils.

The B component used in the present invention is a titanium dioxide pigment. As the titanium dioxide pigment, those usually used for various coloring applications can be used, and they are well known per se. There is also a titanium dioxide pigment composed of 100% by weight of TiO ₂ (in the present invention, the titanium dioxide component of the titanium dioxide pigment is expressed as “TiO ₂ ”, and the entire pigment including the surface treatment agent is referred to as “titanium dioxide pigment”. write). However, surface treatment is usually performed with oxides of various metals such as aluminum, silicon, titanium, zirconium, antimony, tin, and zinc. Also in the present invention, preferred titanium dioxide pigments are those obtained by subjecting a metal oxide to a surface treatment. The metal oxide component for these surface treatments, some may be a mode which is present inside the TiO ₂ particles.

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

  In such silane compounds and siloxane compounds, a part of the alkyl groups may be substituted with phenyl groups, but those having no phenyl group substitution are more preferable. Such an alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group.

  The alkylalkoxysilane compound may contain any of 1 to 3 alkoxy groups, or may be a mixture thereof, preferably 2 to 3 alkoxy groups, particularly preferably 3 alkoxy groups. . Specific examples of the alkylalkoxysilane compound include, for example, methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, methyloctyldimethoxysilane, decyltrimethoxysilane, and octadecyltrimethoxysilane. Is done.

  The content ratio of the alkoxy group and the Si—H group in the siloxane compound is preferably in the range of 0.1 to 1.2 mol / 100 g, more preferably in the range of 0.12 to 1 mol / 100 g, and 0.15 to 0.6 mol / A range of 100 g is more preferable. Such a ratio can be determined by measuring the amount of hydrogen or alcohol generated per unit weight of the siloxane compound by an alkali decomposition method.

In general, the structure of a siloxane compound is constituted by arbitrarily combining the following four types of siloxane units. That is,
M units: (CH ₃ ) ₃ SiO _1/2 , H (CH ₃ ) ₂ SiO _1/2 , H ₂ (CH ₃ ) SiO _1/2 , (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2 Monofunctional siloxane units such as (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 , (CH ₃ ) (C ₆ H ₅ ) (CH ₂ ═CH) SiO _1/2 ,
D unit: (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ ═CH) SiO, (C ₆ H ₅ ) 2SiO, etc. A bifunctional siloxane unit of
T unit: (CH ₃ ) SiO _3/2 , (C ₃ H ₇ ) SiO _3/2 , HSiO _3/2 , (CH ₂ ═CH) SiO _3/2 , (C ₆ H ₅ ) SiO _3/2 etc. A trifunctional siloxane unit of
Q unit: a tetrafunctional siloxane unit represented by SiO ₂ .

  Specific examples of the structure of the siloxane compound include Dn, Tp, MmDn, MmTp, MmQq, MmDnTp, MmDnQq, MmTpQq, MmDnTpQq, DnTp, DnQq, and DnTpQq. Among these, preferred structures of the silicone compound are MmDn, MmTp, MmDnTp, and MmDnQq, and a more preferred structure is MmDn or MmDnTp.

  Here, the coefficients m, n, p, and q in the above formula are integers of 1 or more that indicate the degree of polymerization of each siloxane unit, and the sum of the coefficients in each formula represents the average degree of polymerization of the siloxane compound. . This average degree of polymerization is preferably in the range of 2-150, more preferably in the range of 3-80. Moreover, when any of m, n, p, and q is a numerical value of 2 or more, it can be set as 2 or more types of siloxane units from which the hydrogen atom couple | bonded and an organic residue differ.

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

  A preferred embodiment of the titanium dioxide pigment of the present invention comprises (i) a weight loss at 23 ° C. to 100 ° C. according to its thermogravimetric analysis (TGA) (a) wt%, and a weight loss at 23 ° C. to 300 ° C. (b ) When wt%, 0.05 ≦ (b) − (a) ≦ 0.6 is satisfied, and (ii) the weight ratio derived from the Ti element, Al element, and Si element in the fluorescent X-ray measurement is When (c), (d) and (e) are satisfied, 0.001 ≦ (d) / (c) ≦ 0.01 is satisfied, and 0.001 ≦ (e) / (c) ≦ 0.02 is satisfied. To meet.

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

  When the above (b)-(a) is 0.6 or less, (d) / (c) is 0.01 or less, and (e) / (c) is 0.02 or less, the effect of thermal stability is further improved. Prominently demonstrated. When (b)-(a) is 0.05 or more, and (d) / (c) and (e) / (c) are 0.001 or more, a good hue can be obtained, particularly at high filling. Light reflection characteristics can be obtained.

  Note that the thermogravimetric analysis (TGA) measurement under the above condition (i) is performed under the TGA measurement device under the measurement conditions in which the temperature is increased from 23 ° C. in a nitrogen gas atmosphere to 900 ° C. at a temperature increase rate of 20 ° C./min. . The operation of calculating the weight ratio of the element from the fluorescent X-ray measurement in the above condition (ii) can be calculated based on the calibration line calculated from the element weight and the peak intensity usually obtained from the standard of each element. . In recent years, a quantifiable program is incorporated in a fluorescent X-ray measurement apparatus, and the weight ratio of elements can be directly obtained from the apparatus. Examples of the apparatus include MESA-500 type manufactured by Horiba, Ltd., and can be suitably used for calculating the weight ratio of elements. Such calculation is performed by the basic parameter method in the MESA-500 type.

TiO _{2 in the} component B may be either anatase type or rutile type in crystal form, and they can be mixed and used as necessary. A rutile type is more preferable in terms of initial mechanical properties and long-term weather resistance. A rutile type crystal may contain an anatase type crystal. Furthermore TiO ₂ production process is sulfuric acid method, chlorine method, but those which have been prepared by various other methods can be used, the chlorine method is more preferred. Further, the titanium dioxide pigment of the present invention is not particularly limited in its shape, but is preferably in the form of particles. The average particle diameter of the titanium dioxide pigment is preferably 0.01 to 0.4 μm, more preferably 0.1 to 0.3 μm, and still more preferably 0.15 to 0.25 μm. Such an average particle diameter is calculated by measuring the number of individual single particles and observing the number average thereof through observation with an electron microscope.

The coating with various metal oxides on the surface of TiO ₂ can be performed by various commonly used methods. For example, it is manufactured from the following steps 1) to 8). That is, 1) untreated TiO ₂ after dry pulverization is made into an aqueous slurry, 2) the slurry is wet pulverized and atomized, 3) a fine particle slurry is collected, and 4) a metal salt is soluble in the fine particle slurry. Add compound 5) Neutralize and coat TiO ₂ surface with metal hydrated oxide 6) Remove by-products, adjust slurry pH, filter, and clean with pure water 7) Washed 8) A method of pulverizing the dried product with a jet mill or the like. In addition to this method, for example, a method of reacting TiO ₂ particles with an active metal compound in a gas phase can be mentioned. Further, in the coating of the metal oxide surface treatment agent on the TiO ₂ surface, firing after the surface treatment, surface treatment again after the surface treatment, and firing after the surface treatment and surface treatment again are performed. Is possible. As the surface treatment with the metal oxide, either a high-density treatment or a low-density (porous) treatment can be selected.

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

  The polycarbonate resin composition of the present invention can contain a fluorescent brightening agent as necessary. Inclusion of the fluorescent brightening agent has the effect of increasing the amount of reflected light. Here, the fluorescent whitening agent has an action of absorbing energy in the ultraviolet part of the light and radiating this energy to the visible part. As the optical brightener, known bisbenzoxazole, coumarin, bis (styryl) biphenyl, and the like can be used. Of these, coumarin fluorescent whitening agents are preferred. Examples of the coumarin fluorescent whitening agent include triazine-phenylcoumarin, benzotriazole-phenylcoumarin, and naphthotriazole-phenylcoumarin. For example, a fluorescent brightener represented by the following formula (8) is preferable.

（但し、上記式中Ｒ^１０はアミノ基、アルキル基置換アミノ基、水酸基、および下記式（８−i）、（８−ii）または（８−iii）のいずれかを示し、Ｒ^１１は水素原子またはフルオロアルキル基を示し、Ｒ^１２は水素原子、アルキル基、またはアリール基のいずれかを示す。）

(In the above formula, R ¹⁰ represents an amino group, an alkyl group-substituted amino group, a hydroxyl group, and any one of the following formulas (8-i), (8-ii) or (8-iii), and R ¹¹ represents hydrogen) An atom or a fluoroalkyl group, and R ¹² represents a hydrogen atom, an alkyl group, or an aryl group.)

  The content of the optical brightener is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight, and still more preferably 0.000 to 100 parts by weight of the polycarbonate resin (component A). 001 to 0.1 parts by weight. In such a range, better light reflectivity is achieved.

  The polycarbonate resin composition of the present invention preferably contains a phosphorus stabilizer in order to obtain a better hue and stable fluidity. In particular, a pentaerythritol phosphite compound represented by the following formula (9) is preferably blended as a phosphorus stabilizer.

［式中Ｒ^２１、Ｒ^２２はそれぞれ水素原子、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基ないしアルキルアリール基、炭素数７〜３０のアラルキル基、炭素数４〜２０のシクロアルキル基、または炭素数１５〜２５の２−（４−オキシフェニル）プロピル置換アリール基を示す。なお、シクロアルキル基およびアリール基は、アルキル基で置換されていてもよい。］

[Wherein R ²¹ and R ²² are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an alkylaryl group, an aralkyl group having 7 to 30 carbon atoms, and an alkyl group having 4 to 20 carbon atoms. A cycloalkyl group or a 2- (4-oxyphenyl) propyl-substituted aryl group having 15 to 25 carbon atoms is shown. In addition, the cycloalkyl group and the aryl group may be substituted with an alkyl group. ]

  More specifically, examples of the pentaerythritol type phosphite compound include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and bis (2,6 -Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, Examples thereof include bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, etc. Among them, distearyl pentaerythritol diphosphite, bis (2,4-di-tert- Butylphenyl) pentaerythritol diphosphite and bis (2,6-di -tert- butyl-4-methylphenyl) pentaerythritol diphosphite.

  Examples of other phosphorus stabilizers include various other phosphite compounds, phosphonite compounds, and phosphate compounds.

  Examples of the phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl Monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris (diethylphenyl) phos Phyto, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite Ito, and tris (2,6-di -tert- butylphenyl) phosphite and the like.

  Still other phosphite compounds that react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

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

  Said phosphorus stabilizer can be used individually or in combination of 2 or more types, It is preferable to mix | blend an effective amount of a pentaerythritol type | mold phosphite compound at least. The phosphorus stabilizer is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, still more preferably 0.01 to 0.3 part by weight per 100 parts by weight of the polycarbonate resin (component A). Partly formulated.

  In addition, various other additives (function-imparting agents) may be added to the polycarbonate resin composition of the present invention, for example, plasticizers, light stabilizers, heavy metal deactivators, impact absorbers. Flame retardants, lubricants, antistatic agents, UV absorbers and the like. Furthermore, in the polycarbonate resin composition of the present invention, various organic and inorganic fillers, fibers and the like can be used in combination depending on the application. Examples of the filler include carbon, talc, mica, wollastonite, montmorillonite, and hydrotalcite. Examples of the fibers include natural fibers such as kenaf, various synthetic fibers, glass fibers, quartz fibers, and carbon fibers.

  The polycarbonate resin composition of the present invention includes, for example, aliphatic polyesters, aromatic polyesters, aromatic polycarbonates, polyamides, polystyrenes, polyolefins, polyacryls, ABS, polyurethanes, and various types including polylactic acid. It can also be used by mixing with polymers made of biogenic substances and alloying them.

  Since the polycarbonate resin composition of the present invention has excellent light reflectance, thermal stability, weather resistance, hue, rigidity, and moldability, it is suitably used for various light reflecting materials. More specifically, various lamp reflectors can be mentioned, for example, reflectors for illumination lamps such as fluorescent lamps, backlight reflectors for various display devices such as liquid crystal display devices, reflectors for switches, and reflectors for LED arrays. In addition, a reflecting plate in which these functions are combined is exemplified. That is, the polycarbonate resin composition of the present invention is useful for various applications such as various electronic / electrical equipment, OA equipment, vehicle parts, machine parts, other agricultural materials, transport containers, playground equipment, and miscellaneous goods. The effect is exceptional.

The following examples further illustrate the present invention. However, the present invention is not limited to these examples. Moreover, the part in an Example is a weight part and% is weight%. The evaluation was based on the following method.
(1) Light reflectance: Arithmetic average roughness (Ra) formed by an injection molding machine (SG-150U, manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 300 ° C. and a mold temperature of 100 ° C. is 0.03 μm. A molded plate having a thickness of 2 mm (length 90 mm × width 50 mm) was measured with a color computer (TC-1800MK-II manufactured by Tokyo Denshoku). Evaluation was made with the lowest reflectance value at wavelengths of 450 nm to 850 nm.
(2) UV resistance: A molded plate similar to that in the above evaluation (1) was used, using a xenon weather meter (Suga Test Instruments Co., Ltd .: WEL-SUN: HC-B), black panel temperature 63 ° C, humidity 50 The difference between the hue (YI) after 1000 hours in% and the hue (YI) before processing is indicated as ΔYI. Hue (YI) was measured by Nippon Denshoku Co., Ltd. color difference meter SE2000.
(3) Flexural modulus The bending test was performed according to ISO178. The test piece (shape: length 80 mm × width 10 mm × thickness 4 mm) was molded at a cylinder temperature of 250 ° C. and a mold temperature of 90 ° C. using JSWJ-75EIII manufactured by Nippon Steel Works.
(4) Deflection temperature under load (1.80 MPa): Deflection temperature under high load (1.80 MPa) specified by ISO75-1 and 75-2 using the bending test piece molded in (3) above. It was measured.
(5) Specific viscosity η _sp
The pellet was dissolved in methylene chloride, the concentration was about 0.7 g / dL, and the temperature was measured at 20 ° C. using an Ostwald viscometer (device name: RIGO AUTO VISCOSIMETER TYPE VMR-0525 · PC). The specific viscosity η _sp is obtained from the following formula.
η _sp = t / t _o −1
t: sample solution flow time t _o of: using a solvent only flow time (6) Melt viscosity Toyo Seiki capillary rheometer (Capillograph Model 1D), a capillary length 10.0 mm, capillary diameter 1.0 mm, measured temperature The melt viscosity at 600 sec ⁻¹ was read from the Shear Rate / Viscosity curve obtained as a result of measurement with the measurement speed arbitrarily changed at 250 ° C.
(7) Glass transition temperature Measured by DSC (model DSC2910) manufactured by TA Instruments.
(8) 5% weight loss temperature Measured with TGA (model TGA2950) manufactured by TA Instruments.
(9) Hue (solution b value)
The pellet is dissolved in methylene chloride, the concentration is 15% by weight, and the mixture is put in a sample tube having an optical path length of 30 mm. Subsequently, it measured using the Nippon Denshoku Co., Ltd. color difference meter 300A at 20 degreeC. The b value is derived from the Hunter's color difference formula from the tristimulus values X, Y, and Z specified in JIS Z8722. The lower the value, the closer the hue is to colorless.
(10) Ratio of carbon-carbon double bond component The pellet is dissolved in a heavy solvent (CDCl ₃ ), ¹ HNMR measurement is performed, and the integrated value of the specific proton in the carbonate constituent unit represented by the above formula (1) and the above The ratio of the carbon-carbon double bond component was calculated from the ratio with the integral value of the specific proton derived from the carbon-carbon double bond component represented by the formula (2) or (3). About the method of calculating this ratio, the manufacture example 4 is shown as a specific example below. In addition, JNM JLM-AL400 was used for NMR.
(11) Alkali metal content Samples were dry ashed, dissolved with nitric acid, dissolved in pure water, and the alkali metal content was quantified by atomic absorption spectrophotometry. A Z5000 manufactured by Hitachi, Ltd. was used.

[Reference Example 1] Production of isosorbide A 70% aqueous solution of sorbitol (Sorbit (registered trademark) D-70 (manufactured by Towa Kasei Kogyo Co., Ltd.)) was charged in 1930 parts by weight in a vacuum reactor equipped with a glass stirrer with a capacity of 2 L, and a vacuum of 40 Torr. Then, the mixture was heated to 120 ° C. to distill water, and then 32 parts by weight of 98% concentrated sulfuric acid was added and reacted for 24 hours under reduced pressure to distill 262 parts by weight of water. Cooled to 80 ° C. and neutralized with 40% aqueous sodium hydroxide solution to pH 7.2 (1% aqueous solution) The reaction was heated to 130 ° C. under reduced pressure to remove the water by distilling, 1076 parts by weight of crude isosorbide was obtained, and this crude isosorbide was charged into a vacuum distillation apparatus and heated to a bath temperature of 210 ° C. under a reduced pressure of 9 Torr, and 788 parts by weight of a distillate was obtained over about 3 hours. Next, 760 parts by weight of pure water was added to the above distillate, diluted and dissolved, and then 146 parts by weight of powdered activated carbon was added and stirred at 60 ° C. for 6 hours. 1434 parts by weight of an aqueous solution was obtained, and this aqueous solution was charged into a vacuum distillation apparatus, and water was distilled off at 130 ° C. and 50 Torr, followed by distillation at 190 ° C. and 9 Torr to obtain 734 parts by weight of white isosorbide. The alkali metal content of was 1.1 ppm.

[Reference Example 2] Preparation of isosorbide having different alkali metal concentrations The isosorbide obtained in Reference Example 1 was purified by recrystallization (recrystallization solvent: methanol). The alkali metal content of this recrystallized isosorbide was 0.2 ppm.
Further, the recrystallized isosorbide was distilled and purified again at 190 ° C. and 9 Torr. The alkali metal content of this distilled and purified isosorbide was 0 ppm.
On the other hand, when the alkali metal content of isosorbide (POLYSORB-P) manufactured by Rocket Corporation was measured, it was 4.6 ppm.

[Reference Example 3] Production of diphenyl carbonate 330.8 parts of ion-exchanged water, 106.0 parts of 48.6% caustic soda aqueous solution and phenol (reagent special grade) in a reaction vessel equipped with a stirring blade, thermometer, condenser and gas blowing pipe ) 118.1 parts of sodium phenolate aqueous solution was prepared, and the internal temperature was cooled to 20 ° C. with a water bath. While stirring, 64.16 parts of phosgene gas was blown into the reaction vessel over 40 minutes. During this period, the reaction vessel was cooled with a water bath and the internal temperature was maintained at about 30 ° C. After completion of the phosgene gas blowing, stirring was continued at room temperature for 3 hours to complete the reaction. The produced diphenyl carbonate was collected by filtration, washed 5 times with 400 parts of ion exchange water, and then dried under reduced pressure at 50 ° C. for 10 hours. 127.7 parts of diphenyl carbonate having a melting point of 80 to 81 ° C. (yield based on 95% phenol) was obtained. The alkali metal content of this diphenyl carbonate was measured and found to be 0 ppm (below the detection limit).

  In the following polycarbonate resin production examples 4 to 6, polymers were synthesized using isosorbide obtained in Reference Examples 1 and 2 and diphenyl carbonate obtained in Reference Example 3.

[Production Example 4] Production of polycarbonate resin 1608 parts by weight (11 mol) of isosorbide (hereinafter referred to as “ISS-1”) having an alkali metal (sodium) content of 0 ppm and diphenyl carbonate (hereinafter referred to as “DPC”). 2356 parts by weight (referred to as “TMAH”) as a polymerization catalyst, and 0.31 part by weight (3 × 1 mol of DPC component). 10 ⁻⁴ mol) and sodium hydroxide (hereinafter referred to as “NaOH”) 6.6 × 10 ⁻⁴ parts by weight (1.5 × 10 ⁻⁶ mol with respect to 1 mol of DPC component), and a stabilizer As bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (hereinafter referred to as “P-1”) It was 500ppm added and heated to 180 ° C. in a nitrogen atmosphere under normal pressure to melt against DPC.
When the concentration of the alkali metal and the ratio of the nitrogen-containing basic compound / alkali metal compound in the molten solution is calculated from the charged amount, the concentration of the alkali metal is 0.1 ppm, and the concentration of the nitrogen-containing basic compound / alkali metal compound is The ratio is 828/1.

After the charged components were completely melted, the pressure in the reaction vessel was gradually reduced over 30 minutes with stirring, and the pressure was reduced to 13.3 × 10 ⁻³ MPa while distilling off the produced phenol. After reacting in this state for 20 minutes, the temperature was raised to 200 ° C., then the pressure was gradually reduced over 20 minutes, and the reaction was carried out at 4.00 × 10 ⁻³ MPa for 20 minutes while distilling off the phenol. The mixture was heated to 250 ° C. for 30 minutes and reacted for 30 minutes.
Next, the pressure was gradually reduced, and the reaction was continued at 2.67 × 10 ⁻³ MPa for 10 minutes and 1.33 × 10 ⁻³ MPa for 10 minutes, and further reduced in pressure to reach 4.00 × 10 ⁻⁵ MPa. The temperature was gradually raised to 260 ° C., and the reaction was finally carried out at 260 ° C. and 6.66 × 10 ⁻⁵ MPa for 1 hour. As a result, a polymer having a specific viscosity of 0.41 was obtained. The melt viscosity of this polymer at 250 ° C. and 600 sec ⁻¹ was 2.59 × 10 ³ Pa · s, the glass transition temperature was 167 ° C., the 5% weight loss temperature was 357 ° C., and the solution b value was 3.7.

[Measurement of proportion of carbon-carbon double bond component]
The ¹ HNMR (heavy solvent: CDCl ₃ ) measurement result of the polymer obtained in Production Example 4 is shown in FIG. In FIG. 1, the peak attributed to the carbon-carbon double bond component (chemical shift 6.5 to 6.6) when the integrated intensity of the peak attributed to H ^h of isosorbide (around 4.9 ppm in chemical shift) is 1. The integrated intensity of 7 ppm was 0.0015. Since these peaks all correspond to one proton, the ratio of the carbon-carbon double bond component is
It is calculated as 0.0015 / (1 + 0.0015) × 100 = 0.15 (%).

[Production Example 5] Production of polycarbonate resin Isosorbide having an alkali metal (sodium) content of 0.2 ppm instead of "ISS-1" was used, and 0.11 part by weight of TMAH as a polymerization catalyst (based on 1 mol of DPC component) 1.0 × 10 ⁻⁴ mol) and 1.1 × 10 ⁻⁴ parts by weight of NaOH (0.25 × 10 ⁻⁶ mol with respect to 1 mol of DPC component), and stabilizer P-1 is added to DPC. Polymerization was carried out in the same manner as in Production Example 1 except that 1000 ppm was added, to obtain a polymer having a specific viscosity of 0.36. This polymer had a melt viscosity of 1.91 × 10 ³ Pa · s at 250 ° C. and 600 sec ⁻¹ , a glass transition temperature of 165 ° C., a 5% weight loss temperature of 362 ° C., a solution b value of 2.9, and carbon-carbon. The ratio of double bond components was 0.11%.

[Production Example 6] Production of polycarbonate resin Isosorbide having an alkali metal (sodium) content of 4.6 ppm was used in place of ISS-1, and 0.21 part by weight of TMAH as a polymerization catalyst (2 parts per mole of DPC component). 0.0 × 10 ⁻⁴ mol) was added and polymerized in the same manner as in Production Example 1 except that the stabilizer P-1 was not added to obtain a polymer having a specific viscosity of 0.23. The melt viscosity at 250 ° C. and 600 sec ⁻¹ of this polymer is 0.66 × 10 ³ Pa · s, the glass transition temperature is 158 ° C., the 5% weight loss temperature is 354 ° C., the solution b value is 16.3, carbon-carbon The ratio of double bond components was 0.74%.

[Examples 1 to 4, Comparative Example 1]
The resin composition described in Table 1 was prepared as follows. Each component in the ratio shown in Table 1 was weighed and mixed in a blender, and then melt-kneaded using a vented twin screw extruder to obtain pellets. The additives to be added to the polycarbonate resin were preliminarily prepared with a polycarbonate resin in advance with a concentration of 10 to 100 times the blending amount as a guide, and then the whole was mixed by a blender. The vent type twin screw extruder used was KZW15-25MG manufactured by Technobell. The extrusion conditions were a discharge rate of 14 kg / h, a screw rotation speed of 250 rpm, and a vent vacuum of 3 kPa, and the extrusion temperature was 250 ° C. from the first supply port to the die part. The obtained pellets were dried at 100 ° C. for 12 hours with a hot air circulation dryer, and then a test piece for evaluation was molded using an injection molding machine. The evaluation results are shown in Table 1.

The raw materials used in Table 1 are as follows.
(A component)
A-1: Polycarbonate resin pellets produced in Production Example 4 A-2: Polycarbonate resin pellets produced in Production Example 5 A-3: Polycarbonate resin pellets produced in Production Example 6 (component B)
B-1: Titanium dioxide (Taipaque PC-3 (trade name) manufactured by Ishihara Sangyo Co., Ltd.), the titanium dioxide is a rutile crystal produced by a chlorine method, and is 23 ° C. to 100 ° C. by a thermogravimetric apparatus (TGA). (B)-(a) is 0.57 when the weight loss at 0 ° C. is (a) wt%, and the weight loss at 23 ° C. to 300 ° C. is (b) wt%, and Al element in fluorescent X-ray measurement (This is a titanium dioxide pigment having a / Ti element weight ratio of 0.014 and a Si element / Ti element weight ratio of 0.018)
In addition, the calculation of the weight ratio of each element in the fluorescent X-ray measurement was performed by the basic parameter method using MESA-500 type manufactured by Horiba, Ltd. This calculation method is the same for other titanium dioxide pigments.
B-2: Titanium dioxide (manufactured by Resino Color Industry Co., Ltd. White DCF-T-17007, the titanium dioxide is a rutile crystal produced by the chlorine method at 23 ° C to 100 ° C by a thermogravimetric apparatus (TGA) (B)-(a) is 0.28 when the weight reduction is (a) wt% and the weight reduction at 23 ° C. to 300 ° C. is (b) wt%, and Al element / Ti element in fluorescent X-ray measurement A titanium dioxide pigment having a weight ratio of 0.008 and a Si / Ti element weight ratio of 0.009)
(Other ingredients)
HP: hindered phenol antioxidant (Ciba Specialty Chemicals: Irganox 1076)
CE: Cyclic imino ester ultraviolet absorber (Takemoto Yushi Co., Ltd .: CEi-P)
PSR: Coumarin-based optical brightener (manufactured by Hakkol Chemical Co., Ltd .: Hakkor PSR-B (trade name))

It is a figure of the integral value 0-8 ppm which measured ¹ HNMR of the polycarbonate resin of this invention. It is an enlarged view of the peak of the integral value 6-7 ppm in FIG.

Claims (4)

A polycarbonate resin containing a carbonate constituent unit represented by the following formula (1), wherein the polymer terminal contains a carbon-carbon double bond component represented by the following formula (2) and the following formula (3). Of 0.1 to 80 parts by weight of a titanium dioxide pigment (component B) with respect to 100 parts by weight of a polycarbonate resin (component A) having a total amount of 0.3% or less based on the carbonate constituent unit. Polycarbonate resin composition.

  The polycarbonate resin composition according to claim 1, wherein the component B is a titanium dioxide pigment surface-treated with an organosilicon compound containing an alkoxy group and / or a Si—H group.   When the above component B is (i) weight loss at 23 ° C. to 100 ° C. by thermogravimetric analysis (TGA) is (a) wt%, and weight loss at 23 ° C. to 300 ° C. is (b) wt%, 0.05 ≦ (b) − (a) ≦ 0.6 is satisfied, and (ii) the weight ratio derived from the Ti element, Al element, and Si element in the fluorescent X-ray measurement is (c) wt%, ( d) When wt% and (e) wt%, 0.001 ≦ (d) / (c) ≦ 0.01 is satisfied, and 0.001 ≦ (e) / (c) ≦ 0.02 is satisfied. The polycarbonate resin composition according to claim 1, which is a titanium dioxide pigment (component B).   A light reflecting material formed from the polycarbonate resin composition according to claim 1.

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