JP4915155B2 - Light-reflective resin composition and light-reflective member formed by molding the same - Google Patents

Description

  The present invention relates to a resin composition having excellent light reflection characteristics. More specifically, the present invention relates to a light reflective resin composition mainly composed of an aromatic polycarbonate resin and an alicyclic polyester resin, and a light reflective member formed by molding the same.

  In recent years, in information display devices such as TFTs and other computers and televisions, display devices having high light reflectance such as backlights of liquid crystal display devices, illuminated push switches, and reflectors of photoelectric switches are becoming common. is there. High light reflectance is also required for light reflecting members of electric devices such as electric / electronic devices, advertising lamps, and automotive devices such as automotive meter panels.

  Recently, in addition to the increase in size and thickness of various display devices, the brightness and light intensity of the light source has increased significantly. There is a strong demand for suppression of the decrease.

  As such a light reflecting member, a resin composition mainly composed of a polycarbonate resin is frequently used because of its characteristics. Originally, polycarbonate resin has excellent mechanical properties, thermal properties, optical properties, and electrical properties, and is widely used industrially, including in the automotive field, OA equipment field, and electrical / electronic field. . As an application of the polycarbonate resin to the light reflecting member, a composition in which a white pigment such as titanium oxide is added to the polycarbonate resin (see, for example, Patent Documents 1 and 2), or a polycarbonate resin and a polycarbonate-polysiloxane block co-polymerized. A resin composition (for example, see Patent Document 3) containing a coalescence and a white pigment such as titanium oxide has been proposed.

  On the other hand, a polycarbonate resin, particularly an aromatic polycarbonate resin has a problem that it has a high melt viscosity and is inferior in moldability (fluidity). In particular, as the molded product becomes thinner and larger, it is strongly required to improve the moldability. Furthermore, the aromatic polycarbonate resin has a problem that it is poor in chemical resistance, and there is a limit to use in an application in contact with a solvent.

  On the other hand, as means for improving the fluidity of the aromatic polycarbonate resin, poly (1,4-cyclohexanedimethanol-1,4-cyclohexanedicarboxylate), which is an alicyclic polyester, is added to the aromatic polycarbonate resin. A method has been proposed in which a resin (hereinafter abbreviated as PCC resin) is used in combination to form a transparent polymer alloy. An optical component excellent in transparency, impact resistance, chemical resistance, and weather resistance formed by molding such a transparent polymer alloy has been proposed (see, for example, Patent Document 4).

Further, a transparent / translucent molding composition (Patent Document 5) composed of a polycarbonate resin and an alicyclic polyester resin with improved ductility, chemical resistance and melt flow characteristics has been proposed. 5 describes that an inorganic filler special effect colorant such as titanium oxide may be used for such a polymer alloy.
JP-A-7-242804 JP 7-258554 A JP-A-5-320519 JP 2003-176401 A Japanese translation of PCT publication No. 2004-514011

  However, the resin compositions described in Patent Documents 1 to 3 described above have insufficient light reflectivity. Further, the techniques described in Patent Documents 4 and 5 relate to a technique using the transparency of the polycarbonate resin, and did not suggest any problems related to the light-reflective resin composition.

  An object of the present invention is to provide a resin composition having excellent light reflection characteristics and excellent mechanical characteristics, and a light reflective member formed by molding the resin composition.

As a result of intensive studies to solve the problems described above, the present inventors have found that a resin component (C) comprising 30 to 99 parts by weight of an aromatic polycarbonate resin (A) and 1 to 70 parts by weight of an alicyclic polyester resin (B). ) It was found that the light-reflective resin composition containing 5 to 30 parts by weight of titanium oxide (D) with respect to 100 parts by weight has remarkably excellent light-reflective properties and excellent mechanical properties. The present invention has been completed.

  That is, the gist of the present invention is that titanium oxide (D) is used for 100 parts by weight of a resin component (C) comprising 30 to 99 parts by weight of an aromatic polycarbonate resin (A) and 1 to 70 parts by weight of an alicyclic polyester resin (B). And 3 to 30 parts by weight of a light-reflective resin composition, and a light-reflective member formed by molding the same.

  The light-reflective resin composition of the present invention has remarkably excellent light-reflecting properties, and is excellent in mechanical properties, electrical properties, and melting heat stability. For example, for a backlight of a liquid crystal display device Use as a light reflector for light reflectors (including peripheral members such as the frame of a liquid crystal display backlight), electrical and electronic equipment, lighting equipment such as advertising lights, and automotive equipment such as automotive meter panels. Is possible.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, the “group” of various compounds may have a substituent without departing from the scope of the present invention.

[1] Aromatic polycarbonate resin (A)

  The molecular weight of the aromatic polycarbonate resin (A) used in the present invention may be appropriately selected and determined. Usually, the viscosity average molecular weight [Mv] converted from the solution viscosity is preferably in the range of 10,000 to 50,000.

  By setting the viscosity average molecular weight of the aromatic polycarbonate resin (A) to 10,000 or more, the mechanical strength tends to be further improved, and it is more preferable when used for applications requiring high mechanical strength. On the other hand, when the viscosity average molecular weight is less than 50000, it tends to be able to improve the decrease in fluidity, which is more preferable from the viewpoint of easy molding processability.

  Therefore, the viscosity average molecular weight of the aromatic polycarbonate resin (A) used in the present invention is preferably 12000 to 40000, and particularly preferably 14000 to 30000. In the present invention, two or more types of aromatic polycarbonate resins having different viscosity average molecular weights may be used in combination, and in this case, an aromatic polycarbonate resin having a viscosity average molecular weight outside the above preferred range may be used in combination. .

In the present invention, the viscosity average molecular weight [Mv] means the intrinsic viscosity [η] (unit dl / g) measured with an Ubbelohde viscometer at 20 ° C. using methylene chloride as a solvent, and the Schnell viscosity formula ( η = 1.23 × 10 ⁻⁴ M ^0.83 ).

Here, the intrinsic viscosity [η] is a value calculated by the following equation by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl).

  In addition, the aromatic polycarbonate resin (A) in the present invention may contain an aromatic polycarbonate oligomer in order to improve the appearance of the molded product and the fluidity. The aromatic polycarbonate oligomer has a viscosity average molecular weight [Mv] of preferably 1500 to 9500, more preferably 2000 to 9000. The aromatic polycarbonate oligomer is preferably used in the range of 30% by weight or less of (A).

  The aromatic polycarbonate resin (A) used in the present invention is, for example, a linear or branched heat produced by reacting an aromatic dihydroxy compound and a carbonate precursor, or a small amount of a polyhydroxy compound in combination with these compounds. It is a plastic aromatic polycarbonate polymer or copolymer.

  The aromatic polycarbonate resin (A) used in the present invention is not particularly limited and can be produced by a known method. Specific examples include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.

  Specific examples of the aromatic dihydroxy compound used as a raw material include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A) and 2,2-bis (3,5-dibromo-4-hydroxyphenyl). ) Propane (= tetrabromobisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis ( 4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) pro 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-) Hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxyphenyl) -1,1,1-tri Chloropropane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexachloropropane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3 Bis (hydroxyaryl) alkanes such as 1,3-hexafluoropropane;

Exemplified by 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, etc. Bis (hydroxyaryl) cycloalkanes; cardostructure-containing bisphenols exemplified by 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene and the like ;

  Dihydroxy diaryl ethers exemplified by 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether and the like; 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3, Dihydroxy diaryl sulfides exemplified by 3′-dimethyldiphenyl sulfide and the like; dihydroxy diaryl sulfoxides exemplified by 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide and the like; Dihydroxydiaryl sulfones exemplified by 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone, etc .; hydroquinone, resorcin, 4,4′-dihydroxy Diphenyl, and the like.

  Among these, bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A] is particularly preferable from the viewpoint of impact resistance. These aromatic dihydroxy compounds may be used alone or in combination of two or more in any proportion.

  Carbonate precursors to be reacted with aromatic dihydroxy compounds include carbonyl halides, carbonate esters, haloformates, and the like. Specifically, phosgene; diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dimethyl carbonate, diethyl carbonate and the like Dialkyl carbonates; dihaloformates of dihydric phenols and the like. These carbonate precursors may also be used alone or in combination of two or more in any proportion.

  The aromatic polycarbonate resin (A) used in the present invention may be one having a branched structure (branched polycarbonate resin). This branched polycarbonate resin can be obtained, for example, by copolymerizing a trifunctional or higher polyfunctional aromatic compound.

  Specific examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl- 2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3, 1,3,5-tri (4-hydroxyphenyl) ) Polyhydroxy compounds such as benzene, 1,1,1-tri (4-hydroxyphenyl) ethane;

  3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like. Of these, polyhydroxy compounds are preferable, and 1,1,1-tri (4-hydroxyphenyl) ethane is particularly preferable.

  Moreover, a polyfunctional aromatic compound may substitute and use a part of said aromatic dihydroxy compound, and the usage-amount shall be 0.01-10 mol% with respect to an aromatic dihydroxy compound. Particularly preferred is 0.1 to 2 mol%.

Interfacial Polymerization Method First, the interfacial polymerization method will be described. Specific examples of the method for producing a polycarbonate resin by the interfacial polymerization method include the following methods. First, in the presence of an organic solvent and an aqueous alkali solution that are inert to the reaction, the pH is usually maintained at 9 or higher, and oxidation of the aromatic dihydroxy compound and, if necessary, a molecular weight modifier (terminal terminator) or aromatic dihydroxy compound. An inhibitor or the like is reacted with phosgene. Next, a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt is added and interfacial polymerization is performed to obtain a polycarbonate.

  The addition of the molecular weight regulator is not particularly limited as long as it is from the time of phosgenation to the start of the polymerization reaction. The reaction temperature may be appropriately selected and determined. Usually, the reaction temperature is 0 to 40 ° C., and the reaction time is, for example, several minutes (for example, 10 minutes) to several hours (for example, 6 hours).

  Here, examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene, and aromatic hydrocarbons such as benzene, toluene and xylene. . Examples of the alkali compound used in the alkaline aqueous solution include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.

  Examples of the molecular weight regulator include compounds having a monovalent phenolic hydroxyl group. Examples of the compound having a monovalent phenolic hydroxyl group include m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol and p-long chain alkyl-substituted phenol. The amount of the molecular weight regulator used is preferably 50 to 0.5 mol, more preferably 30 to 1 mol, per 100 mol of the aromatic dihydroxy compound.

  Polymerization catalysts include tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine and pyridine: quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride Etc.

Transesterification method Next, the transesterification method will be described. The reaction by the transesterification method is an ester exchange reaction between a carbonate diester that is a carbonate precursor and an aromatic dihydroxy compound. Examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate and di-tert-butyl carbonate, and substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate. The carbonic acid diester is preferably diphenyl carbonate or substituted diphenyl carbonate, more preferably diphenyl carbonate.

  Generally, a polycarbonate having a desired molecular weight and terminal hydroxyl group amount can be obtained by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound or adjusting the degree of vacuum during the reaction. As a more aggressive method, an adjustment method in which a terminal terminator is added separately during the reaction is also well known.

  In this case, examples of the terminal terminator include monohydric phenols, monovalent carboxylic acids, and carbonic acid diesters. The amount of terminal hydroxyl groups greatly affects the thermal stability, hydrolysis stability, color tone, etc. of the product polycarbonate. Although depending on the application, in order to have practical physical properties, it is preferably 1000 ppm or less, particularly preferably 700 ppm.

  In the aromatic polycarbonate resin (A) produced by the transesterification method, the amount of terminal hydroxyl groups is preferably 100 ppm or more. By setting it as the amount of such terminal hydroxyl groups, the fall of molecular weight can be suppressed and a color tone can also be made more favorable. Accordingly, it is preferable to use an equimolar amount or more of the carbonic acid diester, and more preferably 1.01 to 1.30 mol, per 1 mol of the aromatic dihydroxy compound.

When the aromatic polycarbonate resin (A) used in the present invention is produced by a transesterification method, a transesterification catalyst is usually used. The transesterification catalyst is not particularly limited, but an alkali metal compound and / or an alkaline earth metal compound is preferable. In addition, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound can be used in combination.

The amount of the catalyst is usually 1 × 10 ^{−7 to} 9 × 10 ⁻⁷ mol with respect to 1 mol of the aromatic dihydroxy compound. If the amount of the catalyst is too small, the polymerization activity necessary for the production of the polycarbonate resin having the predetermined molecular weight and the terminal hydroxyl group content tends to be difficult to obtain. Conversely, if the amount is too large, the hue of the resulting aromatic polycarbonate resin deteriorates. And branching also increases and the moldability of the polymer tends to be impaired. Therefore, the amount of the catalyst is 1.5 × 10 ⁻⁷ to 8 × 10 ⁻⁷ mol, particularly 2 × 10 ^{−7 to} 7 × 10 ⁻⁷ mol, with respect to 1 mol of the aromatic dihydroxy compound. preferable.

  Specific examples of the alkali 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, hydrogen Cesium borohydride, sodium phenide boron, potassium phenide boron, lithium phenide boron, cesium phenide boron, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, phosphorus 2 sodium hydrogen, 2 potassium hydrogen phosphate, 2 lithium hydrogen phosphate, 2 cesium hydrogen phosphate, 2 sodium phenyl phosphate, 2 potassium phenyl phosphate, 2 lithium phenyl phosphate, 2 cesium phenyl phosphate, sodium, potassium, Examples thereof include lithium, cesium alcoholate, phenolate, disodium salt of bisphenol A, 2 potassium salt, 2 lithium salt, 2 cesium salt and the like.

  Specific examples of the alkaline earth metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, Examples thereof include barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, and the like.

  Specific 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. Sodium, potassium, lithium, calcium, barium, magnesium, strontium salts such as boron, tributylbenzylboron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, butyltriphenylboron Etc.

  Specific examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, quaternary phosphonium salt, and the like.

Specific examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, and trimethylphenyl. Ammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenyl Ammoni Muhidorokishido, butyl triphenyl ammonium hydroxide, and the like.

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

  The transesterification reaction is generally performed in a multistage process having two or more stages. Specifically, for example, the first stage reaction is performed at 120 to 260 ° C., preferably 180 to 240 ° C. under reduced pressure of 93 to 1.33 kPa for 0.1 to 5 hours, preferably 0.1 to React for 3 hours. Next, there is a production method in which the reaction temperature is raised while raising the degree of vacuum of the reaction system, and finally the polycondensation reaction is performed at a temperature of 240 to 320 ° C. under a reduced pressure of 133 Pa or less.

  The type of reaction may be any of batch type, continuous type, or a combination of batch type and continuous type, and the apparatus used may be a tank type, a tube type or a column type reactor.

  In order to deactivate the transesterification catalyst after the reaction, it is preferable to add an acidic compound or a precursor thereof, specifically, for example, a sulfonic acid compound or a precursor thereof as a deactivator. As such a catalyst deactivator, p-toluenesulfonic acid, methyl p-toluenesulfonate, butyl p-toluenesulfonate and the like are preferable, and these are used alone or in an arbitrary ratio of two or more. May be.

  The amount of the catalyst deactivator used for the transesterification catalyst may be appropriately selected and determined. Specifically, for example, in the case of the acidic compound as described above or a precursor thereof, it is used for the polycondensation reaction. It is preferable to add 0.1 to 50 times mol, especially 0.5 to 30 times mol for the neutralized amount of the basic transesterification catalyst.

  The addition time of the catalyst deactivator is arbitrary as long as it is after the polycondensation reaction, and the addition method is not particularly limited. Depending on the properties of the catalyst deactivator and desired conditions, a method of adding directly, a method of adding by dissolving in an appropriate solvent, a method of using pellets or flaky master batch, and the like can be mentioned.

  The melt polycondensation may be carried out by either a batch method or a continuous method, but it is preferably carried out by a continuous method considering the stability of the aromatic polycarbonate resin (A) used in the present invention. As the catalyst deactivator in the transesterification polycarbonate, it is preferable to use a compound that neutralizes the catalyst, for example, a sulfur-containing acidic compound or a derivative formed therefrom. The amount of the compound that neutralizes such a catalyst is preferably 0.5 to 10 equivalents, more preferably 1 to 5 equivalents, with respect to the alkali metal contained in the catalyst. Furthermore, it is preferable to reduce such a catalyst neutralizing compound as much as possible with respect to the polycarbonate, specifically, 1 to 100 ppm, particularly 1 to 20 ppm with respect to the polycarbonate resin.

Furthermore, as the aromatic polycarbonate resin (A) in the present invention, not only virgin raw materials but also aromatic polycarbonate resins regenerated from used products, so-called material recycled aromatic polycarbonate resins may be used.

  Used products include optical recording media such as optical disks, light guide plates, vehicle window glass, vehicle headlamp lenses, windshields, and other vehicle transparent members, water bottle containers, glasses lenses, soundproof walls, glass windows, waves, etc. Examples include building materials such as plates. Further, non-conforming products, pulverized products obtained from sprues, runners, pellets obtained by melting them, and the like can also be used. The regenerated aromatic polycarbonate resin is preferably 80% by weight or less, more preferably 50% by weight or less of the aromatic polycarbonate resin (A) used in the present invention.

[2] Alicyclic polyester resin (B)
A conventionally well-known arbitrary thing can be used for the alicyclic polyester resin (B) used for this invention. Especially, it is preferable that it is a polyester resin obtained by making the dicarboxylic acid component which has 1, 4- cyclohexanedicarboxylic acid as a main component and a diol component react. Such an alicyclic polyester resin (B) is preferable because it uses a dicarboxylic acid component as a raw material, and unlike the case where a dicarboxylic acid ester is used as a raw material, has fewer alkyl ester terminals.

  Specifically, the alkyl ester terminal in the aliphatic polyester resin used in the present invention is, for example, such that the ratio of the alkyl ester terminal to the total terminal of the alicyclic polyester resin is 5 mol% or less, particularly 1 mol% or less. preferable.

  In the alicyclic polyester resin (B) used in the present invention, for example, a dicarboxylic acid component, a diol component, and a small amount of other components as necessary are esterified or transesterified, and then subjected to a polycondensation reaction. It will be. The dicarboxylic acid component is mainly composed of an alicyclic dicarboxylic acid or an ester-forming derivative thereof. Moreover, a diol component has alicyclic diol as a main component. Here, the “main component” means, for example, that each occupies 80 mol% or more with respect to the dicarboxylic acid component or the diol component.

  The alicyclic dicarboxylic acid or an ester-forming derivative thereof is not particularly limited as long as two carboxyl groups are bonded to the alicyclic structure. Specifically, for example, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-decahydronaphthalenedicarboxylic acid, 1,5-decahydronaphthalenedicarboxylic acid, Examples include 2,6-decahydronaphthalenedicarboxylic acid, 2,7-decahydronaphthalenedicarboxylic acid, and ester-forming derivatives thereof.

  Among these, an alicyclic dicarboxylic acid having 6 to 12 carbon atoms or an ester-forming derivative thereof is preferable, and 1,4-cyclohexanedicarboxylic acid or an ester-forming derivative thereof is particularly preferable. Cyclohexanedicarboxylic acid is preferred.

  When 1,4-cyclohexanedicarboxylic acid is used, the ratio of its trans isomer and cis isomer may be appropriately selected and determined, but from the viewpoint of improving heat resistance, 80/20 to 100/0, 85/15 to 100/0, more preferably 90/10 to 100/0, and particularly preferably 95/5 to 100/0. These dicarboxylic acid components preferably contain alicyclic dicarboxylic acid or an ester-forming derivative thereof at 80 mol% or more, particularly 90 mol% or more, based on the total dicarboxylic acid component.

Examples of other dicarboxylic acid components other than the alicyclic dicarboxylic acid or its ester-forming derivative include aromatic dicarboxylic acids and aliphatic dicarboxylic acids. Specifically, for example, terephthalic acid, phthalic acid, isophthalic acid, 1,4-phenylenedioxydicarboxylic acid, 1,3-phenylenedioxydiacetic acid, 4,4-diphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid Acids, aromatic dicarboxylic acids such as 4,4-diphenylketone dicarboxylic acid, 4,4′-diphenoxyethanedicarboxylic acid, 4,4-diphenylsulfone dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, glutamic acid , Adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecadicarboxylic acid, dodecadicarboxylic acid, and C1-C4 alkyl esters and halides of these carboxylic acids.

  The alicyclic diol component is not particularly limited as long as two hydroxyl groups are bonded to the alicyclic structure. Among these, from the viewpoint of improving heat resistance, an alicyclic diol in which two hydroxyl groups are bonded to a 5-membered or 6-membered ring is preferable.

  Examples of such alicyclic diols include 5-membered members such as 1,2-cyclopentanedimethanol, 1,3-cyclopentanedimethanol, bis (hydroxymethyl) tricyclo, and [5.2.1.0] decane. Ring diols; 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2 , 2-membered ring diols such as 2-bis (4-hydroxycyclohexyl) -propane; Among these, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol are preferable, and 1,4-cyclohexanedimethanol is particularly preferable.

  1,4-Cyclohexanedimethanol is highly reactive because the methylol group is in the para position, is easy to obtain a polyester with a high degree of polymerization, is capable of obtaining a polyester resin with a high glass transition temperature, and is an industrial product. There is an advantage that it is easily available. The ratio of the trans isomer and cis isomer of 1,4-cyclohexanedimethanol is arbitrary and may be appropriately selected and determined, but is preferably 60/40 to 100/0.

  As the diol component, those containing the alicyclic diol as described above in an amount of 80 mol% or more, preferably 90 mol% or more based on the total diol component are preferable. Other diol components include aliphatic diols and aromatic diols. Etc. may be contained. If content of alicyclic diol is less than 80 mol%, heat resistance may be inferior by the compatibility fall with aromatic polycarbonate resin (A).

  Specific examples of the diol component other than the alicyclic diol in the diol component include aliphatic diols such as ethylene glycol, propylene glycol, butanediol, pentanediol and hexanediol; xylylene glycol, 4 Aromatic diols such as 1,4-dihydroxybiphenyl, 2,2-bis (4′-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone and bis (4-β-hydroxyethoxyphenyl) sulfonic acid; Can be mentioned.

  Furthermore, the alicyclic polyester resin (B) used in the present invention may contain a small amount of a copolymer component in addition to the diol component and the dicarboxylic acid component described above. Specific examples of such copolymer components include hydroxycarboxylic acids such as glycolic acid, p-hydroxybenzoic acid, and p-β-hydroxyethoxybenzoic acid; alkoxycarboxylic acids, stearyl alcohol, benzyl alcohol, and stearic acid. Monofunctional components such as behenic acid, benzoic acid, tert-butylbenzoic acid, benzoylbenzoic acid; tricarballylic acid, trimellitic acid, trimesic acid, pyromellitic acid, naphthalenetetracarboxylic acid, gallic acid, trimethylolethane, trimethyl And trifunctional or higher polyfunctional components such as methylolpropane, glycerol, pentaerythritol, sugar ester, and the like. The content of these components is preferably 10 mol% or less in the alicyclic polyester (B).

  When the aliphatic polyester resin (B) used in the present invention is produced by an esterification (or transesterification) reaction between a dicarboxylic acid component and a diol component, the molar ratio between the dicarboxylic acid component and the diol component used in this reaction. The total amount of the diol component is preferably 1 to 2 times the total amount of the dicarboxylic acid component. In particular, when the main component is a diol component having a high boiling point such as 1,4-cyclohexanedimethanol, it is preferably 1 to 1.2 times.

  In the esterification (or transesterification) reaction and the subsequent polycondensation reaction, it is preferable to use a catalyst in order to obtain a sufficient reaction rate. Such a catalyst is not particularly limited as long as it is a catalyst usually used in an esterification (or transesterification) reaction, and any conventionally known catalyst can be used. Specific examples include titanium compounds, germanium compounds, antimony compounds, and tin compounds. Of these, titanium compounds having high activity are preferred.

  Specific examples of such titanium compounds include tetra-n-propyl titanate, tetra-iso-propyl titanate, tetra-n-butyl titanate, and hydrolysates of these organic titanates. These may be used alone or in combination of two or more in any ratio. Moreover, you may use it in combination with a magnesium compound, a phosphorus compound, etc. as needed.

  The amount of the catalyst used may be appropriately selected and determined. Usually, however, it remains in the alicyclic polyester resin (B) to be produced, so that it is 1 to 2000 ppm with respect to the alicyclic polyester resin (B). It is preferable to adjust so that it is 10 to 1000 ppm, more preferably 50 to 1000 ppm, and particularly preferably 100 to 1000 ppm.

  The esterification (or transesterification) reaction between the dicarboxylic acid component and the diol component is usually 150 to 230 ° C, preferably 180 ° C to 220 ° C, and the reaction time is usually 10 minutes to 10 hours. Especially, it is preferable that it is 30 minutes-5 hours.

  After the esterification (or transesterification) reaction, the reaction solution is usually transferred to a polycondensation tank equipped with a stirrer, a distillation pipe and a vacuum addition apparatus. An esterification reaction and a polycondensation reaction can also be performed.

  After the esterification (or transesterification) is completed, a polycondensation catalyst or the like may be added to the reaction solution as necessary, and the polycondensation reaction may be performed while gradually reducing the pressure in the reaction vessel. When the polymerization catalyst is added, the amount is adjusted to 50 to 2000 ppm, particularly 100 to 1000 ppm, based on the total amount of the esterification reaction or transesterification reaction catalyst, based on the produced alicyclic polyester (B). It is preferable.

  The polycondensation reaction may be performed at an esterification reaction completion temperature of -300 ° C or lower, preferably 265 ° C or lower, and usually for 10 minutes to 10 hours, preferably 30 minutes to 5 hours. If the temperature is too high, the polymerization reaction tends to not proceed, probably because thermal decomposition occurs during the polymerization reaction. The internal pressure of the tank may be a pressure that finally becomes 1 KPa or less from normal pressure, and is preferably 0.5 KPa or less.

The intrinsic viscosity of the alicyclic polyester resin (B) used in the present invention is arbitrary and may be appropriately selected and determined, but is preferably 0.4 to 1.5 dl / g, and more preferably 0.5 to It is preferably 1.3 dl / g, more preferably 0.6 to 1.5 dl / g, and particularly preferably 0.7 to 1.4 dl / g. By setting the intrinsic viscosity to 0.4 dl / g or more, the mechanical strength is further improved, and by setting the intrinsic viscosity to 1.5 dl / g or less, the fluidity is further improved and molding becomes more preferable. Furthermore, the obtained polyester resin may be subjected to solid phase polymerization as necessary to have a higher intrinsic viscosity. Here, intrinsic viscosity is calculated | required by measuring at 30 degreeC using a Ubbelohde viscometer by making a phenol / tetrachloroethane (weight ratio 1/1) liquid mixture into a solvent.

  The terminal carboxylic acid concentration of the alicyclic polyester resin (B) used in the present invention is arbitrary and may be appropriately selected and determined. Usually, it is 70 μeq / g or less, particularly 40 μeq / g or less, and further 30 μeq. / G or less, and particularly preferably 10 μeq / g or less. It is preferable for the terminal carboxylic acid concentration to be 70 μeq / g or less because the moist heat resistance of the resin composition of the present invention tends to be further improved.

  The method for adjusting the terminal carboxylic acid concentration (hereinafter sometimes referred to as “terminal acid value”) is not particularly limited. For example, in the production of the alicyclic polyester (B), for example, a raw material is used. Examples include adjustment of the use ratio of 1,4-cyclohexanedicarboxylic acid and 1,4-cyclohexanedimethanol, and methods using alkylene diols, particularly alkylene diols having 2 to 10 carbon atoms, as diol raw materials.

  Moreover, in order to set the terminal acid value of the alicyclic polyester resin (B) used in the present invention to 40 μeq / g or less, for example, a dicarboxylic acid component in which 90 mol% or more is 1,4-cyclohexanedicarboxylic acid, When 90 mol% or more of the diol component is 1,4-cyclohexanedimethanol, the ratio of the diol component to 1 mol of the dicarboxylic acid component is 1.02 to 1.2 mol, preferably 1.02 to 1 It may be 1 mol.

  Further, for example, a dicarboxylic acid component in which 90 mol% or more is 1,4-cyclohexanedicarboxylic acid, 80 to 99.5 mol% is 1,4-cyclohexanedimethanol, and 0.5 to 20 mol% is carbon number. When 2 to 10 alkylene diols are used, the diol component is used in an amount of 1.02 to 1.2 mol, preferably 1.02 to 1.1 mol, per 1 mol of the dicarboxylic acid component.

  The melting point of the alicyclic polyester resin (B) used in the present invention is, for example, a fat mainly composed of 1,4-cyclohexanedicarboxylic acid as a dicarboxylic acid component and 1,4-cyclohexanedimethanol as a diol component. In the case of a cyclic polyester resin, it is usually 200 to 250 ° C., preferably 210 to 230 ° C., particularly preferably 215 to 230 ° C.

In the alicyclic polyester resin (B) used in the present invention, its Yellowness
If the index (YI) is too high so that yellow coloring can be recognized even by visual observation, the light-reflecting resin composition of the present invention is naturally yellow and may affect the reflected light wavelength. Therefore, generally YI is preferably 18 or less, more preferably 15 or less. The lower limit of YI is usually about -5.

  In addition, in the raw material of the alicyclic polyester resin (B) used in the present invention, as a method for producing a raw material 1,4-cyclohexanedicarboxylic acid having a trans isomer of 90 mol% or more, for example, 1,4-cyclohexanedicarboxylic acid cis Or a method of thermal isomerization of a mixture of a cis isomer and a trans isomer. In the known crystallization method using the difference in solubility between cis and trans isomers in water, the obtained 1,4-cyclohexanedicarboxylic acid has a low T-340, and the light transmittance of the resulting alicyclic polyester resin is low. Is insufficient. Therefore, the thermal isomerization method is preferable from the viewpoint that it is preferable to use 1,4-cyclohexanedicarboxylic acid having a trans isomer ratio of 90 mol% or more and T-340 of 85% or more.

  The thermal isomerization is carried out by adding a mixture of cis-1,4-cyclohexanedicarboxylic acid and trans-1,4-cyclohexanedicarboxylic acid or cis-1,4-cyclohexanedicarboxylic acid at 180 ° C. in an inert atmosphere. The heat treatment can be performed in the temperature range below the melting point of trans-1,4-cyclohexanedicarboxylic acid. The melting point of trans-1,4-cyclohexanedicarboxylic acid in the present invention refers to the melting point of trans-1,4-cyclohexanedicarboxylic acid under the actual isomerization reaction conditions.

  The thermal isomerization reaction pressure can be carried out under reduced pressure, normal pressure or increased pressure, but is usually 1.3 to 950 kPa in view of the ease of operation. Furthermore, in order to make T-340 of 1,4-cyclohexanedicarboxylic acid 85% or more, a mixture of cis / trans-1,4-cyclohexanedicarboxylic acid or cis-1,4-cyclohexanedicarboxylic acid is heat-treated. It is preferable to adjust the inert atmosphere at the time of oxygen concentration in the reaction system to 4000 ppm or less, preferably 2000 ppm or less, more preferably 1000 ppm or less. If the oxygen concentration in the system is higher than 4000 ppm, T-340 tends to be less than 85%.

  In order to efficiently obtain trans-1,4-cyclohexanedicarboxylic acid produced by thermal isomerization, trans-1,4-cyclohexanedicarboxylic acid is melted in the melted cis-1,4-cyclohexanedicarboxylic acid while maintaining the temperature range. There is a method in which cyclohexanedicarboxylic acid is precipitated and removed.

  In addition, what is necessary is just to obtain the method of obtaining the mixture of cis-form and trans-form 1,4-cyclohexanedicarboxylic acid used as the raw material in a thermal isomerization method by a conventionally well-known arbitrary method. For example, liquid phase nuclear hydrogenation of terephthalic acid in the presence of solvent, hydrogen and hydrogenation catalyst, and liquid phase nuclear hydrogenation of sodium terephthalate in the presence of water, hydrogen and hydrogenation catalyst for acid precipitation. It is done.

  Furthermore, the alicyclic polyester resin (B) used in the present invention may be formed into a pellet and then subjected to solid phase polymerization as necessary to have a higher intrinsic viscosity.

  The alicyclic polyester resin (B) used in the present invention is preferably one in which 80 mol% or more of diol units is 1,4-cyclohexanedimethanol from the viewpoint of heat resistance of the polyester resin. Also, 80 mol% or more and 99.5 mol% or less of diol units are 1,4-cyclohexanedimethanol units, and 0.5 mol% or more and 20 mol% or less are alkylene diol units having 2 to 10 carbon atoms. Among them, those in which 1,4-cyclohexanedimethanol units are 90 mol% or more and 99.5 mol% or less, and alkylene diol units having 2 to 10 carbon atoms are 0.5 mol% or more and 10 mol% or less. It is preferable because of its high hydrolysis resistance.

[3] Resin component (C)
The resin component (C) used in the present invention comprises 30 to 99 parts by weight of the above-described aromatic polycarbonate resin (A) and 1 to 70 parts by weight of the alicyclic polyester resin (B). When the aromatic polycarbonate resin is less than 30 parts by weight, the load deflection temperature and rigidity are low, and when it exceeds 99 parts by weight, the effect of improving the light reflection characteristics is small.

[4] Titanium oxide (D)
In the present invention, the use of titanium oxide (D) improves the whiteness and light reflection characteristics of the light reflective resin composition of the present invention and the light reflective member formed by molding the same. And The titanium oxide used in the present invention may be appropriately selected and used from any conventionally known ones, and the production method, crystal form, average particle size, and the like are not particularly limited.

The titanium oxide (D) used in the present invention preferably has a particle diameter of 0.05 to 0.5 μm. If the particle diameter is too small, the light reflectivity is inferior. On the other hand, if the particle size is too large, the light reflectivity and surface properties may be deteriorated or the impact strength may be lowered in the light reflective member. Therefore, the particle diameter of titanium oxide (D) used in the present invention is preferably 0.1 to 0.5 μm, particularly preferably 0.15 to 0.35 μm.

  The manufacturing method of the titanium oxide (D) used for this invention is arbitrary, The thing obtained by any method of the conventionally well-known chlorine method and a sulfuric acid method can also be used. Of these, titanium oxide produced by the chlorine method is preferable because it is superior in terms of whiteness and the like compared to titanium oxide produced by the sulfuric acid method. The crystal form of titanium oxide may be either anatase type or rutile type. Among them, the rutile type, which is superior in whiteness, light reflectance, and weather resistance as compared with the anatase type, is preferable.

  Further, the titanium oxide (D) used in the present invention may be one whose surface is treated with an inorganic compound other than titanium oxide, specifically, for example, alumina, silica, zirconia or the like. These inorganic compounds other than titanium oxide are usually used when treating titanium oxide in the production process of titanium oxide (D) for the purpose of improving the handling of titanium oxide.

In the titanium oxide (D) used in the present invention, the content of inorganic substances other than these titanium oxides may be appropriately selected and determined. Usually, it is 2 to 5% by weight in the titanium oxide (D) used in the present invention. is there. If the content of the inorganic compound is too large, especially if the amount of the silica component is too large, the adsorbed water in the inorganic compound used in the treatment may cause poor appearance or dripping during combustion. Problems may arise.
Therefore, when the titanium oxide (D) used in the present invention is treated with an inorganic compound, it is preferable to treat with alumina, zirconia or the like without using silica.

  Furthermore, titanium oxide (D) used in the present invention is preferable because the thermal stability is greatly improved by surface treatment with an organic silane compound or an organic silicone compound. Prior to the surface treatment with the organosilicon compound, the titanium oxide surface may be surface treated with an inorganic compound or the like. A smaller amount of the inorganic compound used for the surface treatment is preferable. For example, it is preferably 2% by weight or less with respect to titanium oxide.

  In addition, such surface treatment with an organosilicon compound improves the uniform dispersibility of titanium oxide (D) in the light-reflective resin composition of the present invention, improves the stability of the dispersed state, and improves the flame retardancy of the resin composition. Furthermore, the affinity with the organic acid metal salt or the like constituting the composition of the present invention is also improved, which is preferable.

  Examples of the surface treatment agent for titanium oxide (D) include an organosilane compound having an alkoxy group, an epoxy group, an amino group, or an Si—H bond, or an organosilicone compound. Among these, it is preferable to use a silicone compound (hydrogen polysiloxane) having a Si—H bond. The amount of the organic silicone compound used as the surface treatment agent is preferably 1 to 5% by weight, more preferably 1.5 to 3% by weight, based on titanium oxide.

In the present invention, the content of titanium oxide (D) is 30 to 99 parts by weight of the aromatic polycarbonate resin (A) and 100 parts by weight of the resin component (C) consisting of 1 to 70 parts by weight of the alicyclic polyester resin (B). Is 5 to 30 parts by weight. If the content is less than 1 part by weight, the light reflectivity tends to be insufficient, and if it exceeds 30 parts by weight, the impact resistance of the molded product tends to be insufficient. Therefore, the content of titanium oxide (D) is preferably 5 to 25 parts by weight, more preferably 10 to 25 parts by weight, particularly 10 to 20 parts by weight, with respect to 100 parts by weight of the resin component (C). Preferably there is.

[5] Organic acid metal salt (E)
Further, the light reflective resin composition of the present invention may further contain an organic acid metal salt (E) for the purpose of improving flame retardancy. Examples of the organic acid metal salt (E) used in the present invention include an organic acid alkali metal salt or an alkaline earth metal salt of an organic acid. Among these, organic sulfonic acid metal salts are preferably used. Specific examples include perfluoroalkane sulfonic acid metal salts, perfluoroalkylene disulfonic acid metal salts, and aromatic sulfonic acid metal salts. Acid metal salts and perfluoroalkylene disulfonic acid metal salts are preferred. The organic acid metal salts may be used alone or in combination of two or more in any proportion.

  Specific examples of the perfluoroalkanesulfonic acid metal salt include alkali metal salts of perfluoroalkanesulfonic acid, alkaline earth metal salts of perfluoroalkanesulfonic acid, and the like. Among them, alkali (earth) metal sulfonates having a perfluoroalkane group having 1 to 8 carbon atoms can be mentioned.

  Specific examples of perfluoroalkanesulfonic acid include perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluorohexanesulfonic acid, perfluoroheptanesulfonic acid, perfluorooctane. A sulfonic acid etc. are mentioned.

  Specific examples of the perfluoroalkylene disulfonic acid metal salt include compounds represented by the following general formula (1) or (2).

（一般式（１）中、Ｍはアルカリ金属又はアルカリ土類金属を示し、ｑはＭがアルカリ金属の場合は２を、Ｍがアルカリ土類金属の場合は１を示し、ｍは１〜１２の整数を示す。）

(In the general formula (1), M represents an alkali metal or alkaline earth metal, q represents 2 when M is an alkali metal, 1 represents M when M is an alkaline earth metal, and m represents 1 to 12. Indicates an integer.)

（一般式（２）中、Ｒは炭素数４〜７個のパーフルオロシクロアルキル基で置換されていても良い、総炭素数２〜１２の直鎖状又は分岐状パーフルオロアルキレン基を示し、Ｍ’はアルカリ金属又はアルカリ土類金属を示し、ｎはＭ’の価数である。）

(In the general formula (2), R represents a linear or branched perfluoroalkylene group having a total carbon number of 2 to 12, which may be substituted with a perfluorocycloalkyl group having a carbon number of 4 to 7, M ′ represents an alkali metal or alkaline earth metal, and n is the valence of M ′.)

  Specific examples of the perfluoroalkanedisulfonic acid metal salt represented by the general formula (1) include perfluoromethanedisulfonic acid, perfluoroethanedisulfonic acid, perfluoropropanedisulfonic acid, perfluoroisopropanedisulfonic acid, and perfluorobutanedisulfone. Examples thereof include salts of acid, perfluoropentane disulfonic acid, perfluorohexane disulfonic acid, perfluoroheptane disulfonic acid, perfluorooctane disulfonic acid, and the like. Among these, a salt of perfluoropropanedisulfonic acid or perfluorobutanedisulfonic acid is preferable from the viewpoint of compatibility with the resin component (C) and imparting flame retardancy.

In general formula (1), if m is too large, the resin component (C in the resin composition of the present invention)
) And the appearance of the resin molded body may be deteriorated. Therefore, m is preferably 1 to 8, among others.

  Specific examples of the perfluoroalkanedisulfonic acid metal salt represented by the general formula (1) include perfluoromethane disulfonic acid, perfluoroethane disulfonic acid, perfluoropropane disulfonic acid, perfluoroisopropane disulfonic acid, and perfluorobutane. Examples thereof include salts of disulfonic acid, perfluoropentane disulfonic acid, perfluorohexane disulfonic acid, perfluoroheptane disulfonic acid, perfluorooctane disulfonic acid, and the like. Among these, a salt of perfluoropropanedisulfonic acid or perfluorobutanedisulfonic acid is preferable from the viewpoint of compatibility with the resin component (C) and imparting flame retardancy.

  Specific examples of the perfluoroalkanedisulfonic acid metal salt represented by the general formula (2) include perfluoroethanedisulfonic acid imide, perfluoropropanedisulfonic acid imide, perfluorobutanedisulfonic acid imide, and perfluoropentanedisulfonic acid. Examples of the salt include imide and perfluorohexanedisulfonic acid imide. Among these, perfluoropropanedisulfonic acid imide or perfluorobutanedisulfonic acid imide salt is compatible with the resin component (C) and from the viewpoint of imparting flame retardancy to the light-reflective resin composition of the present invention. preferable.

  Preferred examples of the aromatic sulfonic acid metal salt include an alkali sulfonic acid alkali metal salt and an aromatic sulfonic acid alkaline earth metal salt, and these may be polymers.

  Specific examples of the aromatic sulfonesulfonic acid metal salt include sodium salt of diphenylsulfone-3-sulfonic acid, potassium salt of diphenylsulfone-3-sulfonic acid, sodium 4 / 4'-dibromodiphenyl-sulfone-3-sulfone Salt, potassium salt of 4 · 4′-dibromodiphenyl-sulfone-3-sulfone, calcium salt of 4-chloro-4′-nitrodiphenylsulfone-3-sulfonic acid, disodium of diphenylsulfone-3 · 3′-disulfonic acid And dipotassium salt of diphenylsulfone-3 · 3′-disulfonic acid.

  The metal in the organic acid metal salt (E) used in the present invention is preferably an alkali metal or an alkaline earth metal. Examples of the alkali metal and alkaline earth metal include sodium, lithium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium and barium.

  Among them, lithium, sodium, and potassium are used as the alkali metal salt, and magnesium and calcium are used as the alkaline earth metal salt, which are compatible with the resin component (C) and the light-reflective resin composition of the present invention. It is preferable from the viewpoint of imparting flame retardancy.

The content of the organic acid metal salt (E) used in the present invention may be appropriately selected and determined. However, if the content is too small, the effect of improving flame retardancy in the light-reflective resin composition of the present invention is sufficient. On the contrary, if the amount is too large, the thermal stability may decrease. Therefore, the content of the organic acid metal salt (E) used in the present invention is 30 to 99 parts by weight of the aromatic polycarbonate resin (A) and 1 to 70 parts by weight of the alicyclic polyester resin (B). ) It is preferably in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight,
Among these, 0.001 to 4 parts by weight, particularly 0.001 to 3 parts by weight is preferable.

[6] Polytetrafluoroethylene (F)
The light reflective resin composition of the present invention may further contain polytetrafluoroethylene (F). The polytetrafluoroethylene (F) used in the present invention preferably has a fibril-forming ability, which is easily dispersed in the polymer and shows a tendency to bond the polymers to form a fibrous structure. Is.

  Polytetrafluoroethylene having fibril-forming ability is classified as type 3 according to the ASTM standard. Examples of the polytetrafluoroethylene having fibril forming ability include Teflon (registered trademark) 6J manufactured by Mitsui / DuPont Fluorochemical Co., Ltd., and Polyflon manufactured by Daikin Chemical Industries.

  Examples of commercially available aqueous dispersions of polytetrafluoroethylene include Teflon (registered trademark) 30J manufactured by Mitsui DuPont Fluorochemical Co., Ltd. and Fullon D-1 manufactured by Daikin Chemical Industries. Furthermore, a polytetrafluoroethylene polymer having a multilayer structure formed by polymerizing a vinyl monomer may be mentioned, and specifically, for example, Metablene (registered trademark) A-3800 manufactured by Mitsubishi Rayon Co., Ltd. may be mentioned. .

  The content of polytetrafluoroethylene in the light-reflective resin composition of the present invention may be appropriately selected and determined. However, if the amount is too small, the effect of improving flame retardancy is insufficient. The appearance of the product may deteriorate. Therefore, the content of polytetrafluoroethylene (F) in the present invention is a resin component (C) 100 comprising 30 to 99 parts by weight of an aromatic polycarbonate resin (A) and 1 to 70 parts by weight of an alicyclic polyester resin (B). It is preferable that it is 0.05-1 weight part with respect to a weight part, and 0.08-0.3 weight part especially.

[7] Phosphorus compound (G)
In the present invention, the following general formula (I) is further added to 100 parts by weight of the resin component (C) comprising 30 to 99 parts by weight of the polycarbonate resin (A) and 1 to 70 parts by weight of the alicyclic polyester resin (B). It is preferable to contain 0.001 to 1 part by weight of at least one phosphorus compound (G) selected from the group consisting of compounds represented by (VI) to (VI). Hereinafter, the compounds represented by the following general formulas (I) to (VI) will be described as (G-1) to (G-6), respectively.

(G-1): Phosphate ester The (G-1) phosphate ester used in the present invention is represented by the following general formula (I).

O = P (OH) _n (OR) _3-n (I)
(In general formula (I), R represents an alkyl group or an aryl group, which may be the same or different, and n represents an integer of 0 to 2.)

  In general formula (I), R is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. Further, an alkyl group, phenyl group, nonylphenyl group, stearylphenyl group, 2,4-di-tert-butylphenyl group, 2,4-di-tert-butyl-methylphenyl group, tolyl having 2 to 25 carbon atoms. It is preferably a group.

  Among them, from the viewpoint of further improving the light reflectivity and hue in the light reflective resin composition of the present invention, in the general formula (I), R represents an alkyl group having 2 to 25 carbon atoms, and n is 1 or 2 It is preferable to show. The alkyl group having 2 to 25 carbon atoms may be linear or branched, and specifically includes, for example, octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group. Group, isodecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, hexadecyl group, octadecyl group and the like are preferable.

(G-2): Phosphite The (G-2) phosphite used in the present invention is represented by the following general formula (II).

（一般式（ＩＩ）中、Ｒ’はアルキル基またはアリール基を示し、各々同一でも異なっていてもよい。）

(In general formula (II), R ′ represents an alkyl group or an aryl group, which may be the same or different.)

  In general formula (II), when R ′ is an alkyl group, an alkyl group having 1 to 30 carbon atoms is preferable, and when R ′ is an aryl group, an aryl group having 6 to 30 carbon atoms is preferable. .

  Preferable specific examples of the phosphite represented by the general formula (II) include distearyl pentaerythritol diphosphite, dinonyl pentaerythritol diphosphite, bisnonylphenyl pentaerythritol diphosphite, bis (2,4 -Di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4) -Ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-isopropylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, etc. Can be mentioned.

  Among these, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol Diphosphite is preferable, and bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite are particularly preferable. .

(G-3) to (G-6): Organophosphate ester metal salt The organophosphate metal salts of (G-2) to (G-6) used in the present invention are represented by the following general formulas (III) to (G-3) to (G-6): It is represented by (VI).

（一般式（ＩＩＩ）中、Ｒ^１〜Ｒ^４はアルキル基またはアリール基を示し、各々同一でも異なっていてもよく、Ｍはアルカリ土類金属および亜鉛より選ばれる金属を示す。）

(In the general formula (III), R ^{1 to} R ⁴ represent an alkyl group or an aryl group, and may be the same or different, and M represents a metal selected from an alkaline earth metal and zinc.)

（一般式（ＩＶ）中、Ｒ^５はアルキル基またはアリール基を示し、Ｍはアルカリ土類金属および亜鉛より選ばれる金属を示す。）

(In general formula (IV), R ⁵ represents an alkyl group or an aryl group, and M represents a metal selected from alkaline earth metals and zinc.)

（一般式（Ｖ）中、Ｒ^６〜Ｒ^１１はアルキル基またはアリール基を示し、各々同一でも異なっていてもよく、Ｍ’は３価の金属イオンとなる金属原子を示す。）

(In the general formula (V), R ^{6 to} R ¹¹ represent an alkyl group or an aryl group, and may be the same or different, and M ′ represents a metal atom that becomes a trivalent metal ion.)

（一般式（ＶＩ）中、Ｒ^１２〜Ｒ^１４は、アルキル基またはアリール基であり、各々同一でも異なっていてもよく、Ｍ’は３価の金属イオンとなる金属原子を示し、２つのＭ’は各々同一でも異なっていてもよい。）

(In the general formula (VI), R ^{12 to} R ¹⁴ are alkyl groups or aryl groups, which may be the same or different, and M ′ represents a metal atom that becomes a trivalent metal ion, 'May be the same or different.

In the general formulas (III) to (VI), R ^{1 to} R ¹⁴ are preferably each an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and more preferably each carbon. These are an alkyl group of 2 to 25, phenyl group, nonylphenyl group, stearylphenyl group, 2,4-di-tert-butylphenyl group, 2,4-di-tert-butyl-methylphenyl group or tolyl group.

From the viewpoint of further improving the light reflectivity and / or hue in the light reflective resin composition of the present invention, each of R ^{1 to} R ¹⁴ is preferably an alkyl group having 2 to 25 carbon atoms, and octyl. Group, 2-ethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, hexadecyl group and octadecyl group are more preferable.

  In general formulas (III) and (IV), M is preferably zinc, and in general formulas (V) and (VI), M 'is preferably aluminum.

As the organophosphate metal salt represented by (G-3) to (G-6) used in the present invention, among others, light reflectivity, hue, and residence heat stability in the light reflective resin composition of the present invention. From the viewpoint of further improving the properties, it is preferable to use (G-3) and (G-4) in combination, and further, the general formulas (III) and (G) corresponding to (G-3) and (G-4) In IV), R _{1 to} R ₅ are preferably alkyl groups having 2 to 25 carbon atoms.

  In particular, the organophosphate metal salt used in the present invention is a mixture of a zinc salt of monostearyl acid phosphate and a zinc salt of distearyl acid phosphate which is (G-3) and / or (G-4) Mention may be made of mixtures of aluminum salts of monostearyl acid phosphate and aluminum salts of distearyl acid phosphate. Specific examples of such preferable organophosphate metal salts include Sakai Chemical Industry Co., Ltd., LBT-1830, Sakai Chemical Industry Co., Ltd., LBT-1813, and the like.

  As for the phosphorus compound (G component) used in the present invention, these (G-1) to (G-6) may be used alone or in combination of two or more at any ratio. Among these, from the viewpoint of further improving the light reflectivity, hue, and residence heat stability in the light reflective resin composition of the present invention, the phosphite ester (G-2) represented by the general formula (II) is used. It is preferable. (G-2) includes bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, among others. Is preferred.

  (G-1) to (G-6) used in the present invention preferably contain 0.001 to 1 part by weight of at least one selected from these with respect to 100 parts by weight of the resin component (C). Above all, (G-2) 0.003-0.3 parts by weight and (G-3) and / or (G-4) 0.003-0.3 parts by weight with respect to 100 parts by weight of the resin component (C) Are preferably used in combination. If the content of the phosphorus compound is less than 0.001 part by weight, the effect of improving light reflectivity, hue, and staying heat stability is small. Conversely, if it exceeds 1 part by weight, the hue and staying heat stability may be deteriorated. .

  The light-reflective resin composition of the present invention may further contain an ultraviolet absorber in order to further improve the light resistance. Among them, as the ultraviolet absorber used in the light-reflective resin composition of the present invention, a malonic acid ester compound, a cyanoacrylate compound, a benzoxazine is used in order to achieve both excellent light resistance, hue, and high light reflectance. It is preferable to use a compound or a hindered benzoate compound.

  Furthermore, it is particularly preferable to use a malonic acid ester compound or a cyanoacrylate compound in terms of suppressing discoloration during melt processing and simultaneously satisfying excellent light discoloration resistance and high light reflectance. Examples of the malonic acid ester compounds include 2- (1-arylalkylidene) malonic acid esters, and specific examples include PR-25, B-CAP, and Clariant Japan.

  Examples of the cyanoacrylate compounds include ethyl-2-cyano-3,3-diphenyl acrylate, methyl-2-cyano-3,3-diphenyl acrylate, and the like, among which ethyl-2-cyano-3,3-diphenyl acrylate Is preferred. Specifically, as 2′-ethylhexyl-2-cyano-3,3-diphenyl acrylate, Uvinul 3030, Uvinul 3035, Uvinul 3039 (all manufactured by BASF Corporation), ethyl-2-cyano-3 , 3-diphenyl acrylate includes SEESORB501 (manufactured by Cypro Kasei Co., Ltd.), and 2′-ethylhexyl-2-cyano-3,3-diphenyl acrylate includes SEESORB 502 (manufactured by Cypro Kasei Co., Ltd.).

  Examples of hindered benzoates include 3,5-di-t-butyl-4-hydroxybenzoic acid, n-hexadecyl ester, and the like. Specifically, UV-2908, manufactured by Cytec Industries, Ltd. Can be mentioned. In particular, those having a longest absorption wavelength of 300 nm or more are preferable because of their high ultraviolet absorption effect. As such a thing, the above-mentioned malonic acid ester etc. are mentioned, for example.

  Content of the ultraviolet absorber used for this invention is 0.05-5 weight part with respect to 100 weight part of resin components (C), Preferably it is 0.1-3 weight part. If the content of the ultraviolet absorber is less than 0.05 parts by weight, the improvement effect is small, and even if it exceeds 5 parts by weight, no further effect can be obtained, and mold deposit may occur.

  In addition, the light reflective resin composition of the present invention preferably contains a fluorescent dye in order to improve the brightness of the molded product. Specifically, the fluorescent dye is, for example, a white or blue fluorescent dye, and has a function of eliminating the yellowishness of the molded product and increasing the brightness. The function is similar to the bluing agent in terms of eliminating the yellowness of the molded product, but the bluing agent simply removes the yellow light of the molded product, whereas the fluorescent whitening agent has a wavelength of less than 400 nm. It differs in that it absorbs ultraviolet rays and changes its energy into visible light having a wavelength of 400 nm or more, particularly blue-violet light.

  As the white or blue fluorescent dye used in the present invention, any conventionally known fluorescent dye can be used. Among them, those having a high molecular weight are preferable from the viewpoint of heat resistance and volatile gases, and examples thereof include stilbene benzoxazole-based and phenylallyltriazolyl coumarin-based fluorescent brighteners.

  The content of the fluorescent dye may be appropriately selected and determined. However, if the content of the fluorescent dye is too low, the yellowing of the molded product is erased and the brightness is increased, and the visible region absorbs ultraviolet rays. The function of radiating blue-violet is not sufficiently exhibited. On the other hand, even if it is too much, an increase in the effect commensurate with the increase in the amount added cannot be expected. Therefore, normally, it is preferable that it is 0.00001-1 weight part with respect to 100 weight part of resin components (C).

  In the light-reflective resin composition of the present invention, for example, a phenol-based stabilizer, a release agent, an antistatic agent, a colorant, a fluidity improver, a flame retardant other than an organic acid metal salt, talc, Inorganic fillers such as mica, silica and glass flakes, fibrous reinforcing materials such as glass fibers and carbon fibers, anti-aggregation agents and the like may be further added.

  The mixing and kneading of the light-reflective resin composition of the present invention may be performed by a method applied to ordinary thermoplastic resins, such as a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, It can be carried out by an axial screw extruder, a multi-screw extruder or the like. The temperature condition for kneading is usually 260 to 300 ° C.

  The light-reflective resin composition of the present invention can be applied to a general thermoplastic resin molding method. For example, injection molding, injection compression molding, and extrusion molding from a pellet-shaped resin composition are possible from the viewpoint of productivity. Furthermore, it can also be set as the target molded object by vacuum forming, pressure forming, etc. from the extruded sheet-like molded product.

  The light reflective member molded from the light reflective resin composition of the present invention having excellent light reflection characteristics, mechanical characteristics, electrical characteristics, and melt heat stability is, for example, a light beam reflection plate for a backlight of a liquid crystal display device. (Including peripheral members such as a frame of a liquid crystal display device backlight), lighting devices such as electric / electronic devices and advertising lights, and light reflecting members of automotive devices such as automotive meter panels.

  The present invention will be described more specifically with reference to the following examples and comparative examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

Raw material resin and various additives PC (aromatic polycarbonate resin): Iupilon S-3000FN, viscosity average molecular weight 21000, manufactured by Mitsubishi Engineering Plastics

  Titanium oxide: PC-3 manufactured by Ishihara Sangyo Co., Ltd.

  Coumarin-based fluorescent brightening agent: 3-phenyl-7- (2H-naphtho (1,2-d) -triazol-2-yl) coumarin Haccor PSR manufactured by Haccor Chemical

  Phosphate ester heat stabilizer: bis (2,4-di-t-butylphenyl) phosphite Adeka Stub PEP-24G manufactured by Asahi Denka Kogyo Co., Ltd.

  Phosphite ester heat stabilizer: Tris (2,4-di-t-butylphenyl) pentaerythritol diphosphite Adeka Stub 2112 manufactured by Asahi Denka Kogyo Co., Ltd.

  Organophosphate metal salt heat stabilizer: Mono and distearyl acid phosphate zinc salt mixture LBT-1830 manufactured by Sakai Chemical Industry Co., Ltd.

  Organic acid metal salt-based flame retardant: Perfluorobutyl sulfonic acid metal salt Megafac F114 manufactured by Dainippon Ink & Chemicals, Inc.

  PTFE (polytetrafluoroethylene resin): Daikin Industries, Ltd. Polyflon F201L

  PCC (alicyclic polyester) resin: Polycyclohexanedimethanol cyclohexanedicarboxylate obtained in Production Example 1 below Intrinsic viscosity 0.957 dl / g, terminal carboxylic acid concentration 12 μeq / g

<Production Example 1>
A stainless steel reactor equipped with a stirrer, reflux condenser, heating device, pressure gauge, thermometer, and decompression device, and with a capacity of 100 liters, 1,4-cyclohexanedicarboxylic acid (trans isomer: cis cis ratio is 96: 4) 101.5 parts by weight, 1,4-cyclohexanedimethanol (trans isomer: cis isomer ratio is 69:31) 88.6 parts by weight and tetra-n-butyl titanate in a 6% by weight butanol solution 0.005 part by weight The reactor was charged and the inside of the reactor was replaced with nitrogen gas. While sealing the inside of the reactor with nitrogen gas, the internal temperature was raised to 150 ° C. in 30 minutes, and further raised from 150 ° C. to 200 ° C. over 1 hour.

  Next, after carrying out the esterification reaction by maintaining the temperature at 200 ° C. for 1 hour, the polycondensation reaction is carried out while gradually increasing the pressure from 200 ° C. to 250 ° C. over 45 minutes while gradually reducing the pressure in the reactor. went. The pressure inside the reactor was maintained at an absolute pressure of 0.1 kPa and the reaction temperature was 50 ° C. and maintained for 3.6 hours to complete the polycondensation reaction. After completion of the polycondensation reaction, the obtained resin was extracted in a strand shape into water, cut and pelletized.

  The intrinsic viscosity and the terminal carboxylic acid concentration measured by the method described later were 0.957 dl / g and 12 μeq / g, respectively. Hereinafter, the alicyclic polyester resin obtained in Production Example 1 is referred to as PCC.

Test method Reflectivity: Measured with UV-3100PC and MPC-3100 manufactured by Shimadzu Corporation using a reflectance measurement test piece of 50 * 50 * 2 [mm]. The measuring method is based on the Shimadzu Corporation method.

  Combustibility: The vertical combustion test was performed using a 1.6 mm-thick combustion test piece in accordance with UL-94.

  Tensile yield strength and tensile fracture strength: In accordance with ISO527-1 and 527-2 standards, the test piece was 3.2 mm thick.

  Bending strength and flexural modulus: In accordance with ISO 178 standard, the test piece was 3.2 mm thick.

[Examples 1 to 5]
Blend the alicyclic polyester and additives in the ratio (parts by weight) shown in Table 1 with respect to 100 parts by weight of PC, blend for 15 minutes with a tumbler, and then cylinder temperature of 300 ° C. with a twin screw extruder. And extruded into pellets. The pellets were molded with an injection molding machine at a cylinder temperature of 280 [deg.] C. and a mold temperature of 80 [deg.] C., and a 50 * 50 mm * 2 mm thick test specimen for measuring reflectance. The evaluation results are shown in Table 1.

[Comparative Example 1]
Similarly to Examples 1 to 5, a test piece was molded from the resin composition having the formulation shown in Table 1, evaluated, and the result is shown in Table 1.

  As is apparent from Table 1, the resin moldings obtained by molding the light-reflecting resin composition of the present invention are all excellent in reflectivity exceeding 95%, and at the same time, have various mechanical properties and flame retardancy. It turns out that it is also excellent. On the other hand, in the comparative example 1 which does not contain an aliphatic polyester resin, the reflectance was insufficient.

Claims (6)

An aromatic polycarbonate resin (A) 30 to 99 parts by weight, relative to cycloaliphatic polyester resin (B) a resin component consisting of 1 to 70 parts by weight (C) 100 parts by weight of 5 to 30 wt titanium oxide (D) Part of the light-reflective resin composition.   The alicyclic polyester resin (B) comprises an alicyclic dicarboxylic acid mainly composed of a 1,4-cyclohexanedicarboxylic acid component and an alicyclic diol mainly composed of 1,4-cyclohexanedimethanol. Item 2. A light-reflective resin composition according to Item 1.   The light-reflective resin composition according to claim 1 or 2, further comprising 0.001 to 5 parts by weight of an organic acid metal salt (E) with respect to 100 parts by weight of the resin component (C).   The light-reflective resin composition according to any one of claims 1 to 3, further comprising 0.05 to 1 part by weight of polytetrafluoroethylene (F) with respect to 100 parts by weight of the resin component (C). Further, 0.001 to 1 part by weight of at least one phosphorus compound (G) selected from the compound group represented by the following general formulas (I) to (VI) is included with respect to 100 parts by weight of the resin component (C). The light-reflective resin composition according to any one of claims 1 to 4.
O = P (OH) _n (OR) _3-n (I)
(In general formula (I), R represents an alkyl group or an aryl group, which may be the same or different, and n represents an integer of 0 to 2.)

(In general formula (II), R ′ represents an alkyl group or an aryl group, which may be the same or different.)

(In the general formula (III), R ^{1 to} R ⁴ represent an alkyl group or an aryl group, and may be the same or different, and M represents a metal selected from an alkaline earth metal and zinc.)

(In general formula (IV), R ⁵ represents an alkyl group or an aryl group, and M represents a metal selected from alkaline earth metals and zinc.)

(In the general formula (V), R ^{6 to} R ¹¹ represent an alkyl group or an aryl group, and may be the same or different, and M ′ represents a metal atom that becomes a trivalent metal ion.)
Formula (VI)

(In the general formula (VI), R ^{12 to} R ¹⁴ are alkyl groups or aryl groups, which may be the same or different, and M ′ represents a metal atom that becomes a trivalent metal ion, 'May be the same or different.   A light reflective member formed by molding the light reflective resin composition according to claim 1.