JP4946089B2 - Light diffusing resin composition and light diffusing member - Google Patents

Description

  The present invention relates to a light diffusing resin composition and a light diffusing member formed by molding the same. Specifically, it has high light diffusivity and total light transmittance, and at the same time has excellent mechanical properties, thermal properties, electrical properties, and weather resistance, and further suppresses discoloration during melt processing and use. The present invention relates to a resin composition and a light diffusing member using the same. Specifically, the present invention relates to a light diffusing resin composition and a light diffusing member that exhibit excellent effects in various light covers, lighting signs, light transmissive screens, various displays, light diffusion sheets for liquid crystal display devices, and the like. .

  Polycarbonate resin has a wide range of uses as a thermoplastic resin with excellent impact resistance, heat resistance, and transparency, and it is lighter and more productive than inorganic glass. It is used for light diffusion sheets such as signboards, light transmission screens, various displays, and liquid crystal display devices.

  In order to impart light diffusibility to the polycarbonate resin, addition of inorganic compound fillers such as glass, silica and aluminum hydroxide has also been proposed, but the mechanical strength decreases, the total light transmittance and weather resistance decrease, There was a problem of discoloration at the time of molding processing or use at high temperature, and it was not practical. In particular, recently, various display devices have become larger and thinner, and higher luminance is required for television applications. Therefore, higher fluidity and higher transmittance are strongly demanded for materials. .

  On the other hand, with the reduction in size and thickness of the final product, a complex and fine shape is being demanded for the light diffusion plate. For this, it is necessary to improve the fluidity of the resin forming the light diffusion plate. For example, as a means to improve the fluidity of polycarbonate resin, polymer alloying with acrylonitrile / butadiene / styrene resin (ABS resin), acrylonitrile / styrene resin (AS resin), etc. has been proposed and put to practical use. As means for improving the chemical resistance of the resin, polymer alloying with a thermoplastic aromatic polyester resin represented by polybutylene terephthalate resin or polyethylene terephthalate resin has been proposed and put into practical use. However, since these polymer alloys are all opaque, it has been difficult to use them for light diffusing plates that require transparency.

  As means for solving the above-mentioned problems, a transparent material comprising an aromatic polycarbonate resin and a poly (1,4-cyclohexanedimethanol-1,4-cyclohexanedicarboxylate) resin (hereinafter sometimes abbreviated as PCC resin). Have been proposed (see, for example, Patent Documents 1 and 2). These show the prevention of coloring of the resulting polymer by using a catalyst deactivator. As the catalyst deactivator, an acidic phosphate, a phosphite having one or more acidic hydrogens, a group 9 or a group 10 Examples include metal phosphates, phosphorus oxoacids, and acid pyrophosphate metal salts.

  However, even this transparent resin is not always satisfactory in its transparency and hue. In particular, when a catalyst deactivator is blended, wet heat resistance and residence heat stability deteriorate, so these improvements have been strongly demanded. In addition, an excellent balance of transparency, hue, impact resistance, moist heat resistance and residence heat stability has been demanded. Moreover, in order to obtain a thin-walled molded product or a large-sized molded product, it is necessary to mold at a high molding temperature, and improvement of impact resistance and stagnant heat stability when molded at a high temperature has been a problem.

On the other hand, a resin composition containing a specific organic phosphite compound (see, for example, Patent Document 3) or a specific phosphate compound is added to prevent coloration or improve thermal stability of a polymer blend composed of a polycarbonate resin and a polyester resin. A resin composition (see, for example, Patent Document 4) is disclosed. However, these resin compositions are intended for aromatic polyesters based on terephthalic acid, and are not specifically described with respect to alicyclic polyesters, and specifically exemplified resin compositions are opaque. It is a thing. Furthermore, there is no suggestion of improving the transparency of the resin composition by blending a phosphite compound or a phosphate compound.

  The techniques described in Patent Documents 3 and 4 improve the thermal decomposition by transesterification of a polycarbonate resin and a polyester resin with a phosphite compound or a phosphate compound, and are transparent by using a specific phosphorus stabilizer in combination. There was no suggestion of improving the balance of color, hue, impact resistance, moist heat resistance, and residence heat stability.

  Further, a crystallization rate containing a resin composition (for example, see Patent Document 5), which is made of a polycarbonate resin, an ABS resin, and a phosphoric acid ester metal salt and excellent in impact resistance, a thermoplastic polyester resin, and an organic phosphoric acid ester metal salt. Although improved resin compositions (for example, see Patent Document 6) and the like are disclosed, transparency, hue, impact resistance, and heat and humidity resistance in a resin composition of an aromatic polycarbonate and an alicyclic polyester resin are disclosed. There was no suggestion about the balance of stagnant heat stability.

  Further, a retardation film having a good color accuracy composed of an aromatic polycarbonate resin and an alicyclic polyester resin has been proposed (see, for example, Patent Document 7), and color is obtained by containing mono- and di-stearyl acid phosphate. It is described that display / color accuracy is improved, and that a phosphorus stabilizer may be contained. However, it only discloses improving the hue by including a specific phosphate compound, and there is also a description about improving the balance of transparency, hue, impact resistance, moist heat resistance, residence heat stability, and light resistance. There was no suggestion.

  On the other hand, as a resin composition excellent in transparency, impact resistance, chemical resistance, and weather resistance, a housing material made of a resin composition containing an alicyclic polyester and polycarbonate (see, for example, Patent Document 8), and electricity. Electronic parts (see, for example, Patent Document 9) have been proposed. It is also described that such a resin composition may contain an inorganic compound such as glass fiber, carbon fiber, talc, clay, mica, glass flake, milled glass, and glass beads. However, these resin compositions still have low thermal stability during melt processing and large yellowing, making them difficult to use as light diffusing members. There was no suggestion.

  Further, as a resin composition having improved ductility, chemical resistance, and melt flow characteristics, a transparent / translucent molding composition comprising a polycarbonate resin and an alicyclic polyester resin has also been proposed (for example, Patent Document 10). reference). However, this polycarbonate resin composition has been difficult to use as a light diffusing member because of its low thermal stability during melt processing and large yellowing.

  Furthermore, although it is described that an elastomer such as ABS is added as an optional component to improve haze reduction and light transmittance, the light diffusibility is insufficient. In addition, in these resin compositions, for example, a transparent elastomer component is added for the purpose of improving low temperature impact resistance. However, the average particle size of the elastomer component is generally There was a problem that sufficient light diffusivity could not be obtained due to the extremely small size of about 100 nm.

Special Table 2002-517538 JP 2003-176401 A Japanese Unexamined Patent Publication No. 3-977752 JP-A 63-265949 JP-T-2004-509174 JP-A-11-35807 JP 2005-165085 A JP 2003-110252 A JP 2003-113252 A Japanese translation of PCT publication No. 2004-514011

  The object of the present invention is to have high light diffusivity and total light transmittance, and at the same time, excellent mechanical properties, thermal properties, electrical properties, weather resistance, and also suppress discoloration during melt processing and use. An object of the present invention is to provide a light diffusing resin composition and a light diffusing member formed by molding the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition containing an aromatic polycarbonate resin containing a specific alicyclic polyester resin, a light diffusing agent, and a specific phosphorus compound has high light. It was found that it has diffusivity and total light transmittance, and at the same time has excellent mechanical properties, thermal properties, electrical properties, weather resistance, and can suppress discoloration during melt processing and use, and has completed the present invention. .

That is, the gist of the present invention is a light diffusing resin composition comprising an aromatic polycarbonate resin (A), an alicyclic polyester resin (B), and fine particles (however, excluding a mesoporous inorganic filler) (D), The weight average diameter of the fine particles (excluding the mesoporous inorganic filler) (D) is 0.7 to 30 μm, and the content thereof is 30 to 99 parts by weight of the aromatic polycarbonate resin (A) and the alicyclic polyester resin ( B) 0.05 to 20 parts by weight with respect to 100 parts by weight of the resin component (C) consisting of 1 to 70 parts by weight, and further, a phosphite ester (E2) represented by the general formula ( II) 0.003 to 0.3 parts by weight per 100 parts by weight of resin component (C), organophosphate metal salt represented by the following general formula (III) and organophosphorus represented by the following general formula (IV) Acid ester metal (E3), and characterized in that it comprises 0.003 to 0.3 parts by weight relative to the resin component (C) 100 parts by weight, the light diffusing resin composition.

（一般式（ＩＩ）中、Ｒ’はアルキル基またはアリール基であり、それぞれ同一であっても異なっていてもよい。）

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

（一般式（ＩＩＩ）中、Ｒ^１〜Ｒ^４は炭素数２〜２５のアルキル基であり、それぞれ同一であっても異なっていてもよい。Ｍはアルカリ土類金属および亜鉛より選ばれる金属を表す。）

(In the general formula (III), R ^{1 to} R ⁴ are each an alkyl group having 2 to 25 carbon atoms and may be the same or different. M represents a metal selected from an alkaline earth metal and zinc. To express.)

（一般式（ＩＶ）中、Ｒ^５は炭素数２〜２５のアルキル基を示し、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 having 2 to 25 carbon atoms , and M represents a metal selected from an alkaline earth metal and zinc.)

The light diffusing resin composition of the present invention has high light diffusibility and total light transmittance, and at the same time, is excellent in mechanical properties, thermal properties, electrical properties, weather resistance, and at the time of melt processing and use. Discoloration is suppressed. The light diffusing resin composition of the present invention having such excellent characteristics includes a lighting cover, a lighting signboard, a transmission screen, a traffic light lens and a lens cover, various displays, a light diffusion sheet of a liquid crystal display device, a light guide plate, etc. As a light diffusing member, it can be used widely.

  Hereinafter, the present invention will be described in detail.

[1] Aromatic polycarbonate resin (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 manufacturing method of aromatic polycarbonate resin (A) used for this invention is not specifically limited, What was manufactured by the conventionally well-known arbitrary methods can be used. 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.

  As aromatic dihydroxy compounds used as raw materials, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), 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-hydroxy) Phenyl) 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) propane, 2,2- (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, , 1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxyphenyl) -1,1,1-trichloropropane, 2,2- Bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexachloropropane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane Bis (hydroxyaryl) alkanes such as;

  Bis such as 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (Hydroxyaryl) cycloalkanes; cardostructure-containing bisphenols such as 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene; 4,4′- Dihydroxydiaryl ethers such as dihydroxydiphenyl ether and 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether;

  Dihydroxy diaryl sulfides such as 4,4′-dihydroxydiphenyl sulfide and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide; 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3 Dihydroxy diaryl sulfoxides such as' -dimethyldiphenyl sulfoxide; dihydroxy diaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone; hydroquinone, resorcin, 4,4 Examples include '-dihydroxydiphenyl.

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.

  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.

  The aromatic polycarbonate resin (A) may be a branched aromatic polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound. 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) benzene, 1, Polyhydroxy compounds such as 1,1-tri (4-hydroxyphenyl) ethane, or 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chloroisatin, 5,7-dichloro Isatin, 5-bromoisatin and the like can be mentioned.

  Among these polyfunctional aromatic compounds, 1,1,1-tri (4-hydroxyphenyl) ethane is particularly preferable. The polyfunctional aromatic compound can be used by substituting a part of the aromatic dihydroxy compound, and the amount used is preferably 0.01 to 10 mol% based on the aromatic dihydroxy compound, Among these, 0.1 to 2 mol% is preferable.

  The reaction by the interfacial polymerization method is usually carried out in the presence of an organic solvent inert to the reaction and an aqueous alkali solution, and the pH is usually kept at 9 or higher, and an aromatic dihydroxy compound and, if necessary, a molecular weight modifier (end terminator) and Use an antioxidant for antioxidants of aromatic dihydroxy compounds, react with phosgene, add a polymerization catalyst such as tertiary amine or quaternary ammonium salt, and obtain polycarbonate by interfacial polymerization . 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. In addition, reaction temperature is 0-40 degreeC, for example, and reaction time is several minutes (for example, 10 minutes)-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.

  The reaction by the melt transesterification method is, for example, a transesterification reaction between a carbonic acid diester 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 can also be mentioned. Examples of the terminal terminator at this time 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, and more preferably 700 ppm or less.

  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) is produced by the transesterification method, a transesterification catalyst is usually used. The transesterification catalyst is optional and 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 may be used in combination. As the transesterification reaction using the above raw materials, the reaction is carried out at a temperature of 100 to 320 ° C., and finally a melt polycondensation reaction is performed under reduced pressure of 2 mmHg or less while removing by-products such as aromatic hydroxy compounds. The method of performing is mentioned.

  The melt polycondensation can be performed by either a batch method or a continuous method, but it is preferably performed by a continuous method in consideration of the stability of the resin composition of 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 compound that neutralizes such a catalyst is preferably added in an amount of 0.5 to 10 equivalents, particularly 1 to 5 equivalents, relative to the alkali metal contained in the catalyst. In addition, the compound that neutralizes such a catalyst is preferably added in an amount of 1 to 100 ppm, more preferably 1 to 20 ppm, based on the polycarbonate.

  The molecular weight of the aromatic polycarbonate resin (A) used in the present invention is arbitrary and may be appropriately selected and determined. Usually, the viscosity average molecular weight [Mv] converted from the solution viscosity is preferably 10,000 to 50,000. . By setting the viscosity average molecular weight of the aromatic polycarbonate resin (A) to 10000 or more, the mechanical strength tends to be further improved, which is more preferable when used for applications requiring high mechanical strength. On the other hand, when the viscosity average molecular weight is 50000 or less, there is a tendency that the decrease in fluidity can be improved, which is more preferable from the viewpoint of easy molding processability.

  The viscosity average molecular weight is preferably 12,000 to 40,000, and more preferably 14,000 to 30,000. As the aromatic polycarbonate resin (A) used in the present invention, two or more different aromatic polycarbonate resins may be mixed. Of course, you may mix the aromatic polycarbonate resin whose viscosity average molecular weight is outside the said suitable range.

Here, the viscosity average molecular weight [Mv] is obtained by using methylene chloride as a solvent and obtaining an intrinsic viscosity [η] (unit: dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer. , Η = 1.23 × 10 ⁻⁴ M ^0.83 . Here, the intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl).

  The aromatic polycarbonate resin (A) used in the present invention contains an aromatic polycarbonate oligomer in order to improve the fluidity of the light diffusing resin composition of the present invention and to improve the appearance of a molded product using the same. It is preferable to do. The aromatic polycarbonate oligomer has a viscosity average molecular weight [Mv] of preferably 1500 to 9500, and more preferably 2000 to 9000. When this aromatic polycarbonate oligomer is used, it is preferably 30% by weight or less in the aromatic polycarbonate resin (A) used in the present invention.

  Further, as the aromatic polycarbonate resin (A) used 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. A building member such as a plate is preferred. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used. The regenerated aromatic polycarbonate resin is preferably 80% by weight or less of (A), more preferably 50% by weight or less.

[2] Alicyclic polyester resin (B);
The alicyclic polyester resin (B) used in the present invention is a polyester resin obtained by reacting a dicarboxylic acid component containing 1,4-cyclohexanedicarboxylic acid as a main component with a diol component. Among them, the alicyclic polyester resin (B) used in the present invention is preferably derived from a dicarboxylic acid component as a raw material, unlike a case where a dicarboxylic acid ester is used as a raw material, and has a low alkyl ester terminal. The ratio of the alkyl ester terminal to the total terminal of the polyester is preferably 5 mol% or less, and preferably 1 mol% or less.

  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, alicyclic dicarboxylic acids having 6 to 12 carbon atoms or ester-forming derivatives thereof are preferable, 1,4-cyclohexanedicarboxylic acid or ester-forming derivatives thereof are more preferable, and 1,4-cyclohexanedicarboxylic acid is particularly preferable. Is preferred. An alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid is preferable because it is easier to obtain and cheaper than an ester-forming derivative.

  When 1,4-cyclohexanedicarboxylic acid is used, the ratio of the trans isomer to the cis isomer is preferably 80/20 to 100/0, particularly 85/15 to 100/0, more preferably 90/10. ~ 100/0, particularly preferably 95/5 to 100/0. By making this ratio into the above-mentioned range, it exists in the tendency for the heat resistance of the alicyclic polyester resin obtained to improve.

  The dicarboxylic acid component of the alicyclic polyester resin (B) used in the present invention is an alicyclic dicarboxylic acid or an ester-forming derivative thereof of 80 mol% or more, preferably 90 mol%, based on the total dicarboxylic acid component. It contains above. Other dicarboxylic acid components include aromatic dicarboxylic acids and aliphatic dicarboxylic acids. Specifically, terephthalic acid, phthalic acid, isophthalic acid, 1,4-phenylenedioxydicarboxylic acid, 1,3-phenylenedioxydiacetic acid, 4,4-diphenyldicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid 4,4-diphenyl ketone dicarboxylic acid, 4,4′-diphenoxyethanedicarboxylic acid, 4,4-diphenylsulfone dicarboxylic acid, aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, succinic acid, glutamic acid, Examples include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecadicarboxylic acid and dodecadicarboxylic acid, and alkyl esters or halides having 1 to 4 carbon atoms.

  The alicyclic diol component is not particularly limited as long as it has two hydroxyl groups bonded to the alicyclic structure, but the alicyclic diol has two hydroxyl groups bonded to a five-membered or six-membered ring. It is preferable that By using a 5-membered or 6-membered alicyclic diol as the alicyclic diol, the heat resistance of the resulting polyester resin can be increased.

  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 diol; 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2, 6-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 preferable because the methylol group is in the para position, and thus has high reactivity, and a polyester resin having a high polymerization degree and a high glass transition temperature can be obtained. The ratio of 1,4-cyclohexanedimethanol to trans form and cis form is 60/40 to 100/0.
It is preferable that

  As the diol component used in producing the aliphatic polyester resin (B) used in the present invention, the alicyclic diol as described above is contained in an amount of 80 mol% or more, particularly 90 mol% or more, based on the total diol component. It is preferable that Examples of other diol components include aliphatic diols and aromatic diols. When the alicyclic diol is less than 80 mol%, compatibility with the aromatic polycarbonate resin (A), transparency, heat resistance, and the like may be deteriorated.

  Specific examples of other diol components include aliphatic diols such as ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol; xylylene glycol, 4,4-dihydroxybiphenyl, 2,2-bis (4 ′ Aromatic diols such as -hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, and bis (4-β-hydroxyethoxyphenyl) sulfonic acid;

  Furthermore, the alicyclic polyester resin (B) used in the present invention may contain a small amount of a copolymer component other than the diol component and the dicarboxylic acid component. Examples of such copolymer components include glycolic acid, p-hydroxybenzoic acid, hydroxycarboxylic acids such as p-β-hydroxyethoxybenzoic acid, alkoxycarboxylic acids, stearyl alcohol, benzyl alcohol, stearic acid, behenic acid, benzoic acid. Monofunctional components such as tert-butylbenzoic acid and benzoylbenzoic acid, tricarballylic acid, trimellitic acid, trimesic acid, pyromellitic acid, naphthalenetetracarboxylic acid, gallic acid, trimethylolethane, trimethylolpropane, glycerol, penta Trifunctional or higher polyfunctional components such as erythritol and sugar ester may be used. These components are preferably 10 mol% or less of the B component.

  In the present invention, as a use ratio in the esterification reaction or transesterification reaction between the dicarboxylic acid component and the diol component, the total amount of the diol component is 1 to 2 times in molar ratio to the total amount of the dicarboxylic acid component. It is preferable. In particular, when the main component is a diol component having a high boiling point such as 1,4-cyclohexanedimethanol, the molar ratio is preferably 1 to 1.2 times.

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

  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. Moreover, you may combine with a magnesium compound, a phosphorus compound, etc. as needed. The amount of the catalyst used is preferably 1 to 2000 ppm, more preferably 10 to 1000 ppm, more preferably 50 to 1000 ppm, and particularly preferably 100 to 1000 ppm with respect to the alicyclic polyester resin (B) to be produced.

The esterification reaction (or transesterification reaction) between the dicarboxylic acid component and the diol component is usually performed at a reaction temperature of 150 ° C. to 230 ° C., preferably 180 ° C. to 220 ° C., and the reaction time is 10 minutes to 10 hours, It is preferably 30 minutes to 5 hours. The reaction solution after the reaction is usually transferred to a polycondensation tank equipped with a stirrer, a distilling tube and a vacuum addition apparatus. The esterification reaction tank is equipped with a vacuum addition apparatus, and the esterification reaction and polycondensation are performed in one tank. A reaction may be performed.

  After the esterification 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 a polymerization catalyst is added, the amount thereof is a total of 50 to 2000 ppm, preferably 100 to 1000 ppm in total with the esterification reaction or transesterification reaction catalyst, based on the polyester that is usually produced. The polycondensation may be performed at an esterification reaction completion temperature of -300 ° C or lower, preferably 265 ° C or lower, usually for 10 minutes to 10 hours, preferably 30 minutes to 5 hours. If the temperature is too high, the polymerization reaction tends not to proceed, probably because thermal decomposition occurs during the polymerization reaction. The internal pressure of the tank is 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 may be appropriately selected and determined, but is usually 0.4 to 1.5 dl / g, particularly 0.5 to 1.3 dl / g, Further, it is preferably 0.6 to 1.5 dl / g, particularly preferably 0.7 to 1.4 dl / g. When the intrinsic viscosity is 0.4 dl / g or more, the mechanical strength is further improved, and when it is 1.5 dl / g or less, the fluidity is further improved and the moldability is improved. Furthermore, the obtained alicyclic polyester resin (B) may be subjected to solid phase polymerization as necessary to have a higher intrinsic viscosity. Here, the intrinsic viscosity is a value obtained by measuring at 30 ° C. using a Ubbelohde viscometer using a phenol / tetrachloroethane (weight ratio 1/1) mixed solution as a solvent.

  The terminal carboxylic acid concentration of the alicyclic polyester resin (B) used in the present invention is preferably 70 μeq / g or less, particularly 40 μeq / g or less, more preferably 30 μeq / g or less, particularly 10 μeq / g or less. Is preferred. It is preferable that the terminal carboxylic acid concentration is 70 μeq / g or less because the heat and humidity resistance of the resin composition of the present invention tends to be further improved.

  The terminal acid value is controlled by, for example, controlling the use ratio of 1,4-cyclohexanedicarboxylic acid and 1,4-cyclohexanedimethanol, which are raw materials, or alkylene diol, This can be carried out by using an alkylene diol having 2 to 10 carbon atoms in combination.

  In order to set the terminal acid value of the alicyclic polyester resin (B) used in the present invention to 40 μeq / g, for example, a dicarboxylic acid component in which 90 mol% or more is 1,4-cyclohexanedicarboxylic acid, and 90 mol% or more is used. When 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 1.1 mol. do it.

  For example, a dicarboxylic acid component in which 90 mol% or more is 1,4-cyclohexanedicarboxylic acid, 80-99.5 mol% is 1,4-cyclohexanedimethanol, and 0.5-20 mol% has 2 carbon atoms. In the case of using an alkylene diol of 10 to 10, a method of using 1.02 to 1.2 mol, more preferably 1.02 to 1.1 mol of the diol component with respect to 1 mol of the dicarboxylic acid component can be mentioned.

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 cyclic polyester resin, preferably 2
It is preferably from 00 to 250 ° C, particularly from 210 to 230 ° C, particularly from 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, naturally, when used in the light diffusing resin composition of the present invention, the transmitted image becomes yellow and the original image cannot be reproduced. Therefore, generally YI is preferably 18 or less, more preferably 15 or less. The lower limit of YI is usually about -5.

  The alicyclic polyester resin (B) used in the present invention has a light diffusing member when the light transmittance is too low, specifically, when the light transmittance is too low when a 2 mm-thick molded plate is used. In such a case, the light beam may not be sufficiently transmitted and the screen may become dark. Therefore, the light transmittance is usually 87% or more, preferably 87.5% or more, and more preferably 88% or more.

  As 1,4-cyclohexanedicarboxylic acid that is a raw material of the alicyclic polyester resin (B) used in the present invention, the light transmittance at a wavelength of 340 nm is large, and the light transmittance of the obtained alicyclic polyester resin is high. It is preferable from the point. When this light transmittance is too low, the YI value of the resulting alicyclic polyester resin tends to increase, and the light transmittance of the alicyclic polyester resin tends to decrease. Specifically, as this light transmittance, the light transmittance measured by the following method (hereinafter sometimes abbreviated as T-340) is preferably 85% or more, more preferably 87% or more.

  This T-340 was measured by using a spectrophotophotometer to put a 2N potassium hydroxide solution into a quartz cell having an optical path length of 10 mm, zero correction, and then adding 1 to 50 ml of 2N potassium hydroxide solution. A solution obtained by dissolving 5.0 g of 4-cyclohexanedicarboxylic acid in a quartz cell having an optical path length of 10 mm is a light transmittance at a wavelength of 340 nm measured for the solution.

  In addition, in the raw material of alicyclic polyester resin (B) used for this invention, as a method of manufacturing raw material 1, 4- cyclohexane dicarboxylic acid whose trans isomer is 90 mol% or more, for example, 1, 4- cyclohexane dicarboxylic acid And 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 acid precipitation after liquid phase nuclear hydrogenation of sodium terephthalate in the presence of water, hydrogen and hydrogenation catalyst Is mentioned.

  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 for this invention consists of 30-99 weight part of aromatic polycarbonate resin (A) mentioned above, and 1-70 weight part of 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 fluidity and weather resistance is small.

[4] Fine particles (D)
As the fine particles (excluding the mesoporous inorganic filler) of the component (D) used in the present invention, any conventionally known fine material other than the mesoporous inorganic filler can be used as long as the weight average diameter is 0.7 to 30 μm. . If the weight average diameter of the fine particles (D) used in the present invention is less than 0.7 μm, the light diffusibility is low and the light source may be seen through. May decrease.

  In the fine particles (D) used in the present invention, it is preferable that the absolute value of the difference in refractive index from the resin component (C) is relatively small. However, if it is too small, the light diffusibility may be lowered. On the contrary, if it is too large, the light transmittance may be lowered. Therefore, it is usually preferably 0.01 or more and 0.2 or less.

  Furthermore, in order for the light diffusing resin composition of the present invention to have excellent light diffusibility, total light transmittance, and discoloration resistance at the time of melt processing and use, the fine particles (D) used in the present invention contain organic light. It is preferably a diffusing fine particle, and specifically, for example, an acrylic or silicone light diffusing fine particle is preferred.

  Examples of the acrylic light diffusing fine particles include fine particles obtained by changing the copolymerization ratio of the acrylic monomer alone or the acrylic monomer and the styrene monomer, and polymerizing by a suspension polymerization method using a crosslinking agent. By selecting the copolymerization ratio of the acrylic monomer and the styrene monomer from the range of 100: 0 to 1:99, the refractive index of the obtained polymer can be in the range of 1.493 to 1.590. .

  Normally, if the copolymerization ratio of the styrene monomer is too high, the light resistance is lowered, and it tends to be yellowish during use. Conversely, if the copolymerization ratio of the acrylic monomer is too high, the fine particles and the resin The difference in refractive index from the component (C) becomes large, and “glare” is noticeable when the light diffusing member is formed, and the visibility may be lowered. Therefore, when the acrylic-styrene copolymer fine particles are used as the fine particles (D) used in the present invention, the blend of the aromatic polycarbonate resin (A) and the alicyclic polyester resin (B) constituting the resin component (C). It is preferable to adjust the refractive index of the acrylic-styrene copolymer fine particles according to the rate.

  Examples of the acrylic monomer include methacrylate monomers such as methyl methacrylate and ethyl methacrylate, acrylate monomers such as methyl acrylate and ethyl acrylate, and acrylamide. Examples of the styrene monomer include styrene, α-methylstyrene, Vinyl toluene etc. are mentioned. In the polymerization or copolymerization of these monomers, other monomers may be copolymerized as necessary with these as the main components. As the crosslinking agent, any conventionally known polyfunctional monomer such as ethylene glycol dimethacrylate, divinylbenzene, 1,6-hexanediol, trimethylpropane trimethacrylate, trimethylpropane trimethacrylate, trimethylpropane triacrylate, or the like is generally used. be able to.

  When silicone-based light diffusing fine particles are used as the fine particles (D) used in the present invention, for example, silicone resin fine particles having a refractive index of 1.45 to 1.46 are preferable. Examples of commercially available silicone-based light diffusing fine particles include Tospearl series manufactured by Toshiba Silicone, Trefill series manufactured by Toray Dow Corning Silicone, and silicone powder manufactured by Shin-Etsu Chemical Co., Ltd.

  Content of microparticles | fine-particles (D) in this invention is 0.05-20 weight part with respect to 100 weight part of resin components (C), Preferably it is 0.1-10 weight part. If the content of the fine particles (D) is less than 0.05 parts by weight, the light diffusibility is low, and even if the thickness of the light diffusible member is thick, the light source can be seen through. Even if the thickness of the conductive member is thin, the total light transmittance is lowered, and further, the mechanical strength and heat resistance are lowered.

  Further, the content of the fine particles (D) in the light diffusing resin composition of the present invention is preferably adjusted according to the thickness of the light diffusing member formed by molding the fine particles (D). Specifically, for example, when the thickness of the light diffusing member is 0.1 to 2 mm, the content of the fine particles (D) is 1 to 20 times with respect to 100 parts by weight of the resin component (C). Is preferred. When the thickness of the light diffusing member is more than 2 mm and 5 mm or less, specifically, acrylic-styrene copolymer fine particles are used, and the content with respect to 100 parts by weight of the resin component (C) is 0.05. It is preferable to set it as -5 weight part.

[5] Phosphorus compound (E);
The present invention is characterized in that the above-mentioned (A), (B) and (D) further contain a phosphorus compound (E). The phosphorus compound (E) used in the present invention is at least one selected from the group consisting of phosphorus compounds represented by the following general formulas (I) to (VI). Specifically, the phosphoric acid esters (E1) represented by the general formula (I), the phosphorous acid esters (E2) represented by the general formula (II), and the general formulas (III) to (VI) ) Organophosphate metal salts represented by (E3). Hereinafter, these will be described.

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

（一般式（ＩＩ）中、Ｒ’はアルキル基またはアリール基であり、それぞれ同一であっても異なっていてもよい。）

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

（一般式（ＩＩＩ）中、Ｒ^１〜Ｒ^４はアルキル基またはアリール基であり、それぞれ同一であっても異なっていてもよい。Ｍはアルカリ土類金属および亜鉛より選ばれる金属を表す。）

(In the general formula (III), R ^{1 to} R ⁴ are an alkyl group or an aryl group, and may be the same or different. 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であり、それぞれ同一であっても異なっていてもよい。Ｍ’は３価の金属イオンとなる金属原子を表す。）

(In general formula (V), R ^{6 to} R ¹¹ are an alkyl group or an aryl group, and may be the same or different. 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、それぞれ
同一であっても異なっていてもよい。Ｍ’は３価の金属イオンとなる金属原子を表し、２つのＭ’はそれぞれ同一であっても異なっていてもよい。）

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

Phosphate esters (E1);
The phosphate ester (E1) used as the phosphorus compound (E) 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 is an alkyl group or an aryl group, and may be the same or different. N represents an integer of 0 to 2.)

  In the general formula (I), R represents an alkyl group or an aryl group, which may be the same or different. Specifically, an alkyl group having about 1 to 30 carbon atoms, phenyl group, nonylphenyl group, stearylphenyl group, 2,4-di-tert-butylphenyl group, 2,4-di-tert-butyl-methylphenyl Group, tolyl group and the like.

  Among them, the phosphate ester (E1) used in the present invention is preferably a phosphate ester represented by the following general formula (I ′) from the viewpoint of transparency and hue.

O = P (OH) _{n ′} (OR) _{3-n ′} (I ′)
(In the formula, R represents an alkyl group having 2 to 25 carbon atoms, which may be the same or different, and n ^′ represents an integer of 1 and / or 2.)

  In this case, as the alkyl group represented by R in the general formula (I ′), each alkyl such as octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, etc. Groups are preferred.

Phosphite (E2)
Phosphites (E2), which are phosphorus compounds (E) used in the present invention, are phosphites 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であり、それぞれ同一であっても異なっていてもよい。）

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

  Specific examples of the phosphite ester (E2) represented by the general formula (II) include distearyl pentaerythritol diphosphite, dinonylpentaerythritol diphosphite, bisnonylphenylpentaerythritol 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. are 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) are particularly preferable from the viewpoints of transparency, hue, and residence heat stability. -4-Methylphenyl) pentaerythritol diphosphite is preferred.

Organophosphate metal salt (E3);
Organophosphate metal salts (E3), which are phosphorus compounds (E) used in the present invention, are organophosphate metal salts represented by the following general formulas (III) to (VI).

（一般式（ＩＩＩ）中、Ｒ^１〜Ｒ^４はアルキル基またはアリール基であり、それぞれ同一であっても異なっていてもよい。Ｍはアルカリ土類金属および亜鉛より選ばれる金属を表す。）

(In the general formula (III), R ^{1 to} R ⁴ are an alkyl group or an aryl group, and may be the same or different. 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であり、それぞれ同一であっても異なっていてもよい。Ｍ’は３価の金属イオンとなる金属原子を表す。）

(In general formula (V), R ^{6 to} R ¹¹ are an alkyl group or an aryl group, and may be the same or different. 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、それぞれ同一であっても異なっていてもよい。Ｍ’は３価の金属イオンとなる金属原子を表し、２つのＭ’はそれぞれ同一であっても異なっていてもよい。）

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

In the general formulas (III) to (VI) described above, R ^{1 to} R ¹⁴ are alkyl groups or aryl groups, specifically, alkyl groups having about 1 to 30 carbon atoms, phenyl groups, nonylphenyl groups, stearyls. Examples include a phenyl group, 2,4-di-tert-butylphenyl group, 2,4-di-tert-butyl-methylphenyl group, tolyl group and the like. Among these, from the viewpoints of transparency and hue, R ^{1 to} R ¹⁴ are preferably an alkyl group having 2 to 25 carbon atoms, especially 10 to 20, particularly 12 to 20 carbon atoms, specifically octyl, 2-ethylhexyl, isooctyl, nonyl, Examples include alkyl groups such as isononyl, decyl, isodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl and the like.

  Further, M in the general formulas (III) to (VI) is preferably zinc in the case of a divalent metal from the viewpoint of transparency, hue, and thermal stability, and when it becomes a trivalent metal. Is preferably aluminum.

The organophosphate metal salt (E3) used in the present invention is selected from those represented by the above general formulas (III) to (VI), and one kind is used alone or two or more kinds are used in combination. Also good. Among them, a mixture of general formula (III) and general formula (IV) is preferable from the viewpoint of transparency, hue, and residence heat stability, and R ^{1 to} R ⁵ in general formulas (III) and (IV) are the above-described alkyl groups. It is preferable that it is preferable.

  Among them, particularly preferable organophosphate metal salts (E3) used in the present invention include a mixture of mono and distearyl acid phosphate zinc salts and a mixture of mono and distearyl acid phosphate phosphate aluminum salts. These are commercially available as, for example, LBT-1830 and LBT-1813 manufactured by Sakai Chemical Industry.

  Content of the phosphorus type compound (E) in this invention is 0.001-1 weight part with respect to 100 weight part of resin components (C). Especially, it is preferable to use together 0.003-0.3 weight part of (E2) and 0.003-0.3 weight part of (E3) with respect to 100 weight part of resin components (C). When the content of the phosphorus compound is less than 0.001 part by weight, the effect of improving the transparency, hue, and residence heat stability is small, and when it exceeds 1 part by weight, the hue and residence heat stability are lowered.

  In order to further improve the weather resistance, the light diffusing resin composition of the present invention preferably contains an ultraviolet absorber. Among them, as an ultraviolet absorber, in order to achieve both excellent light resistance, hue, and high light transmittance, it is possible to use a malonic acid ester compound, a cyanoacrylate compound, a benzoxazine compound, or a hindered benzoate compound. preferable.

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 transmittance. Examples of the malonic acid ester compounds include 2- (1-arylalkylidene) malonic acid esters, and specifically include PR-25, B-CAP (both manufactured by 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 the hindered benzoate compounds include 3,5-di-t-butyl-4-hydroxybenzoic acid, n-hexadecyl ester, and the like. Specifically, UV-2908 (manufactured by Cytec Industries), etc. Is mentioned. As the ultraviolet absorber used in the present invention, malonic acid esters having a longest absorption wavelength of 300 nm or more and a high ultraviolet absorption effect are particularly preferable.

  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 blending ratio of the UV 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.

  The light diffusing 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 gas, 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).

  The light diffusing resin composition of the present invention may further contain, for example, a mold release agent, an antistatic agent, a colorant, a fluidity improver, a flame retardant, an anti-aggregation agent and the like as necessary.

  The method for producing the light diffusing resin composition of the present invention is arbitrary, and can be obtained by any conventionally known mixing and kneading method. For example, a method applied to any conventionally known thermoplastic resin, specifically, a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single-screw extruder, a twin-screw extruder, a multi-screw extruder, etc. The raw materials may be mixed and kneaded using The temperature condition for kneading is usually 260 to 300 ° C.

  The light diffusing member of the present invention can be obtained from the above-described light diffusing resin composition of the present invention by any conventionally known general thermoplastic resin molding method. Specifically, for example, from the viewpoint of productivity, it is preferable to produce by injection molding, injection compression molding, and extrusion molding from a pellet-shaped resin composition. Furthermore, it can also be set as the target molded object by vacuum forming, pressure forming, etc. from the extruded sheet-like molded product.

  Examples of the light diffusing member molded from the light diffusing resin composition of the present invention include a light guide plate, a diffusion plate, a reflection plate, a protective film, a retardation film, and a lighting cover, a lighting signboard, and a transmission type for a liquid crystal display device. These screens, various displays, and the like can be mentioned, and among them, it can be suitably used as an optical member for a liquid crystal display device.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. Table 1 shows the raw materials used in Examples, Reference Examples and Comparative Examples. In addition, the manufacturing method of resin used for the Example, the reference example, and the comparative example, and the evaluation method of the resin composition in each example and the reference example comparative example are as follows.

(1) Production method of alicyclic polyester resin 1,4-cyclohexanedicarboxylic acid was added to a stainless steel reactor equipped with a stirrer, a distilling tube, a heating device, a pressure gauge, a thermometer and a pressure reducing device, and having a capacity of 100 liters. (Trans isomer: cis isomer ratio is 96: 4) 101.5 parts by weight, 1,4-cyclohexanedimethanol (trans isomer: cis isomer ratio is 69:31) 87 parts by weight and tetra-n-butyl titanate 0.005 part by weight of a 6% by weight butanol solution 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 holding at a temperature of 200 ° C. for 1 hour, the polycondensation reaction is carried out while gradually raising the pressure in the reactor while increasing the temperature from 200 ° C. to 250 ° C. over 45 minutes. It was. The pressure inside the reactor was maintained at an absolute pressure of 0.1 kPa and a reaction temperature of 250 ° C. and maintained for 4.5 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 was 0.841 dl / g.

<Method for measuring intrinsic viscosity>
About 0.25 g of a sample was dissolved in about 25 mL of a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (weight ratio 1/1) to a concentration of 1.00 g / dL, and then 30 Cool and hold at 0 ° C., and measure the number of seconds of dropping only the sample solution and solvent with a concentration of 1.00 × 10 ⁻² g / dL using a fully automatic solution viscometer (“2CH type DJ504” manufactured by Chuo Rika Co., Ltd.) And calculated by the following formula.

IV = ((1 + 4KHη _sp ) _0.5 −1) / (2KHC)

Here, η _sp = η / η ₀ −1, η is the sample solution dropping time, η ₀ is the solvent dropping time, C is the sample solution concentration (g / dL), and KH is the Huggins constant. It is. KH was 0.33, and the dissolution conditions of the sample were 30 minutes at 110 ° C. when the sample was a prepolymer.

(2) Viscosity average molecular weight (Mv): An intrinsic viscosity [η] at 20 ° C. in methylene chloride was measured using an Ubbelohde viscometer, and obtained from the following formula.
[Η] = 1.23 × 10 ⁻⁴ × (Mv) ^0.83

(3) Hue (YI) evaluation:
Each of the above measurements was performed on a plate (90 mm × 50 mm × 3 mm) molded at a temperature of 300 ° C. using an injection molding machine (“J50” manufactured by Nippon Steel Works). For the measurement, a spectroscopic color meter (“SE-2000 type” manufactured by Nippon Denshoku Industries Co., Ltd.) was used.

(4) Izod impact strength:
Measurement was performed in accordance with ASTM D-256 using a test piece of 64 mm × 12.4 mm × 3.2 mm molded at 300 ° C. with an injection molding machine (M150 manufactured by Meiki Seisakusho Co., Ltd.). The measurement was performed with a notch.

(5) Total light transmittance and haze:
The total light transmittance and haze of the test piece molded in (3) were measured with a turbidimeter (NDH-2000 type, manufactured by Nippon Denshoku Industries Co., Ltd.).

(6) Diffusion rate:
Using GP-5 GONIOPHOTOMETER made by MURAKAMI COLOR RESEARCH LABORATORY, the measurement conditions are incident light 0 °, tilt angle 0 °, light receiving range 0 ° to 90 °, light beam aperture 2.0, light receiving aperture 3.0. Then, the luminance of the test piece molded in (3) was measured, and the diffusivity (%) was obtained by the following formula.

  Diffusivity (%) = {(20 ° luminance + 70 ° luminance) / (5 ° luminance) × 2} × 100

(Examples 1 to 4, Reference Examples 1 to 6 and Comparative Examples 1 to 8)
After blending each raw material in the ratios shown in Tables 2 and 3, melt-kneaded at a cylinder temperature of 250 ° C. with a single screw extruder with a screw diameter of 40 mm (“VS-40” manufactured by Tanabe Plastics Machinery Co., Ltd.) Pellets were obtained by cutting, and the obtained pellets were dried at 120 ° C. for 5 to 7 hours with a hot-air circulating dryer, and then a molded article for evaluation was molded under the above conditions. And it evaluated by the method mentioned above and the result was shown in Table 2 and Table 3.

Claims (4)

A light diffusing resin composition comprising an aromatic polycarbonate resin (A), an alicyclic polyester resin (B), and fine particles (excluding a mesoporous inorganic filler) (D), wherein the fine particle (however, a mesoporous inorganic filler is added) The weight average diameter of (D) is 0.7 to 30 μm, and the content thereof 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 0.05-20 weight part with respect to 100 weight part of resin components (C) which consists of further, Phosphite ester (E2) represented by general formula ( II) is 100 weight of resin component (C). 0.003 to 0.3 parts by weight relative to parts , an organophosphate metal salt represented by the following general formula (III) and an organophosphate metal salt represented by the following general formula (IV) (E3) The resin composition (C), characterized in that it comprises 0.003 to 0.3 parts by weight per 100 parts by weight, the light diffusing resin composition.

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

(In the general formula (III), R ^{1 to} R ⁴ are each an alkyl group having 2 to 25 carbon atoms and may be the same or different. M represents a metal selected from an alkaline earth metal and zinc. To express.)

(In general formula (IV), R ⁵ represents an alkyl group having 2 to 25 carbon atoms , and M represents a metal selected from an alkaline earth metal and zinc.) The light diffusion according to claim 1, further comprising 0.001 to 1 part by weight of a phosphate ester (E1) represented by the following general formula (I) with respect to 100 parts by weight of the resin component (C). Resin composition.
O = P (OH) _n (OR) _3-n ... (I)
(In general formula (I), R is a C2-C25 alkyl group, and may be the same or different. N represents an integer of 0-2.) The alicyclic polyester resin (B) is composed of an alicyclic dicarboxylic acid unit mainly composed of a 1,4-cyclohexanedicarboxylic acid component and an alicyclic diol unit mainly composed of 1,4-cyclohexanedimethanol. The light-diffusing resin composition according to claim 1 or 2, wherein Light diffusing member obtained by molding the light diffusing resin composition according to any one of claims 1 to 3.