JP2008222787A - Resin composition and resin molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition having an excellent transparency, hue, flowability, impact resistance, moist heat resistance, residence heat stability and light resistance in good balance. <P>SOLUTION: The resin composition comprises 100 pts.wt. of the total of 1-99 pts.wt. of an aromatic polycarbonate resin and 1-99 pts.wt. of an alicyclic polyester resin, 0.001-1 pt.wt. of a specific organophosphate ester compound and 0.01-5 pts.wt. of an organic ultraviolet light absorber containing no phenolic OH groups. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin composition and a resin molded body, and more specifically, a resin excellent in fluidity, transparency, hue, impact resistance, moist heat resistance and light resistance mainly composed of an aromatic polycarbonate and an alicyclic polyester resin. The present invention relates to a composition and a resin molded body.

  Aromatic polycarbonate resin is excellent in transparency, impact resistance, heat resistance, dimensional stability, etc. As general-purpose engineering plastic, various parts such as electric, electronic, OA equipment, other equipment and machines, automobiles It is used in a wide range of fields such as automotive exteriors and automotive exterior parts.

  However, aromatic polycarbonate resins have the problem of high melt viscosity and inferior moldability, and there is a strong demand to improve moldability (fluidity) as the thickness and size of molded products increase. It has been. Furthermore, aromatic polycarbonate resins have the problem of yellowing when exposed to light such as sunlight for a long time, and have been used to improve light resistance by adding UV absorbers, but further light resistance There was a need for improvement. Moreover, there also existed a problem that it was inferior to chemical resistance, and there existed a restriction | limiting in the use in the use which contacts a solvent.

  Aromatic polycarbonate resins are used in various optical components because of their excellent transparency. However, in recent years, further improvement in transparency (total light transmittance) has been required depending on the application. In particular, in applications where high luminance such as a light guide plate is required, the luminance is remarkably improved only by improving the transmittance at a level of 0.1%. It has become. However, the higher the transparency, the more difficult it is to improve the transmittance by a level of 0.1%. In general, blending with a bluing agent is performed, but the transmittance is lowered by blending the bluing agent. That is, in order to obtain a molded product with a clear feeling, it is required to improve the transmittance.

  As a means to improve the fluidity of aromatic polycarbonate resin, it has been proposed to polymerize aromatic polycarbonate resin with acrylonitrile / butadiene / styrene resin (ABS resin) or acrylonitrile / styrene resin (AS resin). It has become.

  As a means of improving the chemical resistance of aromatic polycarbonate resins, it has been proposed to polymerize aromatic polycarbonate resins with thermoplastic aromatic polyester resins such as polybutylene terephthalate resins and polyethylene terephthalate resins. It has been put into practical use.

  However, since the polymer alloys obtained by the methods as described above are all opaque, it is difficult to use them in applications that require transparency.

  As a means for solving the above problems, a transparent material comprising an aromatic polycarbonate resin and a poly (1,4-cyclohexanedimethanol-1,4-cyclohexanedicarboxylate) resin (hereinafter abbreviated as “PCC resin”) is used. Polymer alloys have been proposed (Patent Documents 1 and 2). Furthermore, it is said that it is preferable to prevent coloring by using a catalyst deactivator for such a polymer alloy. As the catalyst deactivator, acidic phosphate, phosphite having one or more acidic hydrogen, Group IB or IIB metal phosphates, phosphorus oxoacids and acid pyrophosphate metal salts have been proposed (Patent Documents 1 and 2). Furthermore, as a resin composition with improved light resistance, a composition containing at least one UV absorber based on polycarbonate, alicyclic polyester resin, benzotriazole, benzophenone and triazine and a catalyst inhibitor (Patent Document 3) is provided. The same catalyst deactivation agents as disclosed above are exemplified.

  However, when an ultraviolet absorber containing a phenolic OH group such as benzotriazole, benzophenone, or triazine is blended, the initial hue is not always satisfactory, and the use as an optical component is limited. Furthermore, the catalyst deactivator described above is not necessarily satisfactory in transparency and hue when an ultraviolet absorber is blended, and there is a problem that the heat and moisture resistance and the residence heat stability are deteriorated. There was a strong demand.

  In addition, it is known that an organic ultraviolet absorber containing no phenolic OH group is blended with an aromatic polycarbonate resin (for example, Patent Documents 4 and 5), but blended with an aromatic polycarbonate resin-alicyclic polyester resin. It is not yet known about the excellent balance of transparency, hue, impact resistance, moist heat resistance, residence heat stability, and light resistance.

  On the other hand, a resin composition containing a specific organic phosphite compound has been proposed in order to prevent coloring of a polymer blend composed of a polycarbonate resin and a polyester resin and to improve thermal stability (Patent Document 6), and a specific phosphate compound was added. A resin composition has been proposed (Patent Document 7). However, the above resin composition is intended for an aromatic polyester mainly composed of terephthalic acid, and the exemplified resin composition is opaque, and contains a specific phosphorus compound and an ultraviolet absorber. There is no suggestion that a blended resin composition having excellent transparency and hue can be obtained. Furthermore, nothing is mentioned about the point which is excellent in the balance of transparency, hue, impact resistance, moist heat resistance, residence heat stability, and light resistance.

  In addition, a resin composition excellent in impact resistance composed of a polycarbonate resin, an ABS resin, and a phosphoric acid ester metal salt has been proposed (Patent Document 8), and a crystallization speed containing a thermoplastic polyester resin and an organic phosphoric acid ester metal salt is proposed. An improved resin composition has been proposed (Patent Document 9). However, nothing is mentioned about the balance of transparency, hue, impact resistance, moist heat resistance, residence heat stability, and light resistance in a resin composition of an aromatic polycarbonate, an alicyclic polyester resin, and an ultraviolet absorber.

Special Table 2002-517538 JP 2003-176401 A JP 11-130955 A JP 2003-253140 A JP-A-2005-241815 Japanese Unexamined Patent Publication No. 3-977752 JP-A 63-265949 JP-T-2004-509174 JP-A-11-35807

  An object of the present invention is to eliminate the above-mentioned drawbacks of the prior art and to provide a resin composition excellent in balance with respect to fluidity, transparency, hue, impact resistance, moist heat resistance and light resistance.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have obtained an organic ultraviolet absorber that does not contain an aromatic polycarbonate resin, an alicyclic polyester resin, a specific organic phosphate compound, and a phenolic OH group. It has been found that the resin composition comprising the above has excellent balance in transparency, hue, fluidity, impact resistance, moist heat resistance, residence heat stability and light resistance, and has completed the present invention.

  That is, the first gist of the present invention is the following general formulas (1), (2), and 1 to 99 parts by weight of the aromatic polycarbonate resin and 1 to 99 parts by weight of the alicyclic polyester resin. 0.001 to 1 part by weight of an organic phosphate compound selected from the group consisting of (3), (4) and the organic phosphate compound represented by the following general formula (5) and phenolic OH The present invention resides in a resin composition comprising 0.01 to 5 parts by weight of an organic ultraviolet absorber containing no group.

(In the general formula (1), 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.)

(In the general formula (2), R ⁵ is an alkyl group or an aryl group, and M represents a metal selected from an alkaline earth metal and zinc.)

(In General Formula (3), 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.)

(In General Formula (4), 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 general formula (5), R is an alkyl group or an aryl group, and may be the same or different. N represents an integer of 0 to 2.)

  And the 2nd summary of this invention exists in the resin molding which consists of said resin composition.

  The resin composition according to the present invention has a good balance of fluidity, transparency, hue, impact resistance, moist heat resistance and light resistance.

  Hereinafter, the present invention will be described in detail. However, the description of the constituent elements described below is a representative example of embodiments of the present invention, and the present invention is not limited to these contents. In the present specification, the “group” of various compounds may have a substituent without departing from the spirit of the present invention.

  First, the essential components and optional components used in the present invention will be described.

<Aromatic polycarbonate resin (component A)>
The aromatic polycarbonate resin used in the present invention is obtained by using an aromatic dihydroxy compound and a carbonate precursor as raw materials, or using a small amount of a polyhydroxy compound in combination therewith, and is linear or branched. It is a thermoplastic polymer or copolymer.

  Examples of the aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane (= tetra Bromobisphenol 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) propane, 2,2-bis ( , 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-trichloropropane, 2,2-bis (4 -Hydroxyphenyl) -1,1,1,3,3,3-hexachloropropane, bis such as 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane And (hydroxyaryl) alkanes.

  Moreover, as aromatic dihydroxy compounds other than the above, for example, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy) Bis (hydroxyaryl) cycloalkanes exemplified by phenyl) -3,3,5-trimethylcyclohexane and the like; 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3- Cardo structure-containing bisphenols exemplified by methylphenyl) fluorene; dihydroxydiaryl ethers exemplified by 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether; '-Dihydroxydiphenyl sulfide, 4,4'-dihydride Dihydroxy diaryl sulfides exemplified by xy-3,3′-dimethyldiphenyl sulfide; dihydroxy exemplified by 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, etc. Diaryl sulfoxides; dihydroxy diaryl sulfones exemplified by 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone, etc .; hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, etc. Is mentioned.

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

  Examples of the carbonate precursor include carbonyl halide, carbonate ester, haloformate, and the like. Specific examples thereof include phosgene; diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl such as dimethyl carbonate and diethyl carbonate. Carbonates; dihaloformates of dihydric phenols and the like. Two or more of these carbonate precursors may be used in combination.

  The aromatic polycarbonate resin used in the present invention 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, In addition to polyhydroxy compounds such as 1,1,1-tri (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chloroisatin, 5,7 -Dichloro isatin, 5-bromo isatin and the like. Of these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferred. The polyfunctional aromatic compound can be used by substituting a part of the aromatic dihydroxy compound, and the amount used is usually 0.01 to 10 mol%, preferably based on the aromatic dihydroxy compound. 0.1 to 2 mol%.

  Examples of the method for producing the aromatic polycarbonate resin 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. Industrially, an interfacial polymerization method or a melt transesterification method is advantageous, and typical examples of these two methods will be described below.

  The reaction by the interfacial polymerization method can be performed, for example, as follows. First, in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, the pH is usually maintained at 9 or higher, and the aromatic dihydroxy compound and phosgene are reacted. At this time, if necessary, a molecular weight modifier (terminal terminator) or an antioxidant of an aromatic dihydroxy compound can be present in the reaction system. Next, a polymerization catalyst such as tertiary amine or quaternary ammonium salt is added to carry out interfacial polymerization.

  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. Moreover, as an alkali compound used for preparation of aqueous alkali solution, alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, are mentioned.

  Examples of the molecular weight regulator include compounds having a monovalent phenolic hydroxyl group, and specific examples thereof include m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol. , P-long chain alkyl-substituted phenol and the like. The usage-amount of a molecular weight regulator is 0.5-50 mol normally with respect to 100 mol of aromatic dihydroxy compounds, Preferably it is 1-30 mol.

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

  The temperature of the phosgenation reaction is usually 0 to 40 ° C., and the reaction time is several minutes (for example, 10 minutes) to several hours (for example, 6 hours). Further, the addition timing of the molecular weight regulator can be appropriately selected between the phosgenation reaction and the start of the polymerization reaction.

  The reaction by the melt transesterification method is performed, for example, by an ester exchange 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. Among these, diphenyl carbonate or substituted diphenyl carbonate is preferable, and diphenyl carbonate is particularly preferable.

  In general, a transesterification catalyst is used in the melt transesterification process. 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 may be used in combination. The temperature of the transesterification reaction is usually 100 to 320 ° C. Then, the subsequent melt polycondensation reaction is finally performed under reduced pressure of 2 mmHg or less while removing byproducts such as aromatic hydroxy compounds.

  The melt polycondensation can be performed by either a batch method or a continuous method, but it is preferably performed by a continuous method. As the catalyst deactivator used in the melt transesterification method, it is preferable to use a compound that neutralizes the transesterification reaction catalyst, for example, a sulfur-containing acidic compound or a derivative formed therefrom. The used amount (addition amount) of the catalyst deactivator is usually 0.5 to 10 equivalents, preferably 1 to 5 equivalents with respect to the alkali metal contained in the catalyst, and usually 1 to 100 ppm with respect to the aromatic polycarbonate. , Preferably 1 to 20 ppm.

  In addition, the terminal hydroxyl group amount of the aromatic polycarbonate resin that greatly affects the thermal stability, hydrolysis stability, color tone and the like of the resin can be appropriately adjusted by any conventionally known method. In the case of the melt transesterification method, an aromatic polycarbonate having a desired molecular weight and terminal hydroxyl group can be obtained by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound and the degree of pressure reduction during the melt polycondensation reaction. . In the case of the melt transesterification method, the ratio of the carbonic acid diester to 1 mol of the aromatic dihydroxy compound is usually an equimolar amount or more, preferably 1.01 to 1.30 mol. As a method for positively adjusting the amount of terminal hydroxyl groups, there may be mentioned a method in which a terminal terminator is added separately during the reaction. Examples of the terminal terminator include monohydric phenols, monovalent carboxylic acids, and carbonic acid diesters.

  The molecular weight of the aromatic polycarbonate resin used in the present invention is usually 10,000 to 50, as viscosity average molecular weight [Mv] converted from solution viscosity, from the viewpoint of mechanical strength and fluidity (ease of moldability). 000, preferably 12,000 to 40,000, more preferably 14,000 to 30,000. Moreover, you may mix 2 or more types of aromatic polycarbonate resin from which a viscosity average molecular weight differs. Furthermore, you may mix the aromatic polycarbonate resin whose viscosity average molecular weight is outside said suitable range as needed.

  Here, the viscosity average molecular weight [Mv] is obtained by using methylene chloride as a solvent, using an Ubbelohde viscometer, and determining the intrinsic viscosity [η] (unit dl / g) at a temperature of 20 ° C. : Means a value calculated from the equation of η = 1.23 × 10 −4 M0.83. Here, the intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity [ηsp] at each solution concentration [C] (g / dl).

  The terminal hydroxyl group concentration of the aromatic polycarbonate resin used in the present invention is usually 1000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. In addition, the lower limit is 10 ppm, preferably 30 ppm, more preferably 40 ppm, particularly for an aromatic polycarbonate resin produced by a transesterification method. By setting the terminal hydroxyl group concentration in the range of 10 ppm or more, a decrease in molecular weight can be suppressed, and the mechanical properties of the resin composition tend to be further improved. Moreover, it exists in the tendency which the residence heat stability and color tone of a resin composition improve more by making the terminal group hydroxyl group density | concentration into the range which does not exceed 1000 ppm.

  The unit of the terminal hydroxyl group concentration is the weight of the terminal hydroxyl group expressed in ppm relative to the weight of the aromatic polycarbonate resin, and the measuring method is a colorimetric determination (Macromol. Chem. 88 215) by the titanium tetrachloride / acetic acid method. (Method of (1965)).

  In addition, the aromatic polycarbonate resin used 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 usually 1,500 to 9,500, preferably 2,000 to 9,000. The amount of the aromatic polycarbonate oligomer used is usually 30% by weight or less based on the aromatic polycarbonate resin.

  Furthermore, in the present invention, not only virgin resins but also aromatic polycarbonate resins regenerated from used products, so-called material recycled aromatic polycarbonate resins, may be used as the aromatic polycarbonate resin. Used products include, for example, 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, etc.・ Construction materials such as corrugated sheet. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used. The ratio of the recycled aromatic polycarbonate resin is usually 80% by weight or less, preferably 50% by weight or less based on the virgin resin.

<Alicyclic polyester resin (component B)>
The alicyclic polyester resin used in the present invention is obtained by esterifying or transesterifying a dicarboxylic acid component, a diol component and, if necessary, another small amount of components, and then polycondensation reaction. The dicarboxylic acid component is mainly composed of an alicyclic dicarboxylic acid or an ester-forming derivative thereof, and the diol component is mainly composed of an alicyclic diol. Here, the “main component” means that it is usually at least 80 mol%, preferably at least 90 mol%, respectively, relative to the dicarboxylic acid component or diol component. When the alicyclic dicarboxylic acid (or its ester-forming derivative) and the alicyclic diol are less than 80 mol%, the compatibility with the aromatic polycarbonate resin is inferior, the transparency is deteriorated, and the heat resistance is further inferior.

  Specific examples of the alicyclic dicarboxylic acid or its ester-forming derivative include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-decahydronaphthalenedicarboxylic acid. 1,5-decahydronaphthalenedicarboxylic acid, 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 preferred.

  When 1,4-cyclohexanedicarboxylic acid is used, the ratio of the trans form to the cis form is usually 80/20 to 100/0, preferably 85/15 to 100/0, more preferably 90/10 to 100. / 0. By satisfying such conditions, the heat resistance of the resulting alicyclic polyester resin is enhanced.

  Other dicarboxylic acid components that can be used in the present invention include aromatic dicarboxylic acids and aliphatic dicarboxylic acids. Specifically, terephthalic acid, phthalic acid, isophthalic acid, phenylenedioxycarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, 4,4′-diphenylketonedicarboxylic acid, 4, Aromatic dicarboxylic acids such as 4'-diphenoxyethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, glutanic acid, adipic acid, pimelic acid, suberic acid, azelaic acid , Sebacic acid, undecadicarboxylic acid, dodecadicarboxylic acid, and alkyl esters or halides having 1 to 4 carbon atoms.

  As the alicyclic diol, a 5-membered or 6-membered alicyclic diol is preferable from the viewpoint of heat resistance of the obtained polyester resin. Specific examples of such alicyclic diols include 5 such as 1,2-cyclopentanedimethanol, 1,3-cyclopentanedimethanol, bis (hydroxymethyl) tricyclo, and [5.2.1.0] decane. Membered diol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2 , 2-bis (4-hydroxycyclohexyl) -propane and other 6-membered ring diols. Among these, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol are preferable, and 1,4-cyclohexanedimethanol is more preferable. 1,4-Cyclohexanedimethanol is highly reactive due to the methylol group in the para position, and it is easy to obtain a polyester having a high polymerization degree, and a polyester resin having a high glass transition temperature is obtained. There is an advantage of being. The ratio of 1,4-cyclohexanedimethanol in the trans form and the cis form is usually 60/40 to 100/0.

  Other diol components that can be used in the present invention include aliphatic diols and aromatic diols. Specifically, aliphatic diols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4′-hydroxyphenyl) propane , Aromatic diols such as bis (4-hydroxyphenyl) sulfone and bis (4-β-hydroxyethoxyphenyl) sulfonic acid.

  The alicyclic polyester resin 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. 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, tricarbaric acid, trimellitic acid, trimesic acid, pyromellitic acid, naphthalenetetracarboxylic acid, gallic acid, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol And trifunctional or higher polyfunctional components such as sugar ester. These components are used in a proportion of 10 mol% or less in the alicyclic polyester resin.

  The use ratio of the dicarboxylic acid component and the diol component in the esterification reaction or transesterification reaction is as follows. That is, the total amount of the diol component is usually 1 to 2 times the molar ratio with respect to 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, the molar ratio is 1 to 1.2 times.

  In the esterification or transesterification reaction and the polycondensation reaction, it is preferable to use a catalyst in order to obtain a sufficient reaction rate. The catalyst is not particularly limited as long as it is a catalyst used in ordinary esterification or transesterification reaction, and widely known catalysts can be adopted. Specific examples include titanium compounds, germanium compounds, antimony compounds, tin compounds, and the like. Of these, titanium compounds are preferred because of their high activity in both the esterification or transesterification reaction and the subsequent polycondensation reaction. Specific examples of the titanium compound include tetra-n-propyl titanate, tetra-iso-propyl titanate, tetra-n-butyl titanate, and hydrolysates of these organic titanates. You may use these in combination of 2 or more types. Moreover, you may combine with a magnesium compound, a phosphorus compound, etc. as needed. The usage-amount of a catalyst is 1-2000 ppm normally with respect to the produced | generated alicyclic polyester resin, Preferably it is 10-1000 ppm.

  The intrinsic viscosity of the alicyclic polyester resin is usually 0.4 to 1.5 dl / g, preferably 0.5 to 1.3 dl / g, from the viewpoint of mechanical strength and fluidity. Further, 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 an 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 is usually 50 eq / t or less, preferably 30 eq / t or less, and more preferably 20 eq / t or less. When the terminal carboxylic acid concentration is too high, the hydrolyzability (moisture heat resistance) decreases.

  The melting point of the alicyclic polyester resin is, for example, in the case of an alicyclic polyester resin mainly composed of 1,4-cyclohexanedicarboxylic acid as a dicarboxylic acid component and 1,4-cyclohexanedimethanol as a diol component. Usually, it is 200-250 degreeC, Preferably it is 210-230 degreeC, More preferably, it is 215-230 degreeC.

<Organic Phosphate Ester Compound (Component C)>
The organophosphate compound used in the present invention is selected from the group consisting of the following general formulas (1), (2), (3), (4) and the following general formula (5). It is an organic phosphate compound that is at least one selected, and two or more types of organic phosphate compounds of general formulas (1) to (5) may be used in combination.

(In the general formula (1), 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.)

(In the general formula (2), R ⁵ is an alkyl group or an aryl group, and M represents a metal selected from an alkaline earth metal and zinc.)

(In General Formula (3), 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.)

(In General Formula (4), 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 general formula (5), 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 formulas (1) to (4), 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 transparency and / or hue, each of R ^{1 to} R ¹⁴ is preferably an alkyl group having 2 to 25 carbon atoms, and includes an octyl group, a 2-ethylhexyl group, an isooctyl group, and a 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 the general formulas (1) to (2), M is preferably zinc. In general formulas (3) to (4), M ′ is preferably aluminum.

  In general formula (5), R is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, more preferably an alkyl group having 2 to 25 carbon atoms, a phenyl group, Nonylphenyl group, stearylphenyl group, 2,4-di-tert-butylphenyl group, 2,4-di-tert-butyl-methylphenyl group, and tolyl group.

  From the viewpoint of further improving transparency and / or hue, an organic phosphate represented by the following general formula (II) is preferred.

  In general formula (II), R ″ is an alkyl group having 2 to 25 carbon atoms, and may be the same or different. n ′ is 1 or 2. Here, examples of the alkyl group include 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, octadecyl group and the like. Can be mentioned.

The organic phosphate compound is preferably a mixture of the organic phosphate compound represented by the general formula (1) and the organic phosphate compound represented by the general formula (2), more preferably the general formula. In (1) and (2), R ^{1 to} R ⁵ are each an alkyl group having 2 to 25 carbon atoms, and particularly preferably, in the general formulas (1) and (2), M is zinc. Furthermore, the ratio of the organic phosphate compound represented by the general formula (1) and the organic phosphate compound represented by the general formula (2) is preferably 1/9 to 9/1.

  Specific examples of the organic phosphate compound include a mixture of a zinc salt of monostearyl acid phosphate and a zinc salt of distearyl acid phosphate, a mixture of an aluminum salt of monostearyl acid phosphate and an aluminum salt of distearyl acid phosphate. It is done. Such preferable organic phosphate compounds are commercially available as “LBT-1830” and “LBT-1813” manufactured by Sakai Chemical Industry, and “JP-518Zn” manufactured by Johoku Chemical Industry.

<Organic UV absorber (component D)>
The organic ultraviolet absorber used in the present invention is an organic ultraviolet absorber that does not contain a phenolic OH group, and any known organic compound that has an ultraviolet absorbing ability and does not contain a phenolic OH group. Can be used. The organic ultraviolet absorber not containing a phenolic OH group is preferably at least one selected from the group consisting of a malonic acid ester compound, a cyanoacrylate compound, a benzoxazine compound, and an oxalic acid anilide compound, and more A malonic ester compound and / or a benzoxazine compound are preferable, and a malonic ester compound is most preferable. These organic ultraviolet absorbers may be used alone or in admixture of two or more.

(Malonic acid ester compounds)
As the malonic acid ester compound used in the present invention, any conventionally known malonic acid ester compound can be used. Among them, 2- (alkylidene) malonic acid esters, particularly 2- (1-arylalkylidene) malon, can be used. Acid esters are preferred from the viewpoint of the initial hue of the resin composition. As the 2- (1-arylalkylidene) malonic acid esters used in the present invention, those represented by the following general formula (A) are preferable.

(In formula (A), X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, or an alkenyl group having 2 to 10 carbon atoms, which may have a substituent, and R _e And R _f each independently represents an alkyl group having 1 to 6 carbon atoms.)

  In the formula (A), X is preferably a hydrogen atom, an alkyl group, an alkoxy group, or an alkenyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. The alkyl group in the alkyl group or alkoxy group represented by X may be linear or branched, and specifically includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, Examples include n-butyl group, i-butyl group, s-butyl group, t-butyl group.

  Moreover, as an alkenyl group, what has an ester group as a substituent is preferable, and the carbon number is 3-10 including the carbon number in a substituent, Preferably it is 4-8. Among these, X itself is preferably a 2- (alkylidene) malonic acid ester which is a malonic acid ester moiety of the above general formula (A), and among them, the same mainly with respect to the benzene ring of the general formula (A). Those having malonic acid ester residues, particularly those having these in the para position are preferred.

In formula (A), R _e and R _f are each preferably an alkyl group having 1 to 4 carbon atoms. The alkyl groups represented by R _e and R _f may be linear or branched, and specifically include methyl, ethyl, n-propyl, i-propyl, n -Butyl group, i-butyl group, s-butyl group, t-butyl group and the like are mentioned. It is more preferable that R _e and R _f are each a methyl group.

  Specific examples of such malonic ester compounds include PR-25 and B-CAP manufactured by Clariant.

(Cyanoacrylate compound)
In the present invention, any conventionally known cyanoacrylate compound can be used. Specific examples thereof include 2-ethyl-2-cyano-3,3-diphenylacrylate, methyl-2-cyano-3,3- Diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, 1,3-bis- [2′-cyano-3,3′-diphenylacryloyloxy] -2,2-bis-[(2- Cyano-3 ′, 3′-diphenylacryloyl) oxy] methylpropane and the like, among which 2-ethyl-2-cyano-3,3-diphenyl acrylate, 1,3-bis- [2′-cyano-3, 3′-diphenylacryloyloxy] -2,2-bis-[(2-cyano-3 ′, 3′-diphenylacryloyl) oxy] methylpropane is preferred, Preferably, 1,3-bis- [2′-cyano-3,3′-diphenylacryloyloxy] -2,2-bis-[(2-cyano-3 ′, 3′-diphenylacryloyl) oxy] methylpropane is there. Examples of such cyanoacrylate compounds include Uvinul 3030, Uvinul 3035, Uvinul 3039 (all manufactured by BASF), SESORB501 (manufactured by Cypro Kasei Co., Ltd.), SEESORB502 (manufactured by Sipro Kasei Co., Ltd.), and the like.

(Benzoxazine compounds)
In the present invention, any conventionally known benzoxazine-based compound can be used, and specific examples thereof include 2,2′-bis (3,1-benzoxazin-4-one), 2,2′-p- Phenylenebis (3,1-benzoxazin-4-one), 2,2'-m-phenylenebis (3,1-benzoxazin-4-one), 2,2 '-(4,4'-diphenylene) Bis (3,1-benzoxazin-4-one), 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one), 2,2 ′-(1,5- Naphthalene) bis (3,1-benzoxazin-4-one), 2,2 ′-(2-methyl-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2 ′-( 2-Nitro-p-phenylene) bis (3,1-benzoxazin-4-one) 2,2 ′-(2-chloro-p-phenylene) bis (3,1-benzoxazin-4-one) and the like, among others, 2,2′-p-phenylenebis (3,1-benzoxazine- 4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazin-4-one) and 2,2 ′-(2,6-naphthalene) bis (3,1- Benzoxazin-4-one) is preferred, and 2,2′-p-phenylenebis (3,1-benzoxazin-4-one) is particularly preferred. Examples of such benzoxazine compounds include CEi-P (trade name) from Takemoto Yushi Co., Ltd. and CYASORB UV-3638 (trade name) from CYTEC.

(Succinic acid anilide compounds)
In the present invention, any conventionally known oxalic acid anilide compound can be used, and specific examples thereof include 2-ethoxy-2′-ethyl succinic acid bisanilide, 2-ethoxy-5-tert-butyl-2′-ethyl. Succinic acid bisanilide, 2-ethoxy-3'-dodecyl succinic acid bisanilide, etc. are mentioned, and 2-ethoxy-2'-ethyl succinic acid bisanilide is preferable. Examples of such oxalic acid anilide compounds include Clariant Sandubore VSU.

<Phosphorous ester compound (component E)>
In the present invention, a phosphite compound represented by the following general formula (6) can be used.

(In the general formula (6), R ′ is an alkyl group or an aryl group, which may be the same or different.)

  In the general formula (6), 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. Specific examples of the phosphite compound include distearyl pentaerythritol diphosphite, dinonyl pentaerythritol diphosphite, bisnonylphenyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) penta Erythritol 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, and the like.

  Among the above, preferred phosphites are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl). -4-methylphenyl) pentaerythritol diphosphite, more preferably bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4) -Methylphenyl) pentaerythritol diphosphite.

<Phosphonite compound (component F)>
In the present invention, a phosphonite compound represented by the following general formula (7) can be used.

(In General Formula (7), R _a is an aryl group or an arylene group, and R _b is an alkyl group or an aryl group, which may be the same or different.)

  Specific examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,5-di-tert-butylphenyl) -4,4 ′. -Biphenylene diphosphonite, tetrakis (2,3,4-trimethylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,3-dimethyl-5-ethylphenyl) -4,4'-biphenylene diphospho Knight, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butyl-5-ethylphenyl) -4, 4'-biphenylenediphosphonite, tetrakis (2,3,4-tri-butylphenyl) -4,4'-biphenylenedi Suhonaito, tetrakis (2,4,6-tri -tert- butylphenyl) -4,4'-biphenylene phosphonite, and the like. Among these, tetrakis (2,4-di-tert-butyl-phenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4, 4′-biphenylene diphosphonite is preferred.

<Antioxidant>
In the present invention, an antioxidant can be used as an optional component. A preferred antioxidant is a hindered phenolic antioxidant. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5- Di-tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4- Hydroxyphenyl] methyl] phosphoate, 3,3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a, a ', a "-(mesity Len-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4- Hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis ( Octylthio) -1,3,5-triazin-2-ylamino) phenol, etc. Among these, pentaerythritol tetrakis [3- (3,5-di-tert-butyl). 4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, these two phenolic antioxidants are from Ciba Specialty Chemicals. , "Irganox 1010" and "Irganox 1076".

<Release agent>
In the present invention, a release agent can be used as an optional component. A preferred release agent is at least one compound selected from aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, and aliphatic hydrocarbon compounds.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes an alicyclic carboxylic acid. The aliphatic carboxylic acid is preferably a monovalent or divalent carboxylic acid having 6 to 36 carbon atoms, and more preferably an aliphatic saturated monovalent carboxylic acid having 6 to 36 carbon atoms. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, melissic acid, tetrariacontanoic acid, montanic acid, Examples include adipic acid and azelaic acid.

  As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as said aliphatic carboxylic acid can be used. Examples of the alcohol that reacts with the aliphatic carboxylic acid to form an ester include saturated or unsaturated monohydric alcohols and saturated or unsaturated polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. In particular, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic saturated monohydric alcohol or polyhydric alcohol having 30 or less carbon atoms is more preferable. These alcohols may be alicyclic compounds. Specific examples of these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol. Etc. These ester compounds of aliphatic carboxylic acid and alcohol may contain aliphatic carboxylic acid and / or alcohol as impurities, or may be a mixture of a plurality of compounds.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of the aliphatic hydrocarbon include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbon. Moreover, these hydrocarbon compounds may be partially oxidized.

<Dye and pigment>
In the present invention, dyes and pigments can be used as optional components. Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes. Examples of inorganic pigments include, for example, sulfide pigments such as carbon black, cadmium red, and cadmium yellow, silicate pigments such as ultramarine blue, titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, and zinc- Iron-based brown, titanium-cobalt green, cobalt-green, cobalt-blue, oxide-based pigments such as copper-chromium black, copper-iron-based black, chromic pigments such as yellow lead and molybdate orange, and feces such as bitumen For example, Russian. Examples of organic pigments and organic dyes include phthalocyanine dyes and pigments such as copper phthalocyanine blue and copper phthalocyanine green, azo compounds such as nickel azo yellow, thioindigo compounds, perinone compounds, perylene compounds, quinacridone compounds, dioxazine compounds And condensed polycyclic dyes such as isoindolinone compounds and quinophthalone compounds, anthraquinone compounds, heterocyclic compounds, and dyes of methyl compounds.

  In particular, from the viewpoint of thermal stability, titanium oxide, carbon black, cyanine compounds, quinoline compounds, anthraquinone compounds, and phthalocyanine compounds are preferable, and carbon black, anthraquinone compounds, and phthalocyanine compounds are more preferable. Specific examples of these include "MACROLEX Blue RR", "MACROLEX Violet 3R", "MACROLEX Violet B" (manufactured by Bayer), "Sumiplast Violet RR", "Sumlast Violet B", and "SumI Blue". As mentioned above, “Diaresin Violet D, Diaresin Blue G”, “Diaresin Blue N” (above, manufactured by Mitsubishi Chemical Corporation) and the like can be mentioned.

<Heat stabilizer>
In the present invention, a heat stabilizer can be used as an optional component. A preferred heat stabilizer is a phosphite compound. Specific examples of the phosphite compound include trioctyl phosphite, tridecyl phosphite, triphenyl phosphite, trisnonylphenyl phosphite, tris (octylphenyl) phosphite, tris (2,4-di-tert- Butylphenyl) phosphite, tridecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite It is done. Among these, tris (2,4-di-tert-butylphenyl) phosphite is preferable.

<Flame retardant (anti-dripping agent)>
In the present invention, a flame retardant can be used as an optional component. Preferred flame retardants include halogenated bisphenol A polycarbonate, brominated bisphenol epoxy resin, brominated bisphenol phenoxy resin, halogenated flame retardants such as brominated polystyrene, triphenyl phosphate, Resorcinol bis (dixylenyl phosphate), hydroquinone bis (dixylenyl phosphate), 4,4'-biphenol bis (dixylenyl phosphate), bisphenol A bis (dialkyl) Silenyl phosphate), resorcinol bis (diphenyl phosphate), hydroquinone bis (diphenyl phosphate), 4,4'-biphenol bis (diphenyl phosphate), bisphenol A bis Phosphate ester flame retardants such as (diphenyl phosphate), diphenyl sulfone-3,3′- Acid dipotassium, potassium diphenylsulfone-3-sulfonic acid, Pa - organometallic salt-based flame retardants such as fluoro potassium butane sulfonic acid, such as a polyorganosiloxane-based flame retardants and the like.

<Other resins>
In the present invention, as an optional component, polyamide resin, polyimide resin, polyetherimide resin, polyurethane resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyolefin resin (polyethylene resin, polypropylene resin, etc.), styrene resin (polystyrene) Other resins such as polymethacrylate resin, phenol resin, epoxy resin, etc. can be used.

<Other additives>
In the present invention, in addition to the above components, other resins and various resin additives can be used. For example, various resin additives include antistatic agents, antifogging agents, lubricants / antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, fillers / fillers, and the like.

  Next, the resin composition according to the present invention will be described. The resin composition according to the present invention is a specific organophosphate compound 0.001 to 1 part by weight with respect to 100 parts by weight in total of 1 to 99 parts by weight of an aromatic polycarbonate resin and 1 to 99 parts by weight of an alicyclic polyester resin. And 0.01 to 3 parts by weight of an organic ultraviolet absorber not containing a phenolic OH group.

  The use ratio [(A) :( B) weight ratio] of the aromatic polycarbonate resin (component A) and the alicyclic polyester resin (component B) is preferably 30:70 to 93: 7, more preferably 40:60. ˜95: 5, particularly preferably 50:50 to 90:10. When the ratio of the aromatic polycarbonate resin (component A) is too small, the heat resistance and impact resistance are lowered, and when it is too much, the fluidity and chemical resistance are lowered.

  The content of the organic phosphate compound is preferably 0.003 to 0.3 parts by weight, more preferably 0.005 to 0.09, based on 100 parts by weight of the total of the aromatic polycarbonate resin and the alicyclic polyester resin. Parts by weight. When the content of the organic phosphate ester compound is excessive or insufficient, the transparency and / or hue is inferior, and when it is too much, the impact resistance, moist heat resistance and residence heat stability are further deteriorated.

  The content of the organic ultraviolet absorber is preferably 0.03 to 3 parts by weight, more preferably 0.05 to 2 parts by weight, particularly 100 parts by weight in total of the aromatic polycarbonate resin and the alicyclic polyester resin. Preferably it is 0.1-1 weight part. When the content of the UV absorber is excessive or insufficient, the light resistance is inferior, and when it is too much, the color tone such as yellowish color becomes strong, so that the toning property is lowered and it is easy to cause mold deposit.

  The content of the phosphite compound is preferably 0.003 to 0.5 parts by weight, more preferably 0.005 to 0.3 parts per 100 parts by weight of the total of the aromatic polycarbonate resin and the alicyclic polyester resin. Part by weight, particularly preferably 0.01 to 0.1 part by weight. When the content of the phosphite compound is excessive or insufficient, the transparency and / or hue is inferior, and when it is too much, the impact resistance, moist heat resistance and residence heat stability may deteriorate.

  The content of the phosphonite compound is preferably 0.003 to 0.5 parts by weight, more preferably 0.005 to 0.3 parts by weight, based on 100 parts by weight of the total of the aromatic polycarbonate resin and the alicyclic polyester resin. Particularly preferred is 0.01 to 0.1 part by weight. When the content of the phosphonite compound is excessive or insufficient, the transparency and / or hue is inferior, and when it is too much, the impact resistance, moist heat resistance and residence heat stability may deteriorate.

  The compounding amount of the above-mentioned phenolic antioxidant is usually 0.01 to 1 part by weight with respect to 100 parts by weight in total of the aromatic polycarbonate resin and the alicyclic polyester resin. When the amount of the phenolic antioxidant is too small, the effect is not exhibited, and when it is too large, it is not economical.

  The compounding quantity of the above-mentioned mold release agent is 0.01-1 weight part normally with respect to a total of 100 weight part of aromatic polycarbonate resin and alicyclic polyester resin. When the compounding amount of the release agent is too small, the effect is not expressed, and when it is too large, problems such as degradation of hydrolysis resistance and mold contamination during injection molding are caused.

  The amount of the dye / pigment described above is usually 1 part by weight or less, preferably 0.3 parts by weight or less, more preferably 0.1 parts by weight, based on 100 parts by weight of the total of the aromatic polycarbonate resin and the alicyclic polyester resin. It is as follows.

  The blending amount of the aforementioned heat stabilizer is usually 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight with respect to 100 parts by weight of the total of the aromatic polycarbonate resin and the alicyclic polyester resin. . When there is too little content of a heat stabilizer, an effect is not expressed, and when too much, hydrolysis resistance may deteriorate.

  The amount of the flame retardant described above is usually 0.01 to 30 parts by weight, preferably 0.03 to 25 parts by weight, and more preferably 0 to 100 parts by weight in total of the aromatic polycarbonate resin and the alicyclic polyester resin. 0.05 to 20 parts by weight.

  The resin composition of the present invention uses various mixers such as a tumbler and a Henschel mixer, and after previously mixing the above components, a Banbury mixer, a roll, a Brabender, a single-screw kneading extruder, a twin-screw kneading extruder It can be produced by melt kneading with a kneader or the like. Moreover, it is also possible to melt and knead the components without mixing them in advance, or by mixing only a part of the components in advance and supplying them to the extruder with a feeder.

  The resin composition of the present invention can be molded by a method such as injection molding, injection compression molding, injection blow molding, extrusion molding or blow molding. Furthermore, the target molded product can be obtained from the extruded film or sheet-shaped molded product by vacuum molding, pressure molding or the like.

  In addition, in the present invention, from the viewpoint of reducing environmental burden such as waste reduction and cost reduction, when manufacturing molded products from resin compositions, non-conforming products, sprues, runners, used products, etc. are recycled. The raw material can be mixed with the virgin material for recycling, so-called material recycling. At this time, it is preferable to use the recycled raw material because it can be used after being pulverized, since it is possible to reduce inconvenience when the molded product is manufactured. The content ratio of the recycled material is usually 70% by weight or less, preferably 50% by weight or less, and more preferably 30% by weight or less as a ratio in the total 100% by weight of the recycled material and the virgin material.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded. The raw materials used in the following examples are as follows. In the following examples, the blending amount means parts by weight.

<Aromatic polycarbonate resin (component A)>
Aromatic polycarbonate resin (1): Bisphenol A type aromatic polycarbonate ("Iupilon S-3000FN" manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 22,500)
Aromatic polycarbonate resin (2): Bisphenol A type aromatic polycarbonate ("Iupilon E-2000FN" manufactured by Mitsubishi Engineering Plastics, viscosity average molecular weight 28,000)

<Alicyclic polyester resin (component B)>
Alicyclic polyester resin: The alicyclic polyester resin described in Production Example 1 below, intrinsic viscosity 0.957 dl / g, terminal carboxylic acid concentration 12.0 eq / t

<Specific organophosphate compound (component C)>
Organophosphate compound (1): A mixture of zinc salt of monostearyl acid phosphate and zinc salt of distearyl acid phosphate (“LBT-1830” manufactured by Sakai Chemical Industry Co., Ltd.)
Organophosphate compound (2): a mixture of zinc salt of monostearyl acid phosphate and zinc salt of distearyl acid phosphate (“JP-518Zn” manufactured by Johoku Chemical Industry Co., Ltd.)
Organophosphate compound (3): Chemical formula: O = P (OH) _{n ′} (OC ₁₈ H ₃₇ ) _{3-n ′} (mixture of n ′ = 1 and 2, “Adekastab AX-71” manufactured by Asahi Denka Kogyo Co., Ltd. )

<Organic ultraviolet absorber not containing phenolic OH group (component D)>
Malonic ester compound: Malonic ester compound having the following structure ("HOSTAVIN B-CAP" manufactured by Clariant)

Cyanoacrylate compound: 1,3-bis-([2′-cyano-3,3-diphenylacryloyl] oxy) -2,2-bis-([2-cyano-3 ′, 3′-diphenylacrylyl] Oxy) methyl) propane ("UVINUL 3030" manufactured by BASF)
Benzoxazine-based compound: 2,2′-p-phenylenebis (3,1-benzoxazin-4-one) (“CYASORB UV-3638” manufactured by CYTEC)
Succinic acid anilide compound: 2-ethoxy-2′-ethyl succinic acid bisanilide (manufactured by Clariant, “Sanduboa VSU”)

<Ultraviolet absorber containing phenolic OH group (other than component D)>
Benzotriazole compound: 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole ("CYASORB UV-5411" manufactured by CYTEC)

<Phosphorous ester compound (component E)>
Phosphite compound (1): bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite (“Adeka Stub PEP-24G” manufactured by Asahi Denka Kogyo Co., Ltd.)
Phosphite compound (2): bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (“Akastab PEP-36” manufactured by Asahi Denka Kogyo Co., Ltd.)

<Phosphonite compound (component F)>
Phosphonite compound: tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite (“Sand Stub P-EPQ” manufactured by Clariant)

<Phosphorus compounds other than components C and E and component F>
Phosphorous acid (manufactured by Wako Pure Chemical Industries, Ltd.): used as a 45% by weight aqueous solution ADK2112: Tris (2,4-di-tert-butylphenyl) phosphite (“Akastab 2112” manufactured by Asahi Denka Kogyo Co., Ltd.)

<Other ingredients>
Antioxidant: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (“Irganox 1010” manufactured by Ciba Specialty Chemicals)
Mold release agent: Pentaerythritol tetrastearate ("Yunistar H476" manufactured by NOF Corporation)

Production Example 1:
A stainless steel reactor having a capacity of 100 liters equipped with a stirrer, a distilling tube, a heating device, a pressure gauge, a thermometer, and a decompression device was charged with 1,4-cyclohexanedicarboxylic acid (trans isomer: cis cis ratio is 96: 4). 101.5 parts by weight, 1,4-cyclohexanedimethanol (trans isomer: cis ratio is 69:31) 88.6 parts by weight and tetra-n-butyl titanate 6 wt% butanol solution 0.005 parts by weight 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, the esterification reaction was performed by maintaining at 200 ° C. for 1 hour, and then the polycondensation reaction was performed while gradually increasing the pressure in the reactor from 200 ° C. to 250 ° C. over 45 minutes. The polycondensation reaction was carried out for 3.6 hours while maintaining the reactor internal pressure at an absolute pressure of 0.1 kPa and the reaction temperature at 250 ° C. After completion of the polycondensation reaction, the obtained resin was extracted in a strand shape into water, cut and pelletized. Intrinsic viscosity and terminal carboxylic acid concentration were 0.957 dl / g and 12 eq / t, respectively. In addition, these physical property measuring methods are mentioned later.

<Method for measuring intrinsic viscosity>
Using a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (weight ratio 1/1), about 0.25 g of a sample was dissolved so that the concentration was about 1.00 g / dL, and the concentration C (g / DL). This solution is cooled to 30 ° C. and held, and the sample solution dropping time (t) and the solvent only dropping time (t0) are measured with a fully automatic solution viscometer (“2CH type DJ504” manufactured by Sentec Co., Ltd.). Measured and calculated by the following formula.

  In the above equation, “ηsp = t / t0-1”, η is the sample solution drop time, η0 is the solvent drop time, C is the sample solution concentration (g / dL), and KH is Haggins It is a constant. KH adopted 0.33.

<Method for Measuring Terminal Carboxylic Acid Concentration (AV)>
0.4 g of pellets are collected in a test tube, added to 25 ml of benzyl alcohol, and heated and dissolved in an oil bath set at 195 ± 3 ° C. for 7 to 9 minutes. The obtained dissolved solution was allowed to cool to room temperature, 2 ml of ethyl alcohol was added, and 0.01 N sodium hydroxide was used with an automatic titrator (“AUT-501” manufactured by Toa Decay Inc.) using a composite pH electrode. -Titration with benzyl alcohol solution.

  A 0.01N sodium hydroxide / benzyl alcohol solution was prepared and standardized in accordance with JIS K8006, and the factor was calculated. The titration amount was determined from the inflection point of the obtained titration curve, and AV was calculated based on the following formula.

  In the above formula, A is a measurement titer (ml), B is a blank titer (ml), F is a 0.01 N sodium hydroxide / benzyl alcohol solution titer, and W is a pellet weight.

Examples 1-11 and Comparative Examples 1-8:
After each component is uniformly mixed with a tumbler mixer in the ratios shown in Table 1 and Table 2, a twin-screw extruder (“TEX30XCT” manufactured by Nippon Steel Works, L / D = 42, barrel number 12) is used and the cylinder is used. The pellets of the resin composition were prepared by feeding to the extruder from the barrel 1 at a temperature of 270 ° C. and a screw speed of 200 rpm, and melt-kneading.

  After the pellets obtained by the above method were dried at 100 ° C. for 8 hours or longer, an injection molding machine (“M150AII-SJ type” manufactured by Meiki Seisakusho) was used, and the cylinder temperature was 270 ° C., the mold temperature was 70 ° C., ASTM test pieces (3.2 mm thick notched test pieces) and flat plate shaped products (90 mm × 50 mm × 3 mm thickness) were produced under the conditions of a molding cycle of 55 seconds, and the following evaluations were performed. However, for the evaluation of staying heat stability (surface appearance and impact resistance), ASTM test pieces and flat molded products were prepared in the same manner as above except that the molding cycle was changed to 4 minutes, and 5 shots were made. The above-mentioned impact resistance and surface appearance were evaluated by using an ASTM test piece and a flat molded product. The results are shown in Tables 1 and 2.

(1) Fluidity (Q value):
The pellets of the resin composition are dried at 100 ° C. for 8 hours or more, and a high load flow tester is used, and the flow rate Q value (unit) of the resin composition per unit time at 280 ° C. and a load of 160 kgf / cm ^2. : Cc / s) was measured to evaluate the fluidity. An orifice having a diameter of 1 mm and a length of 10 mm was used. The higher the Q value, the better the fluidity.

(2) Transparency:
In accordance with JIS K-7105, the total light transmittance was measured with a “NDH-2000 type” turbidimeter manufactured by Nippon Denshoku Industries Co., Ltd. using the flat plate-shaped product (90 mm × 50 mm × 3 mm thickness) prepared above. . The greater the total light transmittance, the better the transparency.

(3) Hue:
The YI value was measured by the transmission method using the flat plate-shaped product (90 mm × 50 mm × 3 mm thickness) produced above and using a spectroscopic colorimeter (“SE2000 type” manufactured by Nippon Denshoku Industries Co., Ltd.). The smaller the YI value, the better the hue.

(4) Impact resistance (Izod impact strength):
Based on ASTM D256, the ASTM test piece (3.2 mm thick notched test piece) prepared above was used, and the Izod impact strength (unit: J / m) was measured at 23 ° C.

(5) Moist heat resistance:
The pellets of the resin composition were subjected to wet heat treatment at 70 ° C. and 95% RH for 500 hours, and then the outflow amount Q value was measured by the same method as in (1) above. From the Q value before and after the wet heat test, the Q value increase rate was calculated according to the following formula. The smaller the Q value increase rate, the smaller the decrease in molecular weight due to the wet heat test, and the better the heat and moisture resistance.

(6) Stability thermal stability:
(A) Surface appearance:
The surface appearance of the flat plate-shaped product produced above (90 mm × 50 mm × 3 mm thickness) was visually observed and evaluated as “◯” when there was no rough skin due to silver streak, and “×” when there was rough skin due to silver streak.

(B) Impact resistance (Izod impact strength):
The ASTM test piece (3.2 mm thick notched test piece) was measured for Izod impact strength (unit: J / m) at 23 ° C. in accordance with ASTM D256.

(7) Light resistance (UV irradiation):
Using the flat molded product (90 mm x 50 mm x 3 mm thickness) prepared above, a weather resistance test by UV irradiation was performed, and the hue (YI value) after the weather resistance test was determined in the same manner as in (3) above. It was measured. As the UV irradiation apparatus, “Super Xenon Weather Meter” manufactured by Suga Test Instruments Co., Ltd. was used. The irradiance at a black panel temperature of 63 ° C., 300-400 nm was 60 W / m ² , and the irradiation time was 500 hours.

(1) The compositions of Examples 1 to 11 contain a specific organic phosphate compound and a specific organic ultraviolet absorber, and have transparency, hue, fluidity, impact resistance, heat and humidity resistance, and residence. Excellent balance in thermal stability and light resistance.

(2) The composition of Comparative Example 1 does not contain an alicyclic polyester resin, and is inferior in transparency, fluidity, and light resistance (hue) as compared with the compositions of Examples.

(3) The compositions of Comparative Examples 2 to 4 do not contain a specific organophosphate compound, and are inferior in transparency, hue, and light resistance (hue) as compared to the compositions of Examples. The compositions of Comparative Examples 2 and 3 are inferior in impact resistance, moist heat resistance and residence heat stability.

(4) The compositions of Comparative Examples 5 to 7 do not contain a specific organophosphate compound (component C) and a specific organic ultraviolet absorber, and are more transparent than the compositions of the examples. In addition, the hue and light resistance (hue) are inferior, and the compositions of Comparative Examples 5 and 6 are inferior in impact resistance, moist heat resistance and residence heat stability.

(5) The composition of Comparative Example 8 does not contain a specific organic ultraviolet absorber, and is inferior in hue and light resistance (hue) as compared with the compositions of Examples.

  The resin composition of the present invention, which is excellent in fluidity, transparency, hue, impact resistance, moist heat resistance and light resistance in a well-balanced manner, is used for optical disks, optical films, lenses, optical communication cables, light emitting device windows, etc. Various optical parts, various covers such as lighting covers, various housings such as PC housings, TV housings, mobile phone housings, electrical / electronic / OA equipment parts such as sensors and switches, headlamp lenses, inner lenses, room lamp lenses, etc. Various automotive parts such as instrument panels and windows, various building materials such as roofing materials, leisure goods such as goggles (underwater glasses) and outdoor sports parts, daily goods such as mechanical pencils, ballpoint pens and toothbrush patterns, bottles and plastics It can be suitably used in a wide range of fields such as various containers such as bags. In particular, it is expected to be used for various optical components that require transparency, hue, and light resistance.

Claims (9)

The following general formulas (1), (2), (3), (4) and the following general formulas are used for a total of 100 parts by weight of 1 to 99 parts by weight of the aromatic polycarbonate resin and 1 to 99 parts by weight of the alicyclic polyester resin. 0.001 to 1 part by weight of an organic phosphate compound which is at least one selected from the group consisting of the organic phosphate compounds represented by (5) and an organic ultraviolet absorber containing no phenolic OH group. A resin composition comprising 01 to 5 parts by weight.
(In the general formula (1), 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.)
(In the general formula (2), R ⁵ is an alkyl group or an aryl group, and M represents a metal selected from an alkaline earth metal and zinc.)
(In General Formula (3), 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.)
(In General Formula (4), 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 general formula (5), R is an alkyl group or an aryl group, and may be the same or different. N represents an integer of 0 to 2.)   The alicyclic polyester resin is a condensate of 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. The resin composition according to Item 1.   The resin composition according to claim 1 or 2, wherein the aromatic polycarbonate resin is 30 to 95 parts by weight and the alicyclic polyester resin is 5 to 70 parts by weight. The phosphite compound represented by the following general formula (6) is contained in an amount of 0.001 to 1 part by weight with respect to a total of 100 parts by weight of the aromatic polycarbonate resin and the alicyclic polyester resin. The resin composition according to any one of the above.
(In the general formula (6), R ′ is an alkyl group or an aryl group, which may be the same or different.) Any one of Claims 1-4 which comprise 0.001-1 weight part of phosphonite compounds represented by following General formula (7) with respect to a total of 100 weight part of aromatic polycarbonate resin and alicyclic polyester resin). A resin composition according to claim 1.
(In General Formula (7), R _a is an aryl group or an arylene group, and R _b is an alkyl group or an aryl group, which may be the same or different.)   The resin according to any one of claims 1 to 5, wherein the organic ultraviolet absorber is at least one selected from the group consisting of a malonic acid ester compound, a cyanoacrylate compound, a benzoxazine compound, and an oxalic acid anilide compound. Composition. The organophosphate compound is a mixture of the organophosphate compound represented by the general formula (1) and the organophosphate compound represented by the general formula (2), and the general formula (1) ) And R ^{1 to} R ⁵ in the general formula (2) are each an alkyl group having 2 to 25 carbon atoms, The resin composition according to claim 1.   The resin composition according to claim 6, wherein the organic ultraviolet absorber is a malonic ester compound.   The resin molding which consists of a resin composition in any one of Claims 1-8.