JP4983427B2 - Thermoplastic resin composition and resin molded product - Google Patents

Description

  The present invention relates to a thermoplastic resin composition comprising an aromatic polycarbonate resin, a polyethylene terephthalate resin, and an organic phosphate compound, and more specifically, fluidity, heat resistance, impact resistance, residence heat stability, chemical resistance, moisture resistance. The present invention relates to a thermoplastic resin composition excellent in heat balance and a resin molded product formed by molding the same.

  Aromatic polycarbonate resin is a general-purpose engineering plastic that excels in transparency, impact resistance, heat resistance, dimensional stability, etc., and its excellent characteristics make it a wide range of parts such as electrical / electronic / OA equipment parts, machine parts, and automotive parts. Used in the field. Furthermore, polymer alloys consisting of aromatic polycarbonate resin and polyester resin improve the chemical resistance and moldability (fluidity), which are the disadvantages of aromatic polycarbonate resin, while taking advantage of the above-mentioned superior features of aromatic polycarbonate resin. This material is used in vehicle interior / exterior parts, various housing members and a wide variety of other fields. In particular, when used for vehicle parts, appearance quality (such as gloss), chemical resistance, and heat-and-moisture resistance are required at a higher level, and materials with excellent balance in physical properties are required.

  In addition, polymer alloys composed of aromatic polycarbonate resin and polyester resin have an excessive transesterification reaction caused by excessive heating during melt-kneading by an extruder or retention in an injection molding machine, resulting in the appearance quality and heat resistance of the molded product. Therefore, there has been a demand for a material that is more excellent in staying heat stability.

  As means for solving the above-mentioned residence heat stability, a resin composition having excellent residence heat stability comprising an aromatic polycarbonate resin and a polyester resin produced in the presence of a germanium polymerization catalyst (see Patent Documents 1 and 2) ) Is proposed, and it is described that the polymerization catalyst used for the production of the polyester resin greatly affects the residence heat stability of the resin composition. However, a polymer alloy comprising a polyester resin produced in the presence of an aromatic polycarbonate resin and a germanium-based polymerization catalyst is not always satisfactory in terms of chemical resistance and moist heat resistance. Furthermore, polyester resins produced in the presence of germanium-based polymerization catalysts are more widely available than polyester resins produced using antimony-based compounds such as antimony trioxide, which is the most widely and commonly used, as a polymerization catalyst. There were also issues with ease and price.

  On the other hand, the resin composition which mix | blended the specific organophosphate compound with the polymer alloy of an aromatic polycarbonate resin and a polyester resin is proposed (patent documents 3-6). However, the above-mentioned patent documents describe fluidity, heat resistance, impact resistance, residence heat stability, chemical resistance, moisture resistance, which are composed of an aromatic polycarbonate resin and a polyethylene terephthalate resin produced using an antimony compound as a polymerization catalyst. It did not disclose an excellent thermoplastic resin composition with good balance in terms of heat.

Japanese Patent Laid-Open No. 51-102043 JP-A-9-143358 Japanese Unexamined Patent Publication No. 3-977752 JP 54-40854 A JP 54-58754 A JP 2007-77208 A

  The present invention has been made in view of the above circumstances, and its purpose is to eliminate the above-mentioned drawbacks of the prior art and to improve fluidity, heat resistance, impact resistance, residence heat stability, chemical resistance, and heat and humidity resistance. An object of the present invention is to provide a thermoplastic resin composition excellent in balance.

  As a result of diligent studies to achieve the above-mentioned problems, the present inventors have found that a specific organophosphate compound in a polymer alloy of a polyethylene phthalate resin produced using an aromatic polycarbonate resin and an antimony compound as a polymerization catalyst. Contains a thermoplastic resin composition (hereinafter simply referred to as “resin composition”) having excellent balance of various resin properties such as fluidity, heat resistance, impact resistance, residence heat stability, chemical resistance, and moist heat resistance. And the present invention has been completed.

  That is, the first gist of the present invention is that an aromatic polycarbonate resin (component A) 40 to 99% by weight and a polyethylene terephthalate resin (component B) 1 to 60% by weight produced using an antimony compound as a polymerization catalyst. (However, the total of component A and component B is 100% by weight), and consists of an organic phosphate compound represented by the following general formulas (1), (2), (3), (4) and (5) It exists in the thermoplastic resin composition which consists of 0.001-3 weight part of organophosphate ester compounds (C component) which is at least 1 type chosen from the group.

In general formula (1), R < ¹ > -R < ⁴ > is an alkyl group or an aryl group, and may be the same or different. M represents a metal selected from alkaline earth metals 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 > -R < ¹¹ > is an alkyl group or an aryl group, and may be the same or different, respectively. M ′ represents a metal atom that becomes a trivalent metal ion.

In general formula (4), R < ¹² > -R < ¹⁴ > is an alkyl group or an aryl group, and may be the same or different, respectively. M ′ represents a metal atom to be a trivalent metal ion, and two M ′ 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 second gist of the present invention resides in a resin molded product formed by molding the above thermoplastic resin composition.

  The thermoplastic resin composition of the present invention is a resin composition having an excellent balance of physical properties that simultaneously satisfies fluidity, heat resistance, impact resistance, residence heat stability, chemical resistance, and wet heat resistance.

  The thermoplastic resin composition of the present invention having such features can be used in a wide range of fields. Electrical / electronic equipment parts, OA equipment, machine parts, vehicle parts, building parts, various containers, leisure goods -It is useful for various applications such as miscellaneous goods, and can be expected to be applied to vehicle exterior / skin parts and vehicle interior parts.

  As vehicle exterior / skin parts, outer door handle, bumper, fender, door panel, trunk lid, front panel, rear panel, roof panel, bonnet, pillar, side molding, garnish, wheel cap, hood bulge, fuel lid, various spoilers, For example, a cowl for a motorbike.

  Examples of vehicle interior parts include an inner door handle, a center panel, an instrument panel, a console box, a luggage floor board, and a display housing for car navigation.

  Hereinafter, the present invention will be described in more detail. In the present specification, “to” means that the numerical values described before and after that are included as the lower limit value and the upper limit value, and the “group” that various compounds have does not depart from the spirit of the present invention. It includes that it may have a substituent.

[1] Aromatic polycarbonate resin (component A):
The aromatic polycarbonate resin used in the present invention (hereinafter sometimes abbreviated as “component A”) uses, as raw materials, an aromatic dihydroxy compound and a carbonate precursor, or a small amount in combination with these. A linear or branched thermoplastic polymer or copolymer obtained by using a polyhydroxy compound.

  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, preferably with respect to the polycarbonate. Is 1-20 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 35,000, and particularly preferably 16,000 to 32,000. 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 700 ppm or less, more preferably 400 ppm or less, and particularly preferably 300 ppm or less. The lower limit is preferably 10 ppm or more, more preferably 20 ppm or more, further 30 ppm or more, and particularly preferably 40 ppm or more. By setting the terminal hydroxyl group concentration to 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 is preferable for the terminal group hydroxyl group concentration to be 1000 ppm or less because the heat resistance and residence heat stability of the resin composition tend to be further improved.

The terminal hydroxyl group unit is the weight of the terminal hydroxyl group expressed in ppm with respect to the weight of the aromatic polycarbonate resin, and the measurement method is 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.

[2] Polyethylene terephthalate resin (component B):
The polyethylene terephthalate resin used in the present invention (hereinafter sometimes abbreviated as “component B”) is a polyester having a structure in which a terephthalic acid unit and an ethylene glycol unit are ester-bonded, and is 50 mol% of the dicarboxylic acid unit. The above is a polymer produced using an antimony compound comprising a terephthalic acid unit and 50 mol% or more of a diol unit comprising an ethylene glycol unit as a polymerization catalyst. And it is preferable that an ethylene terephthalate unit occupies 80 mol% or more of a structural repeating unit, and it is still more preferable to occupy 90 mol% or more. When the ethylene terephthalate unit is less than 80 mol%, the mechanical properties and heat resistance of the polyethylene terephthalate resin are poor.

  The method for producing the polyethylene terephthalate resin of the present invention is arbitrary, but in the presence of a polymerization catalyst for an antimony compound, the dicarboxylic acid component and the diol component are reacted with heating to produce by-produced water or lower alcohol. This is done by discharging the system outside the system. Here, this condensation reaction may be carried out by either a batch or continuous polymerization method, and the degree of polymerization may be increased by solid phase polymerization.

  In the polyethylene terephthalate resin used in the present invention, the dicarboxylic acid component other than terephthalic acid that can be copolymerized is not particularly limited, and any conventionally known one can be used, and the content thereof is dicarboxylic acid component As a ratio in it, it is 20 mol% or less normally, Preferably it is 15 mol% or less, More preferably, it is 10 mol% or less.

  Examples of dicarboxylic acid components other than terephthalic acid include aromatic dicarboxylic acids other than terephthalic acid, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and ester-forming derivatives thereof. Specifically, phthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-benzophenone dicarboxylic acid, 4,4′-diphenoxyethanedicarboxylic acid, 4 , 4'-diphenylsulfone dicarboxylic acid, aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid; 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, alicyclic ring such as 1,4-cyclohexanedicarboxylic acid And dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. These dicarboxylic acid components can be introduced into the polymer backbone as dicarboxylic acids or as dicarboxylic acid derivatives such as dicarboxylic acid esters and dicarboxylic acid halides.

  In the polyethylene terephthalate resin used in the present invention, the diol component other than ethylene glycol that can be copolymerized is not particularly limited, and any conventionally known diol component can be used, and the content thereof is a ratio in the diol component, Usually, it is 20 mol% or less, preferably 15 mol% or less, more preferably 10 mol% or less.

  Examples of diol components other than ethylene glycol include diethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, polypropylene glycol, polytetramethylene glycol, dibutylene glycol, 1,5-pentanediol, neo Aliphatic diols such as pentyl glycol, 1,6-hexanediol, 1,8-octanediol; 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1,4-cyclohexanedi Alicyclic diols such as methylol; aromatic diols such as xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, etc. And the like.

  In the polyethylene terephthalate resin used in the present invention, lactic acid, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, p-β-hydroxyethoxybenzoic acid, etc. Hydroxycarboxylic acid; monofunctional component such as alkoxycarboxylic acid, stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t-butylbenzoic acid, benzoylbenzoic acid, tricarbaric acid, trimellitic acid, trimesic acid, pyromellitic acid, Trifunctional or higher polyfunctional components such as gallic acid, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol and the like can be used as the copolymerization component. Furthermore, polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polyethylene oxide-added bisphenol A, polypropylene oxide-added bisphenol A, polytetrahydrofuran-added bisphenol A, polytetramethylene glycol, etc. It is also possible to partially copolymerize polyalkylene glycol units derived from the polymer chain.

  The feature of the polyethylene terephthalate resin used in the present invention is that an antimony compound is used as a polymerization catalyst. Specific examples of the antimony-based compound include antimony trioxide, antimony acetate, methoxyantimony, sodium antimonate and the like, and antimony trioxide is preferred from the viewpoint of the thermal stability of the resin composition. The content of the antimony compound used as the polymerization catalyst is preferably 50 to 500 ppm, more preferably 100 to 400 ppm as antimony atoms in the polyethylene terephthalate resin, from the viewpoint of residence heat stability of the resin composition and polymerization rate. It is. The content of the antimony atom can be measured by a method such as atomic emission, atomic absorption, Inductively Coupled Pla-sma (ICP) by recovering the metal in the polymer by a method such as wet ashing.

  The intrinsic viscosity of the polyethylene terephthalate resin used in the present invention may be appropriately selected and determined, but is usually 0.5 to 2 dL / g, particularly 0.7 to 1.5 dL / g, particularly 0.95 to 1. It is preferably 3 dL / g. By setting the intrinsic viscosity to 0.5 dL / g or more, particularly 0.95 dL / g or more, mechanical properties, residence heat stability, chemical resistance, and heat-and-moisture resistance tend to be improved in the resin composition of the present invention. And preferred. Conversely, it is preferable that the intrinsic viscosity is less than 2 dL / g, particularly less than 1.3 dL / g, because the fluidity of the resin composition tends to be improved.

  The intrinsic viscosity is a value measured at 30 ° C. using a mixed solvent of phenol / tetrachloroethane (weight ratio 1/1).

  The density | concentration of the terminal carboxyl group of the polyethylene terephthalate resin used for this invention is 1-60microeq / g normally, and it is preferable that it is 3-50microeq / g especially 5-40microeq / g. By setting the terminal carboxyl group to 60 μeq / g or less, the mechanical properties of the resin composition tend to be improved. Conversely, by setting the terminal carboxyl group concentration to 1 μeq / g or more, the heat resistance of the resin composition, It is preferable because the residence heat stability and hue tend to be improved.

  The terminal carboxyl group concentration of the polyethylene terephthalate resin can be determined by dissolving 0.5 g of polyethylene terephthalate resin in 25 mL of benzyl alcohol and titrating with a 0.01 mol / L benzyl alcohol solution of sodium hydroxide. it can.

  Furthermore, the polyethylene terephthalate resin used in the present invention can be not only a virgin raw material but also a polyethylene terephthalate resin regenerated from a used product, that is, a so-called material recycled polyethylene terephthalate resin. Used products include containers, films, sheets, fibers, non-conforming products, sprues, runners, etc., and pulverized products obtained from them or pellets obtained by melting them can also be used. .

[3] Organophosphate compound (component C):
The organic phosphate ester compound (component C) used in the present invention is derived from the organic phosphate ester compounds represented by 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 from the group consisting of the above, and two or more types of organic phosphate compounds of the general formulas (1) to (5) may be used in combination.

In general formula (1), R < ¹ > -R < ⁴ > is an alkyl group or an aryl group, and may be the same or different. M represents a metal selected from alkaline earth metals 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 > -R < ¹¹ > is an alkyl group or an aryl group, and may be the same or different, respectively. M ′ represents a metal atom that becomes a trivalent metal ion.

In general formula (4), R < ¹² > -R < ¹⁴ > is an alkyl group or an aryl group, and may be the same or different, respectively. M ′ represents a metal atom to be a trivalent metal ion, and two M ′ 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 general formulas (1) to (4), R ^{1 to} R ¹⁴ are each preferably an alkyl group having 1 to 30 carbon atoms or a C 1-30 alkyl group from the viewpoint of further improving the residence heat stability, chemical resistance, and heat and moisture resistance. An aryl group having 6 to 30 carbon atoms, more preferably an alkyl group having 2 to 25 carbon atoms, and particularly preferably an alkyl group having 6 to 23 carbon atoms. Further, from the viewpoint of further improving the residence heat stability, chemical resistance, and moist heat resistance, M in general formulas (1) to (2) is preferably zinc, and in general formulas (3) to (4). M ′ is preferably aluminum.

  In general formula (5), R is preferably an alkyl group having 2 to 25 carbon atoms from the viewpoint of further improving the residence heat stability, chemical resistance, and moist heat resistance. May be different. n is 1 or 2. Here, examples of the alkyl group include an 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 an organic phosphate compound represented by the general formula (1) and the organic compound represented by the general formula (2) from the viewpoint of further improving the thermal stability of residence. A mixture of phosphate ester compounds and / or an organic phosphate ester compound represented by the above general formula (5), and more preferably represented by the above general formula (1) from the viewpoint of further improving the heat and moisture resistance. It is a mixture of the organic phosphate compound represented by the general formula (2), and more preferably, in the general formulas (1) and (2), R ^{1 to} R ⁵ are each carbon. An alkyl group of 2 to 25, and particularly preferably, M in the general formula (1) and the general formula (2) is zinc.

  Furthermore, from the viewpoint of further improving the residence heat stability, the weight of the mixture of the organic phosphate ester compound represented by the general formula (1) and the organic phosphate ester compound represented by the general formula (2) The ratio is preferably 10/90 to 90/10, more preferably 20/80 to 60/40, and particularly preferably 30/70 to 50/50.

  Specific examples of the organic phosphate compound include 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, Examples thereof include a mixture of stearyl acid phosphate and distearyl acid phosphate. Such preferable organic phosphate compounds are commercially available as “LBT-1830” and “LBT-1813” manufactured by Sakai Chemical Industry, “JP-518Zn” manufactured by Johoku Chemical Industry, and “Adekastab AX-71” manufactured by Asahi Denka Kogyo. Yes.

[4] Content ratio:
In the thermoplastic resin composition of the present invention, the content ratio of the A component to the C component constituting the thermoplastic resin composition is 40 to 99 wt% of the aromatic polycarbonate resin (A component) in a total of 100 wt% of the A component and the B component. %, Polyethylene terephthalate resin (component B) 1 to 60% by weight, and the organic phosphate compound (component C) 0.001 to 3 parts by weight with respect to a total of 100 parts by weight of the components A and B.

  In the thermoplastic resin composition of the present invention, among the total of 100% by weight of the A component and the B component, the A component is preferably 51 to 95% by weight, particularly 55 to 90% by weight, and the B component is preferably 5%. It is preferably -49% by weight, particularly preferably 10-45% by weight. When the A component is 40% by weight or more, impact resistance tends to be improved, and when it is less than 99% by weight, fluidity and chemical resistance tend to be improved.

  In addition, the C component is 0.003 to 2 parts by weight, more preferably 0.005 to 1 part by weight, particularly 0.01 to 0.2 parts by weight, with respect to 100 parts by weight of the total of the A component and the B component. preferable. When the content of component C is 0.001 part by weight or more, impact resistance, stagnant heat stability, and chemical resistance tend to be improved, and when it is less than 3 parts by weight, impact resistance and stagnant heat are increased. It tends to improve stability, chemical resistance, and heat and humidity resistance.

[5] Rubber polymer (component D)
The thermoplastic resin composition of the present invention preferably contains a rubber polymer (hereinafter sometimes abbreviated as “D component”) for the purpose of improving impact resistance. The rubbery polymer indicates a glass transition temperature of 0 ° C. or lower, particularly −20 ° C. or lower, and includes a polymer obtained by copolymerizing a rubbery polymer with a monomer component copolymerizable therewith. . As the rubbery polymer used in the present invention, any conventionally known polymer which is generally blended with an aromatic polycarbonate resin and can improve its impact resistance can be used.

  Specific examples of the rubbery polymer include polybutadiene rubber, polyisoprene rubber, polybutyl acrylate, poly (2-ethylhexyl acrylate), polyalkyl acrylate rubber such as butyl acrylate / 2-ethylhexyl acrylate copolymer; polyorganosiloxane rubber In addition to silicone rubber such as butadiene-acrylic composite rubber, IPN composite rubber comprising polyorganosiloxane rubber and polyalkyl acrylate rubber, styrene-butadiene rubber, ethylene-α olefin rubber (ethylene-propylene rubber, ethylene- Butene rubber, ethylene-octene rubber, etc.), ethylene-acrylic rubber, fluorine rubber and the like. Two or more of these may be used in combination. Among these, in terms of impact resistance, any one selected from the group of polybutadiene rubber, polyalkyl acrylate rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, and styrene-butadiene rubber. Species are preferred.

  Specific examples of monomer components copolymerizable with the rubber polymer include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, glycidyl (meth) acrylates, etc. Epoxy group-containing (meth) acrylic acid ester compounds; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid and their An anhydride (for example, maleic anhydride etc.) etc. are mentioned. Two or more of these monomer components may be used in combination. Among these, from the viewpoint of impact resistance, it is preferably any one selected from the group of aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds. Yes, and more preferably a (meth) acrylic acid ester compound. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and the like. It is done.

  The rubbery polymer used in the present invention is preferably of the core / shell type graft copolymer type from the viewpoint of impact resistance. In this case, the core layer is at least one rubber component selected from the group of IPN (interpolating polymer network) type composite rubber composed of polybutadiene-containing rubber, polybutyl acrylate-containing rubber, polyorganosiloxane rubber and polyalkyl acrylate rubber. The shell layer is preferably formed of (meth) acrylic acid ester and acrylonitrile-styrene copolymer.

  Preferred examples of the above core / shell type graft copolymer include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-butadiene copolymer (MB), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer. Polymer (MABS), methyl methacrylate-acrylic rubber copolymer (MA), acrylonitrile-styrene-acrylic rubber copolymer (ASA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic Examples thereof include a butadiene rubber copolymer, a methyl methacrylate-acrylic butadiene rubber-styrene copolymer, and a methyl methacrylate- (acrylic silicone IPN rubber) copolymer. Two or more of these may be used in combination.

  Examples of the above-mentioned core / shell type graft copolymer include “STAPHYLOID MG1011” manufactured by Gantz Kasei Co., Ltd., “PARALLOID EXL2315”, “EXL2602” manufactured by Rohm and Haas Japan Co., Ltd., “ Examples include the EXL series such as EXL2603, the KM series such as “KM330” and “KM336P”, the KCZ series such as “KCZ201”, “Metablene S-2001” and “SRK-200” manufactured by Mitsubishi Rayon Co., Ltd.

  Specific examples of other rubbery polymers include styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene / butylene-styrene block copolymer (SEBS), Examples thereof include styrene-ethylene / propylene-styrene block copolymer (SEPS), acrylonitrile-butadiene rubber-styrene copolymer (ABS), and acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES).

  The content of the rubbery polymer is usually 1 to 40 parts by weight, preferably 2 to 30 parts by weight, more preferably 3 to 25 parts by weight with respect to 100 parts by weight of the total of the aromatic polycarbonate resin and the polyethylene terephthalate resin. . When the content of the rubbery polymer is 1 part by weight or more, impact resistance tends to be improved, and when it is less than 40 parts by weight, rigidity, heat resistance, and moist heat resistance tend to be improved.

[6] Other ingredients:
The thermoplastic resin composition of the present invention may contain other resins and various resin additives in addition to the above components A, B, C, and D as needed, as long as the object of the present invention is not impaired.

  Examples of other resins include acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, styrene resins such as polystyrene resins, polyolefin resins such as polyethylene resins and polypropylene resins, polyamide resins, polyimide resins, and polyethers. Examples include imide resins, polyurethane resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polymethacrylate resins, phenol resins, and epoxy resins.

  Various resin additives include antioxidants, heat stabilizers, mold release agents, dyes and pigments, reinforcing agents, flame retardants, impact resistance improvers, weather resistance improvers, antistatic agents, antifogging agents, and lubricants. -Anti-blocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents and the like. Two or more of these may be used in combination. Hereinafter, an example of an additive suitable for the resin composition of the present invention will be specifically described.

  Examples of the antioxidant include hindered phenolic antioxidants. 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 ′, ''-(Mesitylene-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 and the like. Two or more of these may be used in combination.

  Among the above, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate is preferred. These two phenolic antioxidants are commercially available from Ciba Specialty Chemicals under the names “Irganox 1010” and “Irganox 1076”.

  The content of the antioxidant is usually 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the total of the aromatic polycarbonate resin and the polyethylene terephthalate resin. When the content of the antioxidant is less than 0.001 part by weight, the effect as an antioxidant is insufficient, and when it exceeds 1 part by weight, the effect reaches a peak and is not economical.

  The heat stabilizer used in the present invention includes a phosphite compound (a) in which at least one ester in the molecule is esterified with phenol and / or phenol having at least one alkyl group having 1 to 25 carbon atoms. ), Phosphorous acid (b) and tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylene-di-phosphonite (c).

  Specific examples of the phosphite compound (a) 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, distearyl pentaerythritol diphosphite, diphenylpentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol Rudiphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) penta Examples include erythritol diphosphite and bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite. These may be used alone or in combination of two or more. Among the above, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert) -Butyl-4-methylphenyl) pentaerythritol diphosphite is preferred.

  The content of the heat stabilizer is usually 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the total of the aromatic polycarbonate resin and the polyethylene terephthalate resin. When the content of the heat stabilizer is less than 0.001 part by weight, the effect as the heat stabilizer is insufficient, and when it exceeds 1 part by weight, the hydrolysis resistance may deteriorate.

  The release agent includes at least one compound selected from the group consisting of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000, and polysiloxane silicone oil. can give.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. 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 the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol, the same one as the aliphatic carboxylic acid can be used. On the other hand, examples of the alcohol include saturated or unsaturated monovalent or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, 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. Here, aliphatic includes alicyclic compounds. Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol. Etc.

  In addition, said ester compound may contain aliphatic carboxylic acid and / or alcohol as an impurity, and may be a mixture of a some compound.

  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 having a number average molecular weight of 200 to 15000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, as the aliphatic hydrocarbon, alicyclic hydrocarbon is also included. Moreover, these hydrocarbon compounds may be partially oxidized. Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable. The number average molecular weight is preferably 200 to 5,000. These aliphatic hydrocarbons may be a single substance, or may be a mixture of various constituent components and molecular weights, as long as the main component is within the above range.

  Examples of the polysiloxane silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone. Two or more of these may be used in combination.

  Content of a mold release agent is 0.001-2 weight part normally with respect to a total of 100 weight part of aromatic polycarbonate resin and polyethylene terephthalate resin, Preferably it is 0.01-1 weight part. When the content of the release agent is less than 0.001 part by weight, the effect of the release property may not be sufficient. When the content exceeds 2 parts by weight, the hydrolysis resistance is deteriorated and the mold is contaminated during injection molding. There are problems such as.

  Specific examples of inorganic fillers include glass fillers such as glass fibers (chopped strands), short glass fibers (milled fibers), glass flakes, and glass beads; carbon fillers such as carbon fibers, carbon short fibers, carbon nanotubes, and graphite. ; Whisker such as potassium titanate and aluminum borate; Silicate compounds such as talc, mica, wollastonite, kaolinite, zonotolite, sepiolite, attabargite, montmorillonite, bentonite, smectite; silica, alumina, calcium carbonate, etc. . Among these, glass fiber (chopped strand), glass short fiber (milled fiber), glass flake, talc, mica, wollastonite, and kaolinite are preferable. Two or more of these may be used in combination.

  Content of an inorganic filler is 1-150 weight part normally with respect to a total of 100 weight part of aromatic polycarbonate resin and polyethylene terephthalate resin, Preferably it is 3-100 weight part, More preferably, it is 5-60 weight part. When the content of the inorganic filler is less than 1 part by weight, the reinforcing effect may not be sufficient, and when it exceeds 150 parts by weight, the appearance and impact resistance may be inferior and the fluidity may not be sufficient.

  Specific examples of the ultraviolet absorber include organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, and triazine compounds in addition to inorganic ultraviolet absorbers such as cerium oxide and zinc oxide. Of these, organic ultraviolet absorbers are preferred. In particular, benzotriazole compounds, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2, 4-Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2 ′-(1,4-phenylene) bis [4H-3,1-benzoxazine-4- ON], [(4-methoxyphenyl) -methylene] -propanedioic acid-dimethyl ester is preferred.

  Specific examples of the benzotriazole compound include condensates of methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol. Specific examples of other benzotriazole compounds include 2-bis (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-di-tert-butyl-2′-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy- 3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′-methyl Ren-bis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] [methyl-3- [3-tert-butyl-5- (2H- Benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol] condensate. Two or more of these may be used in combination.

  Of the above, preferably 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl]- 2H-benzotriazole, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2,4 -Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl)- 6- (2N-benzotriazol-2-yl) phenol].

  Content of a ultraviolet absorber is 0.01-3 weight part normally with respect to a total of 100 weight part of aromatic polycarbonate resin and polyethylene terephthalate resin, Preferably it is 0.1-1 weight part. When the content of the ultraviolet absorber is less than 0.01 parts by weight, the effect of improving weather resistance may be insufficient, and when it exceeds 3 parts by weight, problems such as mold deposit may occur.

  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; zinc white, petal, chromium oxide, titanium oxide, iron black, titanium yellow, and zinc- Oxide pigments such as iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black and copper-iron black; chromic pigments such as chrome lead and molybdate orange; Examples include Russian pigments. Examples of organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine, and isoindolinone. And condensed polycyclic dyes such as quinophthalone; anthraquinone, heterocyclic, and methyl dyes and the like. Two or more of these may be used in combination. Among these, carbon black, titanium oxide, cyanine-based, quinoline-based, anthraquinone-based, and phthalocyanine-based compounds are preferable from the viewpoint of thermal stability.

  The content of the dye / pigment is usually 5 parts by weight or less, preferably 3 parts by weight or less, more preferably 2 parts by weight or less with respect to 100 parts by weight of the total of the aromatic polycarbonate resin and the polyethylene terephthalate resin. When the content of the dye / pigment exceeds 5 parts by weight, the impact resistance may not be sufficient.

  Examples of the flame retardant include halogenated bisphenol A polycarbonate, brominated bisphenol epoxy resin, brominated bisphenol phenoxy resin, halogenated flame retardant such as brominated polystyrene, phosphate ester flame retardant, diphenylsulfone-3,3 ′. -Organic metal salt flame retardants such as dipotassium disulfonate, potassium diphenylsulfone-3-sulfonate, potassium perfluorobutanesulfonate, and polyorganosiloxane flame retardants are preferable, but phosphate ester flame retardants are particularly preferable. .

  Specific examples of the phosphate ester flame retardant include triphenyl phosphate, resorcinol bis (dixylenyl phosphate), hydroquinone bis (dixylenyl phosphate), 4,4′-biphenol bis (dixylenyl phosphate), bisphenol A Examples thereof include bis (dixylenyl phosphate), resorcinol bis (diphenyl phosphate), hydroquinone bis (diphenyl phosphate), 4,4′-biphenol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), and the like. Two or more of these may be used in combination. In these, resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) are preferable.

  The content of the flame retardant is usually 1 to 30 parts by weight, preferably 3 to 25 parts by weight, and more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the total of the aromatic polycarbonate resin and the polyethylene terephthalate resin. When the content of the flame retardant is less than 1 part by weight, the flame retardancy may not be sufficient, and when it exceeds 30 parts by weight, the heat resistance may be lowered.

  Examples of the anti-dripping agent include fluorinated polyolefins such as polyfluoroethylene, and polytetrafluoroethylene having fibril forming ability is particularly preferable. This shows the tendency to disperse | distribute easily in a polymer and to couple | bond together polymers and to make a fibrous material. Polytetrafluoroethylene having fibril-forming ability is classified as type 3 according to the ASTM standard. Polytetrafluoroethylene can be used in solid form or in the form of an aqueous dispersion. Examples of polytetrafluoroethylene having fibril-forming ability include “Teflon (registered trademark) 6J” or “Teflon (registered trademark) 30J” from Mitsui DuPont Fluorochemical Co., Ltd. and “Polyflon (trade name) from Daikin Industries, Ltd. Is commercially available.

  The content of the dripping inhibitor is usually 0.02 to 4 parts by weight, preferably 0.03 to 3 parts by weight, based on 100 parts by weight of the total of the aromatic polycarbonate resin and the polyethylene terephthalate resin. When the compounding amount of the dripping inhibitor exceeds 5 parts by weight, the appearance of the molded product may be deteriorated.

[7] Manufacturing method of resin composition and manufacturing method of molded article:
In addition to the components A to C, the resin composition of the present invention can be produced by appropriately selecting a conventionally known arbitrary method for resins, additives, and the like.

  Specifically, for example, after mixing components A to D and additive components blended as necessary using various mixers such as a tumbler and a Henschel mixer, a Banbury mixer, a roll, a Brabender, a single screw kneading extrusion The resin composition can be produced by melt-kneading with a machine, a twin-screw kneading extruder, a kneader or the like. Further, the resin composition can be produced without mixing each component in advance, or by mixing only a part of the components and supplying them to an extruder using a feeder and melt-kneading them.

  The method for producing a molded article from the resin composition of the present invention is not particularly limited, and a molding method generally employed for thermoplastic resins, that is, a general injection molding method, an ultra-high speed injection molding method, an injection Compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, molding method using rapid heating mold, foam molding (including supercritical fluid), insert molding, IMC (In-mold coating molding) A molding method, an extrusion molding method, a sheet molding method, a thermoforming method, a rotational molding method, a lamination molding method, a press molding method, or the like can be employed. Moreover, the shaping | molding method using a hot runner system can also be selected.

  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. In this case, it is preferable to use the recycled raw material because it can be used after being pulverized, since it can reduce problems when producing a molded product. The content ratio of the recycled material is preferably 70% by weight or less, more preferably 50% by weight or less, and further preferably 30% by weight or less, out of a total of 100% by weight of the recycled material and the virgin material.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the following examples and comparative examples, the blending amount means parts by weight.

  In obtaining each resin composition of Examples and Comparative Examples, the following raw materials were prepared.

  <Aromatic polycarbonate resin>

  Aromatic polycarbonate resin (1): Bisphenol A type aromatic polycarbonate produced by interfacial polymerization (“Iupilon E-2000FN” manufactured by Mitsubishi Engineering Plastics, viscosity average molecular weight 28,000, terminal hydroxyl group concentration = 150 ppm)

  Aromatic polycarbonate resin (2): Bisphenol A type aromatic polycarbonate produced by an interfacial polymerization method ("Iupilon S-3000FN" manufactured by Mitsubishi Engineering Plastics, viscosity average molecular weight 21,500, terminal hydroxyl group concentration = 150 ppm)

  <Polyethylene terephthalate resin>

  Polyethylene terephthalate resin (1): Polyethylene terephthalate resin manufactured using antimony trioxide (“Novapex GS900” manufactured by Mitsubishi Chemical Corporation, antimony atom content 230 ppm, intrinsic viscosity 1.07 dL / g, terminal carboxyl group concentration 23 μeq / g )

  Polyethylene terephthalate resin (2): Polyethylene terephthalate resin produced using antimony trioxide (“Novapex GM700” manufactured by Mitsubishi Chemical Corporation, antimony atom content 230 ppm, intrinsic viscosity 0.85 dL / g, terminal carboxyl group concentration 27 μeq / g )

  Polyethylene terephthalate resin (3): Polyethylene terephthalate resin produced using germanium dioxide (“Dianite PA200” manufactured by Mitsubishi Rayon Co., Ltd., germanium atom content 57 ppm, intrinsic viscosity 1.07 dL / g, terminal carboxyl group concentration 12 μeq / g)

  <Organic phosphate compound>

  Organophosphate compound (1): A mixture of zinc salt of distearyl acid phosphate and zinc salt of monostearyl acid phosphate (“JP-518Zn” manufactured by Johoku Chemical Industry Co., Ltd., zinc salt of distearyl acid phosphate and monostearyl acid phosphate) Weight ratio of zinc salt 33/67)

  Organophosphate compound (2): A mixture of zinc salt of distearyl acid phosphate and zinc salt of monostearyl acid phosphate (“LBT-1830” manufactured by Sakai Chemical Industry Co., Ltd., zinc salt of distearyl acid phosphate and monostearyl acid phosphate (Weight ratio of zinc salt 25/75)

  Organophosphate compound (3): Mixture of aluminum salt of distearyl acid phosphate and aluminum salt of monostearyl acid phosphate (“LBT-1813” manufactured by Sakai Chemical Industry Co., Ltd., aluminum salt of distearyl acid phosphate and monostearyl acid phosphate (Weight ratio of aluminum salt 25/75)

  Organophosphate compound (4): Mixture of monostearyl acid phosphate and distearyl acid phosphate ("Adekastab AX-71" manufactured by Asahi Denka Kogyo Co., Ltd.)

  <Rubber polymer>

  Rubber polymer (1): Core / shell type graft copolymer (Rohm and Heart) composed of polybutadiene / polystyrene copolymer (core) / alkyl acrylate / alkyl methacrylate copolymer (shell) "Paraloid KCZ201N" made by Su Japan)

  Rubber polymer (2): Core / shell type graft copolymer comprising polyalkyl acrylate (core) / acrylonitrile-styrene copolymer (shell) ("Staffyroid MG1011" manufactured by Ganz Kasei Co., Ltd.)

  Rubber polymer (3): Core / shell type graft copolymer comprising polybutadiene (core) / alkyl acrylate / alkyl methacrylate copolymer (shell) ("EXL2603" manufactured by Rohm and Haas Japan)

  <Other ingredients>

  Thermal stabilizer: Tris (2,4-di-tert-butylphenyl) phosphite ("Adeka Stub AS2112" manufactured by Asahi Denka Kogyo Co., Ltd.)

  Carbon black: Oil furnace carbon black ("# 1000" manufactured by Mitsubishi Chemical Corporation)

[Preparation of resin composition]
After each component shown in Tables 1 and 2 is uniformly mixed with a tumbler mixer at the ratio shown in Tables 1 and 2, a twin screw extruder (manufactured by Nippon Steel Works, TEX30XCT, L / D = 42, number of barrels) 12) was used to feed the resin composition from the barrel 1 to the extruder at a cylinder temperature of 280 ° C., a screw rotation speed of 200 rpm, and a discharge rate of 20 kg / h, followed by melt-kneading to produce pellets of the resin composition.

[Preparation of test piece]
After the pellets obtained by the above method were dried at 120 ° C. for 6 hours or more, using an injection molding machine (“M150AII-SJ type” manufactured by Meiki Seisakusho), the cylinder temperature was 280 ° C., the mold temperature was 80 ° C., Normal molding was performed under conditions of a molding cycle of 55 seconds, and test specimens (ASTM test specimens and flat molded articles (90 mm × 50 mm × 3 mm thickness)) were produced. Further, stay molding was performed in the same manner as described above except that the molding cycle was changed to 5 minutes, and test pieces (ASTM test pieces and flat plate shaped products (90 mm × 50 mm × 3 mm thickness)) were produced for the fifth and subsequent shots.

[Evaluation method]

(1) Fluidity (Q value):
After drying the resin composition pellets at 110 ° C. for 6 hours or longer, using a high load type flow tester, the effluent Q value per unit time (unit: 280 ° C., load 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. It shows that it is excellent in fluidity | liquidity, so that Q value is high.

(2) Impact resistance (Izod impact strength):
Based on ASTM D256, Izod impact strength (unit: J / m) was measured at 23 ° C. using a notched test piece having a thickness of 3.2 mm.

(3) Heat resistance (thermal deformation temperature):
In accordance with ASTM D648, the heat distortion temperature (unit: ° C.) was measured at 1.8 MPa using a normally molded ASTM test piece.

(4) Stability thermal stability:
(A) Surface appearance; Visual:
The surface appearance of the test piece prepared by the above retention molding is visually observed, ◎ if there is no rough skin due to silver streak, ◯ if there is slight skin rough due to silver streak, and rough skin due to silver streak is remarkable. Things were evaluated as x.

(B) Surface appearance; glossiness:
About the flat molded product produced by said stay molding, glossiness was measured at a measurement angle of 60 ° using a gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd., model VG2000). The greater the glossiness, the better the glossiness.

(C) Heat resistance (thermal deformation temperature):
About the ASTM test piece produced by said residence molding, based on ASTM D648, the heat deformation temperature (unit: ° C) was measured at 1.8 MPa.

(5) Chemical resistance (crack generation degree):
A test chemical was applied to a normally molded ASTM tensile specimen (thickness: 3.2 mm) with a deflection of 1% deformation, and the degree of occurrence of cracks was visually evaluated after 1 hour at room temperature. Commercially available regular gasoline was used as a test chemical. In addition, the crack generation degree was evaluated by the ratio of the number of cracks generated in 10 test pieces.

(6) Moist heat resistance (breaking elongation retention):
A normally molded ASTM tensile test piece (thickness: 3.2 mm) was subjected to a wet heat treatment at 75 ° C. and 95% RH for 1000 hours, and then a tensile test was performed to evaluate the elongation at break for untreated materials.

[Examples 1 to 10, Comparative Examples 1 to 7]
Each resin composition described in Tables 1 and 2 was produced and evaluated by the method described above. The results are shown in Tables 1 and 2.

  From the results shown in Tables 1 and 2, the following can be understood. The resin compositions described in Examples 1 to 10 of the present invention have an excellent balance of fluidity, heat resistance, impact resistance, residence heat stability, chemical resistance, and moist heat resistance.

  On the other hand, since the resin composition described in Comparative Examples 1 and 4 does not contain the C component, it is inferior in heat resistance, residence heat stability, and chemical resistance as compared with the resin compositions of the examples. In addition, the resin compositions of Comparative Examples 2, 3, 5, and 6 have a component B outside the scope of this patent provision, and are inferior in chemical resistance and moist heat resistance as compared with the compositions of the examples.

Claims (9)

40 to 99% by weight of aromatic polycarbonate resin (component A), 1 to 60% by weight of polyethylene terephthalate resin (component B) manufactured using an antimony compound as a polymerization catalyst (however, the sum of component A and component B) Is at least one selected from the group consisting of organophosphate compounds represented by the following general formulas (1), (2), (3), (4) and (5) A thermoplastic resin composition comprising 0.001 to 3 parts by weight of an acid ester compound (component C).

(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 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 / or the general formula (5). And R ^{1 to} R ⁵ and R in the general formula (1), the general formula (2), and the general formula (5) each have 2 to 25 carbon atoms. The thermoplastic resin composition according to claim 1, which is an alkyl group.   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 The thermoplastic resin composition according to claim 2, wherein M in the general formula (2) is zinc.   The blending amount of the aromatic polycarbonate resin (component A) is 55 to 90% by weight, and the blending amount of the polyethylene terephthalate resin (component B) is 10 to 45% by weight (however, the total of the component A and the component B is 100% by weight) The thermoplastic resin composition according to any one of claims 1 to 3.   The thermoplastic resin composition according to any one of claims 1 to 4, wherein the intrinsic viscosity of the polyethylene terephthalate resin is 0.95 to 1.3 dL / g.   The thermoplastic resin composition according to any one of claims 1 to 5, wherein the content of component C is 0.01 to 0.2 parts by weight with respect to 100 parts by weight of the total of component A and component B.   The thermoplastic resin composition according to any one of claims 1 to 6, further comprising 1 to 40 parts by weight of a rubbery polymer (component D) with respect to a total of 100 parts by weight of the aromatic polycarbonate resin and the polyethylene terephthalate resin. .   The thermoplastic resin composition according to claim 7, wherein the rubbery polymer is a core / shell type graft copolymer.   A resin molded product formed by molding the thermoplastic resin composition according to claim 1.