JP2012149272A - Aromatic polycarbonate resin composition, and resin molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin composition well balancedly excellent in fluidity, impact resistance, heat resistance, hue, retaining heat stability, chemical resistance, fatigue characteristics and wet heat resistance.SOLUTION: The aromatic polycarbonate resin composition comprises 51 to 99 wt.% of an aromatic polycarbonate resin (A component), 1 to 49 wt.% of a polybutylene terephthalate resin (B component) (here, the total of the A component and the B component is 100 wt.%), and 0.001 to 3 pts.wt of an organophosphate metal salt (C component) based on 100 pts.wt of the total of the A component and the B component, wherein a titanium compound content in the polybutylene terephthalate resin is >1 ppm and ≤75 ppm in terms of titanium atom; the polybutylene terephthalate resin further contains a group 1 metal compound and/or a group 2 metal compound; and the contents of the group 1 metal compound and/or the group 2 metal compound are >1 ppm and ≤50 ppm in terms of respective metal atoms.

Description

  The present invention relates to an aromatic polycarbonate resin composition comprising an aromatic polycarbonate resin, a polybutylene terephthalate resin, and an organophosphate metal salt, and more specifically, fluidity, impact resistance, heat resistance, hue, residence heat stability, The present invention relates to an aromatic polycarbonate resin composition excellent in balance with respect to chemical resistance, fatigue characteristics, and heat and moisture resistance, 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, a polymer alloy composed of an aromatic polycarbonate resin and a polybutylene terephthalate resin has the chemical resistance and molding processability (fluidity) that are disadvantages of the aromatic polycarbonate resin, while taking advantage of the above-mentioned excellent characteristics of the aromatic polycarbonate resin. It is an improved material and is used in vehicle interior / exterior parts, various housing members and a wide range of other fields. In addition, when used for vehicle parts and the like, appearance quality such as hue, chemical resistance, fatigue characteristics, and heat and humidity resistance are required at a higher level, and materials with excellent balance in physical properties are required. .

  An aromatic polycarbonate resin composition (polymer alloy) mainly composed of an aromatic polycarbonate (PC) resin and a polybutylene terephthalate (PBT) resin is a polymer alloy having a micro-form of sea-island structure, and any resin is a sea phase. Depending on whether the (continuous layer) is formed, the characteristics are also greatly different. In the case where the aromatic polycarbonate resin constitutes a continuous layer (the content of the aromatic polycarbonate resin is higher than that of the polybutylene terephthalate resin), it is more resistant than the polymer alloy having a higher content of polybutylene terephthalate resin. While excellent in impact properties and dimensional characteristics, there are problems that fluidity and chemical resistance are low, and that fatigue properties and heat resistance (thermal deformation temperature) are also low. When such a resin composition is used for vehicle parts, a material having higher fatigue characteristics and higher heat resistance has been demanded.

  Furthermore, in a polymer alloy having a high content of aromatic polycarbonate resin, the ester exchange reaction proceeds excessively due to excessive heating during melt kneading by an extruder or during residence in an injection molding machine, the heat resistance and hue of the molded product, There has been a problem that the impact resistance is lowered, and a material having better residence heat stability has been demanded.

  In addition, it is widely practiced that a polymer alloy of an aromatic polycarbonate resin and a polybutylene terephthalate resin is colored to a desired hue using a dye pigment such as titanium oxide, but a dye pigment such as titanium oxide is blended. As a result, various physical properties such as impact resistance, stagnant heat stability, fatigue characteristics, and moist heat resistance also deteriorated.

  As described above, polymer alloy with polybutylene terephthalate resin, which contains a large amount of aromatic polycarbonate resin, has fluidity, impact resistance, heat resistance, hue, residence heat stability, chemical resistance, fatigue characteristics, and moisture resistance. There was a need for an excellent thermal balance.

  As means for solving the above problems, several techniques of combining a polycarbonate resin and a specific polybutylene terephthalate resin have been proposed. For example, a method for providing a thermoplastic resin composition excellent in chemical resistance and wet heat fatigue resistance by setting the melt viscosity stability index of a polymer alloy of polycarbonate resin and polybutylene terephthalate resin to 2.5% or less has been proposed. (See Patent Document 1). Furthermore, a resin composition excellent in color tone, mechanical properties, thermal stability, chemical resistance, and the like, comprising polybutylene terephthalate having a titanium content of more than 33 ppm and not more than 75 ppm as titanium atoms and an aromatic polycarbonate. It has been proposed (see Patent Document 2). However, improvement by polybutylene terephthalate resin having a specific amount of titanium and a specific phosphorus compound has not yet been suggested, and fluidity, impact resistance, heat resistance, hue, residence heat stability, chemical resistance However, it did not disclose a polymer alloy of an aromatic polycarbonate resin and a polybutylene terephthalate resin excellent in balance with respect to fatigue characteristics and heat-and-moisture resistance.

  On the other hand, as a means for solving the problems of hue and thermal stability, a technique of blending a specific phosphorus compound into a polymer alloy of an aromatic polycarbonate resin and a polyester resin is known (see Patent Documents 3 to 7). . However, fluidity, impact resistance, heat resistance, hue, residence heat stability, chemical resistance can be obtained simply by blending a specific phosphorus compound into a polymer alloy of aromatic polycarbonate resin and polybutylene terephthalate resin. However, it is not always satisfactory in the balance between fatigue characteristics and heat-and-heat resistance, and does not disclose a polymer alloy of an aromatic polycarbonate resin and a polybutylene terephthalate resin, which has an excellent balance of physical properties.

JP 2002-294060 A JP 2006-45533 A Japanese Unexamined Patent Publication No. 3-977752 JP-A 63-265949 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, impact resistance, heat resistance, hue, residence heat stability, chemical resistance, fatigue. An object of the present invention is to provide an aromatic polycarbonate resin composition having a good balance between characteristics and wet heat resistance.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that polybutylene having a specific amount of titanium compound in a polymer alloy of aromatic polycarbonate resin and polybutylene terephthalate resin, which has a large content of aromatic polycarbonate resin. Excellent balance between fluidity, impact resistance, heat resistance, hue, retention thermal stability, chemical resistance, fatigue properties, and heat and humidity resistance by using terephthalate resin and containing specific organophosphate metal salt The present invention has been completed by finding that it is an aromatic polycarbonate resin composition (hereinafter sometimes simply referred to as “resin composition”).

  That is, the first gist of the present invention is that the aromatic polycarbonate resin (component A) 51 to 99% by weight, the polybutylene terephthalate resin (component B) 1 to 49% by weight (however, the sum of the components A and B) Is an aromatic polycarbonate resin composition consisting of 0.001 to 3 parts by weight of an organophosphate metal salt (C component) with respect to 100 parts by weight of the total of A component and B component, The titanium compound content in the polybutylene terephthalate resin is more than 1 ppm and not more than 75 ppm as a titanium atom, and the polybutylene terephthalate resin further contains a Group 1 metal compound and / or a Group 2 metal compound, Alternatively, the content of the Group 2 metal compound is more than 1 ppm and not more than 50 ppm in terms of the metal atom, The aromatic metal salt is at least one selected from the group consisting of organophosphate metal salts represented by the following general formulas (1), (2), (3) and (4) It resides in a polycarbonate resin composition.

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.

  The second gist of the present invention resides in a resin molded product obtained by molding the above aromatic polycarbonate resin composition.

  The aromatic polycarbonate resin composition of the present invention is a resin having an excellent balance of physical properties, which simultaneously satisfies various physical properties such as fluidity, impact resistance, heat resistance, hue, residence heat stability, chemical resistance, fatigue characteristics, and heat and moisture resistance. It is a composition.

  The aromatic polycarbonate resin composition of the present invention having such features can be used in a wide range of fields, such as electric / electronic equipment parts, OA equipment, machine parts, vehicle parts, building members, various containers, leisure It is useful for various applications such as goods and 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.

Example of an esterification reaction step or transesterification step Illustration of an example of polycondensation process Illustration of an example of polycondensation process

  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. 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 M ^0.83 . 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 and fatigue 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] Polybutylene terephthalate resin (component B):
The polybutylene 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 a 1,4-butanediol unit are ester-bonded, and a dicarboxylic acid A polymer in which 50 mol% or more of units are composed of terephthalic acid units and 50 mol% or more of diol units is composed of 1,4-butanediol units, and the content of titanium compound is more than 1 ppm and not more than 75 ppm as titanium atoms. This is a polybutylene terephthalate resin.

  The proportion of terephthalic acid units in all dicarboxylic acid units is preferably 70 mol% or more, more preferably 80 mol% or more, particularly preferably 95 mol% or more, and 1,4-butanediol unit in all diol units. The ratio is preferably 70 mol% or more, more preferably 80 mol% or more, and particularly preferably 95 mol% or more. By setting the terephthalic acid unit or the 1,4-butanediol unit to 50 mol% or more, it is possible to suppress a decrease in the crystallization rate of the polybutylene terephthalate resin and to improve the moldability.

  In the polybutylene terephthalate resin used in the present invention, the dicarboxylic acid component other than terephthalic acid is not particularly limited, and any conventionally known one can be used. Specifically, for example, phthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-benzophenone dicarboxylic acid, 4,4′-diphenoxyethanedicarboxylic acid, Fatty compounds such as aromatic dicarboxylic acids such as 4,4′-diphenylsulfone dicarboxylic acid and 2,6-naphthalenedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid Examples thereof include aliphatic dicarboxylic acids such as cyclic dicarboxylic acid, 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 skeleton as a dicarboxylic acid or using a dicarboxylic acid derivative such as a dicarboxylic acid ester or a dicarboxylic acid halide as a raw material.

  In the polybutylene terephthalate resin used in the present invention, the diol component other than 1,4-butanediol is not particularly limited, and any conventionally known diol component can be used. Specifically, for example, ethylene glycol, diethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, polypropylene glycol, polytetramethylene glycol, dibutylene glycol, 1,5-pentanediol, neopentyl glycol 1,6-hexanediol, 1,8-octanediol and other aliphatic diols, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1,4-cyclohexanedimethylol, etc. Aromatic diols such as alicyclic diol, xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, etc. That.

  In the polybutylene 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. Monofunctional components such as hydroxycarboxylic acid, alkoxycarboxylic acid, stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t-butylbenzoic acid, benzoylbenzoic acid, tricarballylic 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.

  The polybutylene terephthalate resin used in the present invention can be obtained, for example, by polycondensing 1,4-butanediol and terephthalic acid (or dialkyl terephthalate) in the presence of a catalyst such as a titanium compound. The polybutylene terephthalate resin used in the present invention is characterized in that the titanium content is more than 1 ppm and not more than 75 ppm as titanium atoms. This value is the weight ratio of titanium atoms to polybutylene terephthalate resin. The titanium atom content can be measured by recovering the metal in the polymer by a method such as wet ashing and using a method such as atomic emission, atomic absorption, Inductively Coupled Plasma (ICP).

  The lower limit of the titanium content is preferably 1 ppm as titanium atoms, more preferably 10 ppm, more preferably 20 ppm, particularly 25 ppm, and the upper limit is preferably 75 ppm as titanium atoms, especially 50 ppm, especially 45 ppm. If the titanium content is less than 1 ppm as titanium atoms, the polymerization reaction rate of the polybutylene terephthalate resin will decrease, and the polymerization reaction will have to proceed at a high temperature for a long time. Is not only promoted, but also the reaction does not proceed during kneading with the aromatic polycarbonate, and the mechanical properties and fatigue characteristics of the polymer alloy are reduced, which is not preferable.

  On the other hand, if the titanium content exceeds 75 ppm as titanium atoms, not only gas generation during kneading or molding and deterioration of thermal stability will be caused, but control of the transesterification reaction will be difficult, and polymer with aromatic polycarbonate will become difficult. This is not preferable because the heat resistance, residence heat stability and recycling characteristics of the alloy are deteriorated, and the mechanical properties and color tone are lowered.

  The polybutylene terephthalate resin used in the present invention contains a titanium compound as described above, and this titanium compound is preferably a polycondensation catalyst for the polybutylene terephthalate resin. The titanium compound used as the polycondensation catalyst is not particularly limited. Specifically, for example, inorganic titanium compounds such as titanium oxide and titanium tetrachloride; titanium alcoholates such as tetramethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate And the like; and titanium phenolates such as tetraphenyl titanate; Of these, titanium alcoholates are preferable, tetraalkyl titanates are more preferable, and tetrabutyl titanate is particularly preferable.

  The polybutylene terephthalate resin used in the present invention contains a Group 1 metal compound and / or a Group 2 metal compound in addition to the titanium compound. The content of the Group 1 metal compound and / or the Group 2 metal compound in the polybutylene terephthalate resin is preferably more than 1 ppm and 50 ppm or less in terms of metal atoms. In addition, content of a metal atom can be measured similarly to the measuring method of the above-mentioned titanium.

  The lower limit of the content of the Group 1 metal compound and / or the Group 2 metal compound is preferably 3 ppm, particularly 5 ppm, in terms of metal atoms. Further, the upper limit is preferably 50 ppm in terms of the metal atom, more preferably 30 ppm, especially 20 ppm. By setting the content of the Group 1 metal compound and / or the Group 2 metal compound to 1 ppm or more, the mechanical properties and fatigue characteristics of the resin composition tend to be improved, and the Group 1 metal compound and / or the Group 2 metal compound are improved. When the content of is less than 50 ppm, the heat resistance, residence heat stability and hue of the resin composition tend to be improved.

  The polybutylene terephthalate resin used in the present invention contains a Group 1 metal compound and / or a Group 2 metal compound titanium compound as described above. These compounds are polycondensation catalysts for the polybutylene terephthalate resin and titanium compound catalysts. A catalyst is preferred. The group 1 metal compound and / or the group 2 metal compound used as the polycondensation catalyst is not particularly limited. Specifically, for example, the group 1 metal compound is a hydroxide of lithium, sodium, potassium, rubidium, cesium. Oxides; alcoholates; various organic acid salts such as acetates, phosphates and carbonates; Examples of Group 2 metal compounds include hydroxides of beryllium, magnesium, calcium, strontium and barium; oxides; alcoholates; various organic acid salts such as acetates, phosphates and carbonates; Compounds.

  These may be used alone or in combination. Of these, compounds such as lithium, sodium, potassium, magnesium, and calcium are preferable from the viewpoints of handling and availability, and catalytic effects, and magnesium compounds that are excellent in catalytic effect and color tone are more preferable.

  Specific examples of the magnesium compound include magnesium acetate, magnesium hydroxide, magnesium carbonate, magnesium oxide, magnesium alkoxide, and magnesium hydrogen phosphate. Of these, organic acid salts are preferable, and magnesium acetate is particularly preferable.

  The concentration of the terminal carboxyl group of the polybutylene terephthalate resin used in the present invention is preferably 1 to 39 μeq / g, more preferably 5 to 35 μeq / g, and particularly preferably 10 to 30 μeq / g. By setting the terminal carboxyl group to 39 μeq / g or less, the mechanical properties and fatigue characteristics of the resin composition tend to be improved. Conversely, by setting the terminal carboxyl group concentration to 1 μeq / g or more, the resin composition Heat resistance, residence heat stability and hue tend to be improved, which is preferable.

  The terminal carboxyl group concentration of the polybutylene terephthalate resin is obtained by dissolving 0.5 g of polybutylene terephthalate resin in 25 mL of benzyl alcohol and titrating with 0.01 mol / L benzyl alcohol solution of sodium hydroxide. be able to.

  At the end of the polybutylene terephthalate resin, there may be a hydroxyl group and a vinyl group in addition to the carboxyl group, and a methoxycarbonyl group derived from the raw material may remain as the other, particularly when dimethyl terephthalate is used as the raw material. Many may remain.

  In addition, the terminal methoxycarbonyl group in polybutylene terephthalate resin causes toxic methanol, formaldehyde, formic acid, etc. to be generated due to heat generated during molding during resin molding.For example, formic acid is added to metal molding equipment and this. It may affect the associated vacuum related equipment. Therefore, in the polybutylene terephthalate resin used in the present invention, the amount (concentration) of the terminal methoxycarbonyl group is preferably 0.5 μeq / g or less, particularly 0.3 μeq / g or less, more preferably 0.2 μeq / g or less. In particular, it is preferably 0.1 μeq / g or less.

  The terminal vinyl group concentration of the polybutylene terephthalate resin used in the present invention is usually 0.1 to 15 μeq / g, preferably 0.5 to 10 μeq / g, particularly preferably 1 to 8 μeq / g. If the terminal vinyl group concentration is too high, the color tone of the resin composition will be deteriorated, and the terminal vinyl group concentration tends to further increase due to the heat history during molding. In the case of the manufacturing method, the color tone may be further deteriorated.

Each said terminal group density | concentration can be quantified by dissolving a polybutylene terephthalate resin in a mixed solvent of deuterated chloroform / hexafluoroisopropanol = 7/3 (volume ratio) and measuring ¹ H-NMR. At this time, in order to prevent overlap with the solvent signal, a very small amount of a basic component such as heavy pyridine may be added.

  The intrinsic viscosity of the polybutylene terephthalate resin used in the present invention may be appropriately selected and determined, but is usually 0.5 to 2 dL / g, particularly 0.6 to 1.5 dL / g, more preferably 0.8 to 1. .3 dL / g, particularly 0.95 to 1.25 dL / g is preferred. By setting the intrinsic viscosity to 0.5 dL / g or more, the mechanical properties, fatigue properties, and residence heat stability in the resin composition of the present invention tend to be improved. Conversely, by setting the intrinsic viscosity to less than 2 dL / g, 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).

  Furthermore, the polybutylene terephthalate resin used in the present invention can be not only a virgin raw material but also a polybutylene terephthalate resin regenerated from a used product, that is, a so-called material recycled polybutylene 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. .

  Next, the manufacturing method of the polybutylene terephthalate resin used for this invention is demonstrated. The production method of polybutylene terephthalate resin is roughly classified into a so-called direct polymerization method using dicarboxylic acid as a main raw material and a transesterification method using dialkyl dicarboxylate as a main raw material. The former is different in that water is produced in the initial esterification reaction, and the latter is produced in the initial transesterification reaction.

  Moreover, the manufacturing method of polybutylene terephthalate resin is divided roughly into a batch method and a continuous method according to a raw material supply or a polymer discharge form. A method in which the initial esterification reaction or transesterification reaction is performed in a continuous operation, and then the polycondensation to be performed is performed in a batch operation. There is also an operation method.

  The polybutylene terephthalate resin used in the present invention is a polybutylene terephthalate resin produced by a direct polymerization method from the viewpoint of raw material availability, ease of distillate treatment, superiority of raw material units, and effects of the present invention. Is preferably used. In the present invention, from the viewpoint of productivity, stability of product quality, and effects of the present invention, it is preferable to employ a method of continuously supplying raw materials and continuously performing an esterification reaction or transesterification reaction. In particular, it is preferable to produce a polybutylene terephthalate resin by a so-called continuous method in which a polycondensation reaction subsequent to an esterification reaction or a transesterification reaction is also carried out continuously.

  In the method for producing a polybutylene terephthalate resin used in the present invention, at least a portion of 1,4-butanediol is independently produced from terephthalic acid (or dialkyl terephthalate) in the presence of a titanium catalyst in an esterification reaction vessel. A step of continuously esterifying (or transesterifying) terephthalic acid (or dialkyl terephthalate) and 1,4-butanediol while being supplied to the esterification reaction vessel (or transesterification reaction vessel) is preferably employed. .

  That is, as a method for producing the polybutylene terephthalate resin used in the present invention, haze and foreign matters derived from the catalyst are reduced, and the catalytic activity is not lowered. Therefore, the raw material slurry or solution is supplied together with terephthalic acid or dialkyl terephthalate. In addition to 1,4-butanediol, it is preferable to supply 1,4-butanediol to the esterification reactor or transesterification reactor independently of terephthalic acid or dialkyl terephthalate. Hereinafter, the 1,4-butanediol may be referred to as “separately supplied 1,4-butanediol”.

  The “separately supplied 1,4-butanediol” can be filled with fresh 1,4-butanediol independent of the process. "Separately supplied 1,4-butanediol" collects 1,4-butanediol distilled from the esterification reaction tank or transesterification reaction tank with a condenser or the like and holds it as it is or in a temporary tank or the like Then, it can be refluxed to the reaction vessel, or can be supplied as 1,4-butanediol having a purity improved by separating and purifying impurities. Hereinafter, “separately supplied 1,4-butanediol” composed of 1,4-butanediol collected by a condenser or the like may be referred to as “recycled 1,4-butanediol”. From the viewpoint of effective utilization of resources and simplicity of equipment, it is preferable to allocate “recycled 1,4-butanediol” to “separately supplied 1,4-butanediol”.

  In addition, 1,4-butanediol distilled from the esterification reaction tank or transesterification reaction tank usually contains components such as water, alcohol, tetrahydrofuran (THF), dihydrofuran, etc. in addition to the 1,4-butanediol component. Contains. Therefore, after collecting 1,4-butanediol from the above-mentioned distillate with a condenser or the like, it is separated and purified from components such as water, alcohol and THF while being collected and returned to the reaction vessel. Is preferred.

  In the present invention, it is preferable to return 10% by weight or more of “separately supplied 1,4-butanediol” directly to the reaction liquid phase part. Here, the reaction liquid phase part refers to the liquid phase side of the gas-liquid interface in the esterification reaction tank or transesterification reaction tank. To return directly to the reaction liquid phase part, use piping or the like. "Separately supplied 1,4-butanediol" indicates that it is directly supplied to the liquid phase part without going through the gas phase part. The ratio of returning directly to the liquid phase part of the reaction liquid is preferably 30% by weight or more, more preferably 50% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more. When the amount of “separately supplied 1,4-butanediol” returned directly to the reaction liquid phase is small, the titanium catalyst tends to be deactivated.

  Moreover, the temperature of “separately supplied 1,4-butanediol” when returning to the reactor is usually 50 to 220 ° C., preferably 100 to 200 ° C., more preferably 150 to 190 ° C. When the temperature of “separately supplied 1,4-butanediol” is too high, the amount of THF by-product tends to increase, and when it is too low, the heat load tends to increase, leading to energy loss.

  Examples of the polycondensation catalyst for the polybutylene terephthalate resin used in the present invention include the above-described titanium compounds, Group 1 metal compounds and / or Group 2 metal compounds (hereinafter referred to as “titanium catalyst”, “Group 1 metal catalyst”, “ In addition to “Group 2 metal catalyst”, for example, tin and compounds thereof may be mentioned.

  Tin is usually used as a tin compound, specifically, for example, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, cyclohexahexylditin oxide, didodecyltin oxide, triethyltin hydroxide, Triphenyltin hydroxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, tributyltin chloride, dibutyltin sulfide, butylhydroxytin oxide, methylstannic acid, ethylstannic acid, butylstannic acid, etc. Can be mentioned.

  However, in general, tin and tin compounds deteriorate the color tone of the polybutylene terephthalate resin. Therefore, it is preferable that the content of the tin compound in the polybutylene terephthalate resin used in the present invention is low. . Specifically, it is preferable that the content of the tin compound is usually 200 ppm or less, particularly 100 ppm or less, more preferably 10 ppm or less in terms of tin atoms.

  In the production of the polybutylene terephthalate resin used in the present invention, another catalyst can be used as the catalyst. Specifically, for example, antimony compounds such as antimony trioxide; germanium compounds such as germanium dioxide and germanium tetroxide; manganese compounds; zinc compounds; zirconium compounds; cobalt compounds; orthophosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, etc. And phosphorus compounds such as esters and metal salts thereof; and the like.

  In order to prevent deactivation of the catalyst, 10% by weight or more of the titanium catalyst used in the esterification reaction (or transesterification reaction) is placed in the liquid phase of the reaction liquid independently of terephthalic acid (or dialkyl terephthalate). Direct supply is preferred. Here, the reaction liquid phase part indicates the liquid phase side of the gas-liquid interface in the esterification reaction tank or transesterification reaction tank, and the direct supply to the reaction liquid phase part uses a pipe, etc. This means that the catalyst is supplied directly to the liquid phase part without going through the gas phase part of the reactor. The proportion of the titanium catalyst added directly to the reaction liquid phase is preferably 30% by weight or more, more preferably 50% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more.

  The above titanium catalyst can be directly supplied to the reaction liquid phase part of the esterification reaction tank or transesterification reaction tank with or without being dissolved in a solvent or the like. In order to reduce adverse effects such as heat denaturation from the heat medium jacket, it is preferable to dilute with a solvent such as 1,4-butanediol. The concentration at this time is usually 0.01 to 20% by weight, particularly 0.05 to 10% by weight, particularly preferably 0.08 to 8% by weight, as the concentration of the titanium catalyst with respect to the whole solution. From the viewpoint of reducing foreign matter, the water concentration in the solution is usually 0.05 to 1.0% by weight, and the temperature during the preparation of the solution is usually 20 to 150 ° C., particularly from the viewpoint of preventing deactivation and aggregation. It is preferable that it is 30-100 degreeC, especially 40-80 degreeC. In addition, the catalyst solution is preferably mixed with separately supplied 1,4-butanediol and piping and supplied to the esterification reaction tank or the transesterification reaction tank from the viewpoint of preventing deterioration, preventing precipitation, and preventing deactivation.

  The Group 1 metal catalyst and / or the Group 2 metal catalyst can be supplied to the esterification reaction tank or the transesterification reaction tank, but the supply position is not particularly limited, and the reaction is carried out from the reaction gas phase portion of these reaction tanks. You may supply to a liquid upper surface, and you may supply directly to a reaction liquid phase part. At this time, it may be supplied together with the raw material terephthalic acid and the titanium catalyst, or may be supplied independently.

  Among these, from the viewpoint of the stability of the catalyst, it is preferable that the terephthalic acid or the titanium catalyst is supplied to the upper surface of the reaction liquid independently from the reaction liquid gas phase. As a method for supplying the Group 2 metal catalyst, for example, when the Group 2 catalyst is solid at room temperature, it can be supplied to the reaction solution as a solid, but the supply amount is stabilized and adverse effects such as heat denaturation are caused. In order to reduce, it is preferable to dissolve in a solvent such as water or 1,4-butanediol and supply as a solution. The concentration of the Group 2 metal catalyst in this solution is usually 0.01% by weight or more, preferably 0.05% by weight or more, and particularly preferably 0.08% by weight or more, and the upper limit is 20% by weight or less. It is preferably 10% by weight or less, particularly preferably 8% by weight or less.

  Moreover, you may add a group 1 metal catalyst and / or a group 2 metal catalyst to the polycondensation reaction tank following an esterification reaction tank or a transesterification reaction tank, and the oligomer piping attached to it. In this case, the addition method also stabilizes the supply amount and reduces adverse effects such as heat denaturation, such as water, a solvent such as 1,4-butanediol, and a copolymer component such as polytetramethylene ether glycol. It is preferable to melt | dissolve and supply as a solution, and the density | concentration in this case is the same as the above-mentioned solution density | concentration.

  Next, an example of a continuous method employing a direct polymerization method will be described as a method for producing a polybutylene terephthalate resin. First, the dicarboxylic acid component having terephthalic acid as a main component and the diol component having 1,4-butanediol as a main component are mixed in a raw material mixing tank to form a slurry, and in one or a plurality of esterification reaction tanks In the presence of a titanium catalyst, the temperature is usually 180 to 260 ° C., preferably 200 to 245 ° C., more preferably 210 to 235 ° C., and usually 10 to 133 kPa, preferably 13 to 101 kPa, more preferably 60 to 90 kPa. Under the pressure (absolute pressure; the same shall apply hereinafter), usually for 0.5 to 10 hours, preferably 1 to 6 hours, to obtain an oligomer by continuous esterification reaction.

  The oligomer is then transferred to a polycondensation reaction vessel and polycondensed in the presence of a polycondensation catalyst in one or more polycondensation reaction vessels. In this case, it is preferably continuously at a temperature of usually 210 to 280 ° C., preferably 220 to 260 ° C., more preferably 230 to 250 ° C., and usually 20 kPa or less, preferably 10 kPa in at least one polycondensation reaction tank. In the following, the polycondensation reaction is carried out usually under a reduced pressure of 5 kPa or less and with stirring, usually for 2 to 15 hours, preferably 3 to 10 hours. The polymer obtained by the polycondensation reaction is usually transferred from the bottom of the polycondensation reaction tank to a polymer extraction die and extracted in the form of a strand, and while being cooled with water or after being cooled with water, it is cut with a cutter to form pellets and chips. And so on.

  In the case of the direct polymerization method, the molar ratio of terephthalic acid and 1,4-butanediol preferably satisfies the following formula.

  B / TPA = 1.1-5.0 (mol / mol)

  In the above formula, B is the number of moles of 1,4-butanediol supplied from the outside to the esterification reaction tank per unit time, and TPA is the amount of terephthalic acid supplied from the outside to the esterification reaction tank per unit time. The number of moles.

  The above "1,4-butanediol supplied from the outside to the esterification reaction tank" means, as raw material slurry or solution, in addition to 1,4-butanediol supplied together with terephthalic acid or dialkyl terephthalate. Is the total of 1,4-butanediol entering the reaction vessel from outside the reaction vessel, such as 1,4-butanediol supplied independently, 1,4-butanediol used as a solvent for the catalyst.

  When the above B / TPA value is smaller than 1.1, the conversion rate is lowered and the catalyst is deactivated. When the B / TPA value is larger than 5.0, not only the thermal efficiency is lowered but also by-products such as THF are increased. Tend to. The value of B / TPA is preferably 1.5 to 4.5, more preferably 2.0 to 4.0, and particularly preferably 3.1 to 3.8.

  An example of a continuous process employing the transesterification process is as follows. First, in a transesterification reaction tank or tanks, in the presence of a titanium catalyst, usually at a temperature of 110 to 260 ° C., preferably 140 to 245 ° C., more preferably 180 to 220 ° C., usually 10 to 133 kPa, The oligomer is obtained by continuous transesterification under a pressure of preferably 13 to 120 kPa, more preferably 60 to 101 kPa, usually for 0.5 to 5 hours, preferably 1 to 3 hours.

  The oligomer is then transferred to a polycondensation reaction tank, and preferably continuously in the presence of a polycondensation reaction catalyst in one or more polycondensation reaction tanks, usually 210-280 ° C, preferably 220-260 ° C. More preferably, at a temperature of 230 to 250 ° C., in the at least one polycondensation reaction tank, the pressure is usually 20 kPa or less, preferably 10 kPa or less, more preferably 5 kPa or less, with stirring, usually 2 to 15 hours. The polycondensation reaction is preferably performed in 3 to 10 hours.

  In the case of the transesterification method, the molar ratio of dialkyl terephthalate to 1,4-butanediol preferably satisfies the following formula.

  B / DAT = 1.1 to 2.5 (mol / mol)

  In the above formula, B is the number of moles of 1,4-butanediol supplied from the outside to the esterification reaction tank per unit time, and DAT is supplied from the outside to the esterification reaction tank per unit time. Number of moles of dialkyl terephthalate.

  When the B / DAT value is smaller than 1.1, the conversion rate and the catalytic activity are decreased. When the B / DAT value is larger than 2.5, not only the thermal efficiency is decreased, but also by-products such as THF are reduced. It tends to increase. The value of B / DAT is preferably 1.1 to 1.8, more preferably 1.2 to 1.5.

  In the present invention, the esterification reaction or transesterification reaction is preferably performed at a temperature equal to or higher than the boiling point of 1,4-butanediol in order to shorten the reaction time. The boiling point of 1,4-butanediol depends on the reaction pressure, but is 230 ° C. at 101.1 kPa (atmospheric pressure) and 205 ° C. at 50 kPa.

  As the esterification reaction tank or the transesterification reaction tank, any conventionally known one can be used, for example, any type such as a vertical stirring complete mixing tank, a vertical heat convection mixing tank, and a tower type continuous reaction tank. There may be. Also, a single tank may be a plurality of tanks of the same kind or different kinds of tanks in series or in parallel. Among them, a reaction tank having a stirring device is preferable, and as a stirring device, a turbine stator type high-speed rotating stirrer, a disk mill type stirrer, a rotor mill type stirrer in addition to a normal type including a power unit, a bearing, a shaft, and a stirring blade. A type that rotates at high speeds can also be used.

  The form of stirring is not particularly limited, and in addition to the usual stirring method in which the reaction solution in the reaction tank is directly stirred from the top, bottom, side, etc. of the reaction tank, a part of the reaction solution is connected to the reactor by piping. A method of circulating the reaction solution by taking it outside and stirring it with a line mixer or the like can also be employed. Known types of stirring blades can be selected, and specific examples include propeller blades, screw blades, turbine blades, fan turbine blades, disk turbine blades, fiddler blades, full zone blades, and Max blend blades.

  In the production of the polybutylene terephthalate resin, usually, a plurality of reaction vessels are used, preferably 2 to 5 reaction vessels, and the molecular weight is sequentially increased. Usually, a polycondensation reaction is performed following the initial esterification reaction or transesterification reaction.

  The polycondensation reaction step of the polybutylene terephthalate resin may use a single reaction vessel or a plurality of reaction vessels, but preferably uses a plurality of reaction vessels. The form of the reaction tank may be any type such as a vertical stirring complete mixing tank, a vertical heat convection mixing tank, a tower type continuous reaction tank, or the like. Among them, a reaction tank having a stirring device is preferable, and as a stirring device, a turbine stator type high-speed rotating stirrer, a disk mill type stirrer, a rotor mill type stirrer in addition to a normal type including a power unit, a bearing, a shaft, and a stirring blade. A type that rotates at high speeds can also be used.

  The form of stirring is not particularly limited, and in addition to the usual stirring method in which the reaction solution in the reaction tank is directly stirred from the top, bottom, side, etc. of the reaction tank, a part of the reaction solution is connected to the reactor by piping. A method of circulating the reaction solution by taking it outside and stirring it with a line mixer or the like can also be employed. In particular, it is recommended that at least one of the polycondensation reaction tanks use a horizontal reactor having a surface rotation axis in the horizontal direction and excellent self-cleaning properties.

  Moreover, in order to suppress coloring and deterioration, and to suppress the increase in the terminal of vinyl groups and the like, the reaction is usually performed under a high vacuum of 1.3 kPa or less, particularly 0.5 kPa or less, particularly 0.3 kPa or less in at least one reaction vessel. It is preferable. The reaction temperature is usually 225 to 255 ° C, preferably 230 to 250 ° C, particularly 233 to 245 ° C.

  Furthermore, the polycondensation reaction step of the polybutylene terephthalate resin is performed by once producing a polybutylene terephthalate resin having a relatively small molecular weight, for example, an intrinsic viscosity of about 0.1 to 1.0 by melt polycondensation. Solid phase polycondensation (solid phase polymerization) can also be performed at a temperature below the melting point of the butylene terephthalate resin.

  Hereinafter, a preferred embodiment of a method for producing a polybutylene terephthalate resin used in the present invention will be described with reference to the accompanying drawings. FIG. 1 is an explanatory view of an example of an esterification reaction step or transesterification reaction step employed in the present invention, and FIGS. 2 and 3 are explanatory views of an example of a polycondensation step employed in the present invention.

  In FIG. 1, terephthalic acid as a raw material is usually mixed with 1,4-butanediol in a raw material mixing tank (not shown), and supplied to the reaction tank (A) in the form of slurry from the raw material supply line (1). When the raw material is dialkyl terephthalate, it is usually fed to the reaction tank (A) in a molten state. On the other hand, the titanium catalyst is preferably supplied from a catalyst supply line (3) after being made into a solution of 1,4-butanediol in a catalyst adjustment tank (not shown). FIG. 1 shows a mode in which a catalyst supply line (3) is connected to a recycle line (2) for recycle 1,4-butanediol, and both are mixed and then supplied to the liquid phase part of the reaction tank (A). It was.

  The gas distilled from the reaction tank (A) is separated into a high-boiling component and a low-boiling component in the rectifying column (C) through the distillation line (5). Usually, the main component of the high boiling component is 1,4-butanediol, and the main component of the low boiling component is water and THF in the case of the direct polymerization method, and alcohol, THF, and water in the case of the transesterification method. .

  The high-boiling components separated in the rectification column (C) are extracted from the extraction line (6) and partly circulated from the recirculation line (2) to the reaction tank (A) via the pump (D). , Part is returned from the circulation line (7) to the rectification column (C). Further, the surplus is extracted outside from the extraction line (8). On the other hand, the light boiling components separated in the rectification column (C) are extracted from the gas extraction line (9), condensed in the condenser (G), and temporarily passed through the condensate line (10) to the tank (F). Can be stored.

  A part of the light boiling components collected in the tank (F) is returned to the rectification column (C) through the extraction line (11), the pump (E) and the circulation line (12), and the remainder is extracted. It is extracted outside through the line (13). The condenser (G) is connected to an exhaust device (not shown) via a vent line (14). The oligomer produced | generated within the reaction tank (A) is extracted through an extraction pump (B) and an extraction line (4).

  In the process shown in FIG. 1, the catalyst supply line (3) is connected to the recirculation line (2), but both may be independent. Moreover, the raw material supply line (1) may be connected to the liquid phase part of the reaction vessel (A).

  In FIG. 2, the oligomer supplied from the above-described extraction line (4) shown in FIG. 1 is polycondensed under reduced pressure in the first polycondensation reaction tank (a) to become a prepolymer, and then extracted. It supplies to a 2nd polycondensation reaction tank (d) through a gear pump (c) and an extraction line (L1).

  If it is necessary to add Group 1 and / or Group 2 metal catalysts, these catalysts are diluted with a solvent such as 1,4-butanediol in a preparation tank (not shown) and adjusted to a predetermined concentration. Via (L7), it is connected to a 1,4-butanediol supply line (L8), further diluted with 1,4-butanediol, and then supplied to the oligomer extraction line (4). The same applies to FIG.

  In the second polycondensation reactor (d), polycondensation usually proceeds at a lower pressure than that of the first polycondensation reactor (a) to become a polymer. The obtained polymer was extracted in the form of a melted strand from the die head (g) through the extraction gear pump (e) and the extraction line (L3), cooled with water, etc., and then the rotary cutter (h ) To form pellets.

  Further, in FIG. 3, the polymer obtained in the second polycondensation reactor (d) is supplied to the third polycondensation reaction tank (k) via the extraction gear pump (e) and the extraction line (L3). To do. The third polycondensation reaction tank (k) is a horizontal reaction tank composed of a plurality of stirring blade blocks and equipped with a biaxial self-cleaning type stirring blade.

  Usually, in the second polycondensation reaction tank (d), polycondensation proceeds at a lower pressure than in the first polycondensation reaction tank (a), and in the third polycondensation reaction tank (k), polycondensation proceeds further. It becomes a polymer.

  The polymer obtained in the third condensation reactor (k) is withdrawn in the form of a melted strand from the dice head (g) through the extraction gear pump (m) and the extraction line (L5). After being cooled, it is cut with a rotary cutter (h) into pellets.

  Reference numerals (L2), (L4), and (L6) in FIGS. 2 and 3 are vent lines of the respective polycondensation reaction tanks (a), (d), and (k).

[3] Organophosphate metal salt (component C):
The organophosphate metal salt used in the present invention (hereinafter sometimes abbreviated as “C component”) is represented by the following general formulas (1), (2), (3), and (4). An organophosphate metal salt that is at least one selected from the group consisting of organophosphate metal salts, and uses a combination of two or more organophosphate metal salts of general formulas (1) to (4) May be.

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 formulas (1) to (4), R ^{1 to} R ¹⁴ are each preferably carbon from the viewpoint of further improving hue, heat resistance, residence heat stability, chemical resistance, fatigue characteristics, and moist heat resistance. 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, and particularly preferably an alkyl group having 6 to 23 carbon atoms. It is. Further, from the viewpoint of further improving the hue, heat resistance, residence heat stability, chemical resistance, and fatigue characteristics, M in the general formulas (1) to (2) is preferably zinc, and the general formula (3) to (3) M 'in (4) is preferably aluminum.

The organic phosphate metal salt is preferably an organic compound represented by the general formula (1) from the viewpoint of further improving the hue, heat resistance, residence heat stability, chemical resistance, fatigue characteristics, and wet heat resistance. It is a mixture of a phosphoric acid ester metal salt and an organic phosphoric acid ester metal salt represented by the general formula (2). More preferably, in the general formulas (1) and (2), R ^{1 to} R ⁵ are each a carbon number. 2 to 25 alkyl groups, and particularly preferably, M in the general formula (1) and the general formula (2) is zinc. Furthermore, from the viewpoint of further improving the hue, heat resistance, and residence heat stability, the organic phosphoric acid esterified metal salt represented by the general formula (1) and the organic phosphoric acid represented by the general formula (2) The weight ratio of the mixture of ester metal salts 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 metal salt include a mixture of zinc salt of monostearyl acid phosphate and zinc salt of distearyl acid phosphate, a mixture of aluminum salt of monostearyl acid phosphate and aluminum salt of distearyl acid phosphate, etc. Can be mentioned. Such preferable organic phosphoric acid ester metal salts are commercially available as “LBT-1830” and “LBT-1813” manufactured by Sakai Chemical Industry, and “JP-518Zn” manufactured by Johoku Chemical Industry.

[4] Content ratio:
In the aromatic polycarbonate resin composition of the present invention, the content ratio of the component A to component C constituting the aromatic polycarbonate resin (component A) is 51 to 99 in a total of 100% by weight of the component A and component B. % By weight, polybutylene terephthalate resin (component B) 1 to 49% by weight, and based on a total of 100 parts by weight of the components A and B, 0.001 to 3 parts by weight of an organic phosphate metal salt (component C) .

  In the aromatic polycarbonate resin composition of the present invention, among the total 100% by weight of component A and component B, component A is preferably 55 to 90% by weight, especially 60 to 85% by weight, It is preferably 10 to 45% by weight, particularly 15 to 40% by weight. When the A component is 51% 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, heat resistance, hue, residence heat stability, chemical resistance, and fatigue characteristics tend to be improved, and the content is less than 3 parts by weight. As a result, impact resistance, heat resistance, hue, residence heat stability, chemical resistance, fatigue characteristics, and moist heat resistance tend to be improved.

[5] Rubber polymer (component D):
The aromatic polycarbonate resin composition of the present invention preferably contains a rubbery 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 rubber polymer is usually 1 to 40 parts by weight, preferably 2 to 30 parts by weight, and 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 polybutylene terephthalate resin. is there. 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] Titanium oxide (E component):
The aromatic polycarbonate resin composition of the present invention preferably contains titanium oxide (hereinafter sometimes abbreviated as “E component”) for the purpose of coloring a desired hue, and is a resin containing titanium oxide. The effect of the present invention is further manifested in the composition. The content of titanium oxide is usually from 0.01 to 10 parts by weight, preferably from 0.03 to 7 parts by weight, more preferably from 0.05 to 7 parts by weight, based on 100 parts by weight of the total of the aromatic polycarbonate resin and the polybutylene terephthalate resin. 5 parts by weight. If the content of titanium oxide is less than 0.01 parts by weight, the colorability may be inferior, and if it is 10 parts by weight or more, the impact resistance, residence heat stability, fatigue characteristics, and wet heat resistance may be inferior.

  Various titanium oxides can be used as titanium oxide, and the average particle diameter of titanium oxide is usually 0.05 to 0.5 μm. If the average particle size is less than 0.05 μm, the thermal stability and heat-and-moisture resistance are inferior. If it exceeds 0.5 μm, the hue (whiteness) is inferior, and the surface of the molded product is roughened and the impact strength is reduced. Cheap. The average particle diameter of titanium oxide is preferably 0.1 to 0.5 μm, more preferably 0.15 to 0.35 μm.

  The titanium oxide used in the present invention is preferably titanium oxide produced by a chlorine method. Titanium oxide produced by the chlorine method is superior in terms of whiteness and the like compared to titanium oxide produced by the sulfuric acid method. As a crystal form of titanium oxide, rutile type titanium oxide is preferable, which is superior in whiteness as compared with anatase type titanium oxide.

  Further, it is preferable to use titanium oxide that has been surface-treated with an organic compound. Specific examples of the organic compound include an organosilane compound or an organosilicone compound having an alkoxy group, an epoxy group, an amino group, a Si—H bond, etc., preferably a silicone compound having a Si—H bond, and particularly preferred. Is methyl hydrogen polysiloxane.

[7] Other ingredients:
The aromatic polycarbonate resin composition of the present invention contains other resins and various resin additives in addition to the above A, B, C, D and E components as long as they do not impair the purpose of the present invention. Also good.

  Other resins include, for example, polyester resins other than polybutylene terephthalate resins such as polyethylene terephthalate resin and polytrimethylene terephthalate resin, styrene series such as acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, and polystyrene resin. Examples thereof include polyolefin resins such as resins, polyethylene resins, and polypropylene resins, polyamide resins, polyimide resins, polyetherimide 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”.

  Content of antioxidant is 0.001-1 weight part normally with respect to a total of 100 weight part of aromatic polycarbonate resin and polybutylene terephthalate resin, Preferably it is 0.01-0.5 weight part. 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.

  Content of a heat stabilizer is 0.001-1 weight part normally with respect to a total of 100 weight part of aromatic polycarbonate resin and polybutylene terephthalate resin, Preferably it is 0.01-0.5 weight part. 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 polybutylene 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.

  The content of the inorganic filler is usually 1 to 150 parts by weight, preferably 3 to 100 parts by weight, and more preferably 5 to 60 parts by weight with respect to 100 parts by weight as the total of the aromatic polycarbonate resin and the polybutylene terephthalate resin. 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 polybutylene 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 sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; zinc white, petal, chromium oxide, iron black, titanium yellow, and zinc-iron brown. , Titanium Cobalt Green, Cobalt Green, Cobalt Blue, Oxide Pigment such as Copper-Chromium Black, Copper-Iron Black, Chromic Acid Pigment such as Yellow Lead and Molybdate Orange; Ferrocyan Pigment such as Bitumen Is mentioned. 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, 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, and more preferably 2 parts by weight or less based on 100 parts by weight of the total of the aromatic polycarbonate resin and the polybutylene 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 as a total of the aromatic polycarbonate resin and the polybutylene 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 polybutylene terephthalate resin. When the compounding amount of the dripping inhibitor exceeds 5 parts by weight, the appearance of the molded product may be deteriorated.

[8] 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, A to E components and additive components blended as necessary are mixed in advance using various mixers such as a tumbler and a Henschel mixer, and then Banbury mixer, roll, Brabender, 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)

  Aromatic polycarbonate resin (3): Bisphenol A type aromatic polycarbonate produced by an interfacial polymerization method (“Iupilon H-4000FN” manufactured by Mitsubishi Engineering Plastics, viscosity average molecular weight 15,500, terminal hydroxyl group concentration = 150 ppm)

  <Polybutylene terephthalate resin>

PBT-1 (Production Example 1):
Through the esterification step shown in FIG. 1 and the polycondensation step shown in FIG. 3, a polybutylene terephthalate resin was produced in the following manner. First, a 60 ° C. slurry mixed at a ratio of 1.80 moles of 1,4-butanediol with respect to 1.00 moles of terephthalic acid is passed through the raw material supply line (1) from the slurry preparation tank in advance with an esterification rate of 99%. To a reaction vessel (A) for esterification having a screw type stirrer filled with polybutylene terephthalate oligomer was continuously fed to 40.0 kg / h.

  At the same time, the bottom component of the rectification column (C) at 185 ° C. is fed from the recirculation line (2) at 18.4 kg / h, and the catalyst feed line (3) is fed with 6. 5% of tetrabutyl titanate as the catalyst. A 0 wt% 1,4-butanediol solution was fed at 127 g / h (40 ppm relative to the theoretical polymer yield). The water content in this solution was 0.20% by weight.

  The internal temperature of the reaction tank (A) is 230 ° C., the pressure is 78 kPa, and the produced water, THF and excess 1,4-butanediol are distilled from the distillation line (5), and the rectification column (C) It separated into a high boiling component and a low boiling component. The high-boiling component at the bottom of the column after the system has been stabilized is 98% by weight or more of 1,4-butanediol, and the extraction line (8) so that the liquid level of the rectifying column (C) is constant. A part of it was extracted outside. On the other hand, the low boiling component was extracted from the top of the column in the form of gas, condensed by the condenser (G), and extracted from the extraction line (13) to the outside so that the liquid level of the tank (F) was constant.

  A certain amount of the oligomer generated in the reaction tank (A) is extracted from the extraction line (4) using the pump (B) so that the average residence time of the liquid in the reaction tank (A) is 3.0 hr. The liquid level was controlled. The oligomer extracted from the extraction line 4 was continuously supplied to the first polycondensation reaction tank (a). After the system was stabilized, the esterification rate of the oligomer collected at the outlet of the reaction vessel (A) was 97.4%.

  The internal temperature of the first polycondensation reaction tank (a) was 240 ° C., the pressure was 2.7 kPa, and the liquid level was controlled so that the residence time was 120 minutes. An initial polycondensation reaction was performed while extracting water, THF, and 1,4-butanediol from a vent line (L2) connected to a decompressor (not shown). The extracted reaction liquid was continuously supplied to the second polycondensation reaction tank (d).

  The internal temperature of the second polycondensation reaction tank (d) is 245 ° C., the pressure is 140 Pa, the liquid level is controlled so that the residence time is 60 minutes, and a vent line (L4) connected to a decompressor (not shown). ), Polycondensation reaction was further carried out while extracting water, THF and 1,4-butanediol. The obtained polymer was continuously supplied to the third polycondensation reaction tank (k) via the extraction line (L3) by the extraction gear pump (e). The internal temperature of the third polycondensation reaction tank (k) was 239 ° C., the pressure was 600 Pa, the residence time was 80 minutes, and the polycondensation reaction was further advanced. The obtained polymer was continuously extracted in the form of a strand from the die head (g) and cut with a rotary cutter (h). The analytical values of the resulting polybutylene terephthalate are summarized in Table 1. Hereinafter, the polybutylene terephthalate resin obtained in Production Example 1 is referred to as PBT-1.

  The analytical value in Production Example 1 was measured by the following method.

(1) Esterification rate:
It calculated from the acid value and the saponification value by the following formula. The acid value was obtained by dissolving the oligomer in dimethylformamide and titrating with a 0.1N KOH / methanol solution. The saponification value was determined by hydrolyzing the oligomer with a 0.5N KOH / ethanol solution and titrating with 0.5N hydrochloric acid.

  Esterification rate = ((saponification value−acid value) / saponification value) × 100

(2) Titanium atom and group 1 and group 2 metal atom concentrations in the polybutylene terephthalate resin:
The polybutylene terephthalate resin was wet-decomposed with high-purity sulfuric acid and nitric acid for electronic industry and measured using a high resolution ICP (Inductively Coupled Plasma) -MS (Mass Spectrometer; manufactured by ThermoQuest).

(3) Intrinsic viscosity (IV) of polybutylene terephthalate resin:
It calculated | required in the following way using the Ubbelohde type viscometer. That is, using a mixed solvent of phenol / tetrachloroethane (weight ratio 1/1), at 30 ° C., the number of falling seconds of only the polymer solution having a concentration of 1.0 g / dL and the solvent was measured and determined from the following formula.

IV = ((1 + 4K _H η _sp ) ^0.5 −1) / (2K _H C)

However, n _sp = n / n ₀ -1, n is the polymer solution falling seconds, n ₀ is the solvent dropping seconds, C is the polymer solution concentration (g / dL), and K _H is the Huggins constant. 0.33.

(4) Terminal carboxyl group concentration of polybutylene terephthalate resin:
In 25 mL of benzyl alcohol, 0.5 g of polybutylene terephthalate resin was dissolved and titrated using a 0.01 mol / L benzyl alcohol solution of sodium hydroxide.

(5) Terminal methoxycarbonyl group concentration of polybutylene terephthalate resin:
About 100 mg of polybutylene terephthalate resin was dissolved in 1 mL of a mixed solvent of deuterated chloroform / hexafluoroisopropanol = 7/3 (volume ratio), 36 μL of deuterated pyridine was added, and ¹ H-NMR was measured and determined at 50 ° C. “Α-400” or “AL-400” manufactured by JEOL Ltd. was used for the NMR apparatus.

PBT-2 (Production Example 2):
In Production Example 1 (PBT-1), the slurry is supplied to 41 kg / h, and the bottom component of the rectifying column (C) is supplied from the recirculation line (2) at 17.2 kg / h, and the catalyst is supplied. The esterification reaction was carried out in the same manner as PBT-1, except that a 6.0 wt% 1,4-butanediol solution of tetrabutyl titanate at 65 ° C. was fed at 97 g / h as a catalyst from the line (3).

  Furthermore, the pressure of the first polycondensation reaction tank (a) is 2.1 kPa, the pressure of the second polycondensation reaction tank (d) is 130 Pa, the residence time is 90 minutes, and the internal temperature of the third polycondensation reaction tank (k). Was performed in the same manner as in Production Example 1 (PBT-1) except that the temperature was 240 ° C., the pressure was 130 Pa, and the residence time was 60 minutes. The analysis values of the obtained PBT are collectively shown in Table 1. Hereinafter, the polybutylene terephthalate resin obtained in Production Example 2 is referred to as PBT-2.

PBT-3 (Production Example 3):
The esterification step in the reactor (A) was performed in the same manner as in Production Example 1 (PBT-1). Magnesium acetate tetrahydrate is dissolved in pure water, 1,4-butanediol is added, and magnesium acetate tetrahydrate, pure water, and 1,4-butanediol are 5% by weight and 20% by weight, respectively. , 75% by weight in a preparation tank (not shown). The temperature at this time was 25 ° C. This solution was supplied to the 1,4-butanediol line (L8) through the supply line (L7), and a predetermined amount was supplied to the oligomer extraction line (4) as a solution having a lower concentration.

  The internal temperature of the first polycondensation reactor (a) is 246 ° C., the pressure is 2.4 kPa, and the residence time is 120 minutes. The internal temperature of the second polycondensation reactor (d) is 239 ° C., the pressure is 150 Pa, and the residence time is 130 minutes. The internal temperature of the third polycondensation reactor (k) was 238 ° C., the pressure was 130 Pa, and the residence time was 70 minutes. The analysis values of the obtained PBT are collectively shown in Table 1. Hereinafter, the polybutylene terephthalate resin obtained in Production Example 3 is referred to as PBT-3.

PBT-4 (Production Example 4):
In Production Example 1 (PBT-1), the catalyst solution was supplied at 254 g / h, the pressure of the second polycondensation reactor (d) was 200 Pa, the pressure of the third polycondensation reactor (k) was 650 Pa, and the residence time Was carried out in the same manner as in Production Example 1 (PBT-1) except that the time was changed to 70 minutes. The analysis values of the obtained PBT are collectively shown in Table 1. Hereinafter, the polybutylene terephthalate resin obtained in Production Example 4 is referred to as PBT-4.

PBT-5 (Production Example 5):
In a 200 L stainless steel reaction vessel equipped with a turbine type stirring blade, dimethyl terephthalate (DMT) 272.9 mol, 1,4-butanediol 327.5 mol, tetrabutyl titanate 0.126 mol (theoretical yield as titanium amount) 100 ppm per polymer) was charged and sufficiently substituted with nitrogen. Subsequently, the system was heated, and after 60 minutes, at a temperature of 210 ° C. and atmospheric pressure under nitrogen, the produced methanol, 1,4-butanediol, and THF were distilled out of the system and subjected to a transesterification reaction for 2 hours ( The reaction start time was the time when the predetermined temperature was reached).

  After transferring the oligomer obtained above to a stainless steel reactor having an internal volume of 200 L having a vent pipe and a double helical stirring blade, it was allowed to reach a temperature of 245 ° C. and a pressure of 100 Pa over 60 minutes. A condensation reaction was performed. When the predetermined power was reached, the reaction was terminated, and the polymer was extracted in the form of a strand and cut into a pellet. The analysis values of the obtained PBT are collectively shown in Table 1. Hereinafter, the polybutylene terephthalate resin obtained in Production Example 5 is referred to as PBT-5.

  <Organic phosphate metal salt>

  Organophosphate metal salt: zinc salt of distearyl acid phosphate and zinc salt of monostearyl acid phosphate (“JP-518Zn” manufactured by Johoku Chemical Industry Co., Ltd., zinc of distearyl acid phosphate and zinc of monostearyl acid phosphate Salt weight ratio 33/67)

  <Organic phosphorus compounds>

  Organophosphorus compound (1): Mixture of monostearyl acid phosphate and distearyl acid phosphate (Adeka Stub AX-71 manufactured by Asahi Denka Kogyo Co., Ltd.)

  Organophosphorus compound (2): bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (“ADK STAB PEP-36” manufactured by Asahi Denka Kogyo Co., Ltd.)

  <Rubber polymer>

  Rubber polymer (1): Core / shell type graft copolymer comprising polyalkyl acrylate (core) / acrylonitrile-styrene copolymer (shell) ("Staffyroid MG1011" manufactured by Ganz Kasei Co., Ltd.)

  Rubber polymer (2): Core / shell type graft copolymer comprising polybutadiene (core) / alkyl acrylate / alkyl methacrylate copolymer (shell) (“EXL2603” manufactured by Rohm and Haas Japan)

<Titanium oxide>
Titanium oxide: Titanium oxide surface-treated with methylhydrogenpolysiloxane ("CP-K" manufactured by Resino Color Industries)

[Preparation of resin composition]:
After each component shown in Table 2 and Table 3 is uniformly mixed with a tumbler mixer in the ratio shown in Table 2 and Table 3, 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 270 ° C., a screw rotation speed of 200 rpm, and a discharge rate of 30 kg / h, and melt-kneaded to produce pellets of the resin composition.

[Preparation of test piece]:
After drying the pellet obtained by the above method at 110 ° C. for 6 hours or more, using an injection molding machine (“M150AII-SJ type” manufactured by Meiki Seisakusho), the cylinder temperature is 270 ° C., the mold temperature is 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 3 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 more, using a high load type flow tester, the flow rate Q value of the composition per unit time at 280 ° C. and a load of 160 kgf / cm 2 (unit: 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 0.45 MPa using a normally molded ASTM test piece.

(4) Hue (YI value):
The YI value of the normally molded flat molded product was measured by a reflection method (suppression plate: white plate) using a spectroscopic colorimeter (Nippon Denshoku Industries Co., Ltd., SE2000 type). The smaller the YI value, the better the hue.

(5) 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) Hue (YI value):
About the flat molded article produced by said stay molding, YI value was measured by the reflection method (suppression board; white board) using the spectroscopic color meter (Nippon Denshoku Industries Co., Ltd. make, SE2000 type | mold). The smaller the YI value, the better the hue.

(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 0.45 MPa.

(6) Chemical resistance (number of cracks generated):
A test chemical was applied to a normally molded ASTM tensile test piece (thickness: 3.2 mm) with a deformation of 0.7% applied, and the degree of occurrence of cracks was evaluated visually 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.

(7) Fatigue properties (bending fatigue failure):
In accordance with ASTM D671, a test was performed at 23 ° C. and an actual stress of 19 MPa using a normally molded Type A test piece, and the number of times of failure was evaluated.

(8) Moist heat resistance (breaking elongation retention):
A normally formed ASTM tensile test piece (thickness: 3.2 mm) was subjected to a wet heat treatment at 75 ° C. and 95% RH for 500 hours, and then a tensile test was performed.

[Examples 1 and 2, Reference Examples 1 to 5, Comparative Examples 1 to 7]:
Each resin composition described in Tables 2 and 3 was produced and evaluated by the above-described method. The results are shown in Tables 2 and 3.

  From the results shown in Tables 2 and 3, the following can be understood. The resin compositions described in Examples 1 and 2 of the present invention have fluidity, impact resistance, heat resistance, hue, as compared with the resin compositions described in Reference Examples 1 to 5 and Comparative Examples 1 to 7. Excellent balance of residence heat stability, chemical resistance, fatigue properties, and heat and humidity resistance.

1: Raw material supply line 2: Recirculation line 3: Catalyst supply line 4: Extraction line 5: Distillation line 6: Extraction line 7: Circulation line 8: Extraction line 9: Gas extraction line 10: Condensate line 11: Extraction line 12: Circulation line 13: Extraction line 14: Vent line A: Reaction tank B: Extraction pump C: Rectification tower D: Pump E: Pump F: Tank G: Capacitor L1: Extraction line L3 : Extraction line L5: Extraction line L2: Vent line L4: Vent line L6: Vent line L7: Group 1 / Group 2 metal compound catalyst supply line L8: 1,4-butanediol supply line a: First polycondensation reaction Tank d: Second polycondensation reaction tank k: Third polycondensation reaction tank c: Extraction gear pump e: Extraction gear pump m: Extraction gear pump g: Die head h: Rotary cutter

Claims (10)

Aromatic polycarbonate resin (component A) 51 to 99% by weight, polybutylene terephthalate resin (component B) 1 to 49% by weight (the total of component A and component B is 100% by weight), component A and component B Is an aromatic polycarbonate resin composition comprising 0.001 to 3 parts by weight of an organophosphate metal salt (component C) with respect to a total of 100 parts by weight, and the titanium compound content in the polybutylene terephthalate resin is titanium. The polybutylene terephthalate resin further contains a group 1 metal compound and / or a group 2 metal compound, and the content of the group 1 metal compound and / or the group 2 metal compound is More than 1 ppm in terms of metal atom and 50 ppm or less, and the organic phosphate metal salt is represented by the following general formula (1), ( ), (3) and (4) in the aromatic polycarbonate resin composition which is characterized in that at least one selected from the group consisting of organic phosphoric acid ester metal salt represented.

(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.
Fat composition.   The aromatic polycarbonate resin composition according to claim 1, wherein the terminal carboxyl group concentration of the polybutylene terephthalate resin is 1 to 39 µeq / g.   The aromatic polycarbonate resin composition according to claim 1 or 2, wherein the content of the titanium compound in the polybutylene terephthalate resin is more than 20 ppm and not more than 50 ppm as a titanium atom.   The aromatic polycarbonate resin composition according to any one of claims 1 to 3, wherein the polybutylene terephthalate resin has a terminal methoxycarbonyl group concentration of 0.5 µeq / g or less.   The aromatic polycarbonate resin composition according to any one of claims 1 to 4, wherein the polybutylene terephthalate resin contains a magnesium compound as a group 2 metal compound.   The blending amount of the aromatic polycarbonate resin (component A) is 55 to 90% by weight, and the blending amount of the polybutylene terephthalate resin (component B) is 10 to 45% by weight (however, the sum of the component A and the component B is 100% by weight). %)) The aromatic polycarbonate resin composition according to any one of claims 1 to 5. The organophosphate metal salt is a mixture of the organophosphate metal salt represented by the general formula (1) and the organophosphate metal salt represented by the general formula (2), and the general The aromatic polycarbonate resin composition according to any one of claims 1 to 6, wherein R ^{1 to} R ⁵ in the formula (1) and the general formula (2) are each an alkyl group having 2 to 25 carbon atoms.   The aromatic polycarbonate resin composition according to claim 7, wherein in the organic phosphate metal salt, M in the general formula (1) and the general formula (2) is zinc.   The content of the organophosphate metal salt is 0.01 to 0.2 parts by weight with respect to 100 parts by weight as a total of the aromatic polycarbonate resin and the polybutylene terephthalate resin. Thermoplastic resin composition.   A resin molded product formed by molding the aromatic polycarbonate resin composition according to claim 1.

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