JP2007176969A - Aromatic polycarbonate resin composition and resin molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin composition having well balanced and excellent fluidity, impact and chemical resistances, fatigue characteristics, residence thermal stability and recycling characteristics. <P>SOLUTION: The aromatic polycarbonate resin composition is characterized as follows. The aromatic polycarbonate resin composition is composed of an aromatic polycarbonate resin (component A) and a polybutylene terephthalate resin (component B). The content of the aromatic polycarbonate resin (component A) is 51-99 pts.wt. and the content of the polybutylene terephthalate resin (component B) is 1-49 pts.wt. in 100 pts.wt. of the sum total of the aromatic polycarbonate resin (component A) and the polybutylene terephthalate resin (component B). In the polybutylene terephthalate resin (component B), the content of a titanium compound is >1 to ≤75 ppm expressed in terms of titanium atom. The concentration of terminal carboxy groups is ≤39 μeq/g. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an aromatic polycarbonate resin composition mainly composed of an aromatic polycarbonate resin and a polybutylene terephthalate resin. More specifically, an aromatic polycarbonate resin composition excellent in various properties such as fluidity, impact resistance, chemical resistance, fatigue characteristics, heat resistance, and retention heat stability, and at the same time excellent in recycling characteristics, and The present invention relates to a molded resin product.

  Aromatic polycarbonate resin is a general-purpose engineering plastic with excellent transparency, impact resistance, heat resistance, dimensional stability, etc., and its excellent characteristics make it a wide range of electrical, electronic, OA equipment parts, machine parts, vehicle parts, etc. Used in the field. Furthermore, a polymer alloy comprising an aromatic polycarbonate resin and a polybutylene terephthalate resin is a material with improved chemical resistance and molding processability, which are disadvantages of the aromatic polycarbonate resin, while taking advantage of the above-mentioned excellent features of the aromatic polycarbonate resin. It is used in vehicle interior / exterior parts, various housing members and other wide fields.

  An aromatic polycarbonate resin composition (polymer alloy) mainly composed of an aromatic polycarbonate resin and a polybutylene terephthalate (PBT) resin is a polymer alloy having a sea-island structure micro-form, and any resin is a sea phase (continuous layer). ), The characteristics vary greatly. 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 polymer alloys with 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, and the heat resistance of the resin composition decreases. There was a problem to do.
Further, vehicle parts and the like are painted for design and coloring, and a material having higher heat resistance that can withstand the coating temperature has been desired. In recent years, it has become essential to recycle used products, non-conforming products, sprue and other resin products, return them to virgin raw materials, and process them into resin products through a melt molding process. Materials that are less likely to suffer a decrease in heat resistance even when subjected to heat have become very important.
In this way, the polymer alloy with polybutylene terephthalate resin, which has a high content of aromatic polycarbonate resin, is excellent in fluidity, impact resistance, chemical resistance, fatigue characteristics, residence heat stability, and recycling characteristics. There is a need for a material having an excellent balance of physical properties, such as being excellent.

  In order to solve this problem, for example, as a means for solving the problem of the above-mentioned residence heat stability, a technique of blending a phosphorus compound into a polymer alloy of an aromatic polycarbonate resin and a polyester resin is known (for example, Patent Documents). 1 and 2). However, simply adding a phosphorus compound is not always satisfactory in terms of the balance of impact resistance, fatigue characteristics, heat resistance, residence heat stability, and recycling characteristics.

Furthermore, a thermoplastic resin composition is disclosed that is a polymer alloy composed of a polycarbonate resin and a polybutylene terephthalate resin and has a melt viscosity stability index of 2.5% or less (see Patent Document 3). Specifically, a technique is disclosed in which a branched component of a polycarbonate resin, a terminal carboxy concentration of a polybutylene terephthalate resin, and a specific stabilizer are combined.
However, the technique disclosed in Patent Document 3 and the specifically exemplified compositions are not always satisfactory in the balance of impact resistance, fatigue characteristics, heat resistance, residence heat stability, and recycling characteristics. Furthermore, the titanium content of the polybutylene terephthalate resin is only generally described, and the importance of the polybutylene terephthalate resin having a specific amount of titanium content and a specific amount of terminal carboxy concentration is disclosed. It was not a thing.

  On the other hand, a thermoplastic resin composition excellent in mechanical properties composed of a polybutylene terephthalate resin having a specific end group concentration and a polycarbonate resin has been proposed (see Patent Document 4). However, simply adjusting the terminal group concentration does not necessarily satisfy the balance of impact resistance, fatigue characteristics, heat resistance, residence heat stability, and recycling characteristics, and polybutylene containing a large amount of aromatic polycarbonate resin. It did not disclose a technique excellent in fluidity, impact resistance, chemical resistance, fatigue characteristics, heat resistance, residence heat stability, and recycling characteristics in a polymer alloy with a terephthalate resin.

  In addition, the polybutylene terephthalate resin specifically exemplified as the composition has a high titanium content, and in a polymer alloy with a polybutylene terephthalate resin with a high content of aromatic polycarbonate resin, the residence heat stability and recycling characteristics There was a problem of being inferior.

  On the other hand, a composition in which a transesterification reaction between a polybutylene terephthalate resin produced using a polycondensation catalyst containing a phosphorus component and a titanium component and a polycarbonate resin is suppressed has been proposed (see Patent Document 5). However, it is not sufficient to simply use a phosphorus component and a titanium component as a polycondensation catalyst. The polybutylene terephthalate resin specifically exemplified as the composition has a high titanium content and is a resin composition with an aromatic polycarbonate resin. As a result, the balance of impact resistance, fatigue characteristics, heat resistance, stagnant heat stability, recycling characteristics, etc. was not satisfactory.

  Furthermore, with respect to 100 parts by weight of polybutylene terephthalate resin having a titanium content of 33 ppm or less as titanium atoms, mechanical properties, crystallization speed, and hydrolysis resistance are improved by containing 5 to 100 parts by weight of polycarbonate resin and other components. A resin composition has been proposed (see Patent Document 6). However, the technology described in Patent Document 6 merely discloses a polymer alloy technology with a polycarbonate resin having a high content of polybutylene terephthalate resin, and a field in which a polymer alloy having a high content of aromatic polycarbonate resin is applied. Only a different technology was disclosed.

Japanese Unexamined Patent Publication No. 3-977752 JP-A 63-265949 JP 2002-294060 A JP 2004-18558 A JP 7-138354 A JP 2004-307794 A

The object of the present invention is to eliminate the above-mentioned disadvantages of the prior art, and to have excellent fluidity, impact resistance, chemical resistance, fatigue characteristics, heat resistance, and retention heat stability, as well as excellent recycle characteristics. It is providing a group polycarbonate resin composition.

  As a result of intensive research to achieve the above object, the inventors of the present invention have a high content of aromatic polycarbonate resin, and in a polymer alloy of aromatic polycarbonate resin and polybutylene terephthalate resin, as polybutylene terephthalate resin, By using a specific amount of titanium compound and a specific terminal carboxyl group concentration, various properties such as fluidity, impact resistance, chemical resistance, fatigue characteristics, heat resistance, residence heat stability and recycling characteristics The present inventors have found that the resin physical properties are improved at the same time and the aromatic polycarbonate resin composition (hereinafter sometimes simply referred to as “resin composition”) has an excellent physical property balance, and the present invention has been completed.

  That is, the gist of the present invention is an aromatic polycarbonate resin composition comprising an aromatic polycarbonate resin (component A) and a polybutylene terephthalate resin (component B), the aromatic polycarbonate resin (component A) and polybutylene. Of the total 100 parts by weight of the terephthalate resin (component B), the aromatic polycarbonate resin (component A) is 51 to 99 parts by weight, the polybutylene terephthalate resin (component B) is 1 to 49 parts by weight, and the polybutylene terephthalate resin ( B component), the titanium compound content is more than 1 ppm as titanium atom and 75 ppm or less, and the terminal carboxyl group is 39 μeq / g or less, and an aromatic polycarbonate resin composition is molded. It relates to a molded resin product.

The aromatic polycarbonate resin composition of the present invention is a resin composition with excellent physical property balance that simultaneously satisfies various physical properties such as fluidity, impact resistance, chemical resistance, fatigue characteristics, heat resistance, residence heat stability, and recycling characteristics. It is a thing.
The aromatic polycarbonate resin composition of the present invention having such features can be used in a wide range of fields, such as electrical / 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. Vehicle interior parts include inner door handles, center panels, instrument panels, console boxes, luggage floor boards, display housings for car navigation, and the like.

  Hereinafter, the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. In the present specification, the “group” of various compounds may have a substituent without departing from the spirit of the present invention.

[1] Aromatic polycarbonate resin (component A)
The aromatic polycarbonate resin which is the A component used in the present invention (hereinafter sometimes abbreviated as “A component”) includes, for example, an aromatic dihydroxy compound and a carbonate precursor, or a small amount of them together. A linear or branched thermoplastic aromatic polycarbonate polymer or copolymer obtained by reacting a polyhydroxy compound or the like.

  As the aromatic polycarbonate resin (component A) used in the present invention, those obtained by any conventionally known production method can be used. Specific examples include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Among them, it is advantageous in the chemical industry to use an interfacial polymerization method or a melt transesterification method. Hereinafter, these two methods will be described as examples of the method for producing an aromatic polycarbonate resin.

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

  Exemplified by 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, etc. Bis (hydroxyaryl) cycloalkanes to be prepared;

Cardostructure-containing bisphenols exemplified by 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and the like; 4,4′-dihydroxydiphenyl ether, Dihydroxydiaryl ethers exemplified by 4′-dihydroxy-3,3′-dimethyldiphenyl ether and the like;

Dihydroxydiaryl sulfides exemplified by 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, and the like; 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy- Dihydroxydiaryl sulfoxides exemplified by 3,3′-dimethyldiphenyl sulfoxide and the like; dihydroxydiaryl sulfones exemplified by 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone and the like And the like; hydroquinone, resorcin, 4,4′-dihydroxydiphenyl and the like.

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

As the carbonate precursor to be reacted with the aromatic dihydroxy compound, carbonyl halide, carbonate ester, haloformate and the like are used. Specifically, phosgene; diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dimethyl carbonate, diethyl carbonate and the like Dialkyl carbonates; dihaloformates of dihydric phenols and the like. These carbonate precursors may also be used alone or in combination of two or more.

  The aromatic polycarbonate resin (component A) 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, 1, Polyhydroxy compounds exemplified by 1,1-tri (4-hydroxyphenyl) ethane, etc., or 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 preferable. The polyfunctional aromatic compound can be used by substituting a part of the aromatic dihydroxy compound, and the amount used is preferably 0.01 to 10 mol% with respect to the aromatic dihydroxy compound. ~ 2 mol% is preferred.

  The reaction by the interfacial polymerization method is, for example, in the presence of an organic solvent inert to the reaction and an aqueous alkali solution, usually maintaining the pH at 9 or higher, and adding an aromatic dihydroxy compound as necessary to a molecular weight modifier (terminal terminator). Reacting with phosgene together with an antioxidant of an aromatic dihydroxy compound. Next, a method of obtaining a polycarbonate by adding a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt and performing interfacial polymerization can be mentioned. 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 may be appropriately selected and determined between the phosgenation reaction and the start of the polymerization reaction.

Here, examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene, and aromatic hydrocarbons such as benzene, toluene and xylene. . Examples of the alkali compound used in the alkaline aqueous solution include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
Examples of the molecular weight regulator include compounds having a monovalent phenolic hydroxyl group. Examples of the compound having a monovalent phenolic hydroxyl group include m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol and p-long chain alkyl-substituted phenol.

  The usage-amount of a molecular weight regulator becomes like this. Preferably it is 0.5-50 mol with respect to 100 mol of aromatic dihydroxy compounds, More 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 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. Of these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable.

In the aromatic polycarbonate resin, the amount of terminal hydroxyl groups greatly affects the thermal stability, hydrolysis stability, color tone and the like of the product polycarbonate, and may be appropriately adjusted by any conventionally known method. In the melt transesterification reaction, usually, the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound and the degree of pressure reduction during the transesterification reaction are adjusted to obtain an aromatic polycarbonate having the desired molecular weight and terminal hydroxyl group content adjusted. Can do. Usually, in the melt transesterification reaction, the diester carbonate is used in an equimolar amount or more with respect to 1 mol of the aromatic dihydroxy compound, and it is preferably used in an amount of 1.01-1.30 mol.
Further, as a more aggressive adjustment method, there is a method of adding a terminal terminator separately at the time of reaction, and examples of the terminal terminator in this case include monohydric phenols, monovalent carboxylic acids, and carbonic acid diesters. It is done.

  When producing polycarbonate by the melt transesterification method, a transesterification catalyst is usually used. The transesterification catalyst is not particularly limited, but an alkali metal compound and / or an alkaline earth metal compound is preferable. In addition, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound may be used in combination. As the transesterification reaction using the above raw materials, the reaction is carried out at a temperature of 100 to 320 ° C., and finally a melt polycondensation reaction is performed under reduced pressure of 2 mmHg or less while removing by-products such as aromatic hydroxy compounds. Just do it.

  The melt polycondensation can be performed by either a batch method or a continuous method. Among these, in consideration of the stability of the aromatic polycarbonate resin used in the present invention and the resin composition of the present invention, it is preferable to carry out in a continuous manner. As the catalyst deactivator used in the melt transesterification method, it is preferable to use a compound that neutralizes the transesterification reaction catalyst, such as a sulfur-containing acidic compound or a derivative formed therefrom. The compound that neutralizes such a catalyst is preferably added in an amount of 0.5 to 10 equivalents, more preferably 1 to 5 equivalents, relative to the alkali metal contained in the catalyst. In addition, the compound that neutralizes such a catalyst is preferably added in an amount of 1 to 100 ppm, more preferably 1 to 20 ppm, based on the polycarbonate.

The molecular weight of the aromatic polycarbonate resin (component A) used in the present invention may be appropriately selected and determined, but the viscosity average molecular weight [Mv] converted from the solution viscosity is preferably in the range of 10,000 to 50,000. By setting the viscosity average molecular weight of the aromatic polycarbonate to 10,000 or more, the mechanical strength tends to be further improved, and it is more preferable when used for applications requiring high mechanical strength. On the other hand, when the viscosity average molecular weight is less than 50000, it tends to be possible to further improve the decrease in fluidity, which is more preferable from the viewpoint of easy molding processability.
The viscosity average molecular weight is more preferably 12000 to 40000, and further preferably 14000 to 30000. Moreover, you may mix 2 or more types of aromatic polycarbonate resin from which a viscosity average molecular weight differs. Of course, you may mix the aromatic polycarbonate resin whose viscosity average molecular weight is outside the said suitable range.

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

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

  Further, as the aromatic polycarbonate resin (component A) used in the present invention, not only virgin raw materials but also aromatic polycarbonate resins regenerated from used products, so-called material recycled aromatic polycarbonate resins may be used. . Used products include optical recording media such as optical disks, light guide plates, vehicle window glass, vehicle headlamp lenses, windshields, and other vehicle transparent members, water bottle containers, glasses lenses, soundproof walls, glass windows, waves, etc. A building member such as a plate is preferred. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used. The regenerated aromatic polycarbonate resin is preferably 80% by weight or less, more preferably 50% by weight or less of the component A.

[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 50 mol% or more of the unit is composed of a terephthalic acid unit, 50 mol% or more of the diol unit is a polymer composed of 1,4-butanediol unit, and the titanium compound content exceeds 1 ppm and is 75 ppm or less as a titanium atom. And a polybutylene terephthalate resin having a terminal carboxyl group of 39 μeq / g or less.

  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, a decrease in the crystallization rate of the B component can be suppressed, and the moldability can be improved.

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 (component B) used in the present invention, the diol component other than 1,4-butanediol is not particularly limited, and any conventionally known one 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. Alicyclic diol, xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4
And aromatic diols such as -hydroxyphenyl) propane and bis (4-hydroxyphenyl) sulfone.

  In the polybutylene terephthalate resin (component B) used in the present invention, lactic acid, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, p-β-hydroxyethoxy Monofunctional components such as hydroxycarboxylic acid such as benzoic acid, alkoxycarboxylic acid, stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t-butylbenzoic acid, benzoylbenzoic acid, tricarballylic acid, trimellitic acid, trimesic acid, Trifunctional or higher polyfunctional components such as pyromellitic acid, gallic acid, trimethylolethane, trimethylolpropane, glycerol, and pentaerythritol can be used as the copolymerization component.

  The polybutylene terephthalate resin (component B) 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 feature of the polybutylene terephthalate resin (B) component used in the present invention resides 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 Pla-sma (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 (component B) 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 (component B) used in the present invention preferably 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 (component B) 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. When the content of the Group 1 metal compound and / or the Group 2 metal compound is 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 When the content of is less than 50 ppm, the heat resistance, residence heat stability and recycling characteristics of the resin composition tend to be improved.

  The polybutylene terephthalate resin (component B) used in the present invention contains a group 1 metal compound and / or a group 2 metal compound titanium compound as described above, and these compounds are polycondensation of polybutylene terephthalate resin (component B). It is preferably a catalyst or a co-catalyst for a titanium compound catalyst. The group 1 metal compound and / or the group 2 metal compound used as the polycondensation catalyst is not particularly limited. Specifically, examples of the group 1 metal compound include hydroxides of lithium, sodium, potassium, rubidium, and cesium. Oxides; alcoholates; various organic acid salts such as acetates, phosphates and carbonates; Examples of Group 2 metal compounds include beryllium, magnesium, calcium, strontium, and barium hydroxides; oxides; alcoholates; various organic acid salts such as acetates, phosphates, and carbonates; Compounds.

These may be used alone or in combination. Among them, lithium, sodium, potassium, magnesium, calcium, and other compounds are preferable from the viewpoints of handling and availability, and catalytic effect, and lithium or magnesium compounds that are excellent in catalytic effect and color tone are preferable, especially magnesium compounds. Is preferred.
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 terminal carboxyl group concentration of the polybutylene terephthalate resin (component B) used in the present invention is 39 μeq / g or less, preferably 5 to 35 μeq / g, particularly preferably 10 to 30 μeq / g. By setting the terminal carboxyl group concentration to 39 μeq / g or less, the mechanical properties and fatigue properties of the resin composition tend to be improved. By setting the terminal carboxyl group concentration to 5 μeq / g or more, the resin composition Heat resistance, residence heat stability and recyclability 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 by the heat generated during molding during resin molding.For example, formic acid is attached to metal molding equipment and this. May affect the vacuum related equipment. Therefore, in the polybutylene terephthalate resin (component B) used in the present invention, the terminal methoxycarbonyl group concentration 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.

  Further, the terminal vinyl group concentration of the polybutylene terephthalate resin (component B) used in the present invention is usually 0.1 to 15 μeq / g, particularly 0.5 to 10 μeq / g, particularly 1 to 8 μeq / g. Is preferred. If the terminal vinyl group concentration is too high, the color tone of the resin composition may be deteriorated, and the terminal vinyl group concentration tends to further increase due to the thermal history during molding. In this case, the color tone may further deteriorate.

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 (component B) 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, and more preferably 0. It is preferable that it is 0.8-1.3 dL / g, especially 0.95-1.25 dL / g. 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 (component B) used in the present invention is not limited to virgin raw materials, but polybutylene terephthalate resin regenerated from used products, so-called material-recycled polybutylene terephthalate resin can be used. . 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 (B component) 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 (component B) used in the present invention was produced by a direct polymerization method from the viewpoint of raw material availability, ease of distillate treatment, superiority of raw material basic units, and effects of the present invention. It is preferable to use polybutylene terephthalate resin. 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 the polybutylene terephthalate resin (component B) used in the present invention, at least a part of 1,4-butanediol is terephthalic acid (or dialkyl terephthalate) in the presence of a titanium catalyst in an esterification reaction vessel. Independently, the step of supplying to an esterification reaction tank (or transesterification reaction tank) and continuously esterifying (or transesterifying) terephthalic acid (or dialkyl terephthalate) and 1,4-butanediol is preferable. Adopted.

  That is, as a method for producing the polybutylene terephthalate resin (component B) used in the present invention, haze and foreign matters derived from the catalyst are reduced and the catalytic activity is not lowered. Therefore, as raw material slurry or solution, together with terephthalic acid or dialkyl terephthalate In addition to the supplied 1,4-butanediol, it is preferable to supply 1,4-butanediol to the esterification reaction vessel or transesterification reaction vessel 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. In addition, “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. It can also be refluxed to the reaction vessel, or can be supplied as 1,4-butanediol with increased purity 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 an esterification reaction vessel or transesterification reaction vessel usually contains components such as water, alcohol, tetrahydrofuran (THF), and dihydrofuran in addition to the 1,4-butanediol component. It is out. 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 the “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 other means. “Supply 1,4-butanediol” means 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 used in the production of the polybutylene terephthalate resin (component B) 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 catalysts”). In addition to “a group 1 metal catalyst” and “a group 2 metal catalyst”), for example, tin or a compound thereof may be used.

  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, since tin and tin compounds generally deteriorate the color tone of the polybutylene terephthalate resin, 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 (component B) 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 phosphorous 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 or directly supplied to the reaction liquid phase part of the esterification reaction tank or transesterification reaction tank 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. The catalyst solution is preferably mixed with separately supplied 1,4-butanediol and piping and supplied to the esterification reaction tank or 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 part 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 or 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 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 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. (The 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 or the like. 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 or the like. 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 preferably 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 (component B) 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). Accumulated.

  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 is supplied to the second polycondensation reaction tank (d) through the gear pump (c) and the 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) through 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 further proceeds, 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 cooling, 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] Phosphorus compound The polycarbonate resin composition of the present invention preferably contains a phosphorous compound in order to improve heat resistance and residence heat stability within a range not impairing the effects of the present invention. As the phosphorus compound, any conventionally known compound can be used. Specifically, phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, polyphosphoric acid, acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, acidic calcium pyrophosphate, potassium phosphate And phosphates of Group 1 or 2B metals such as sodium phosphate, cesium phosphate, and zinc phosphate, organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds.
In these, the organic phosphate compound represented by the following general formula (I) and / or the organic phosphite compound represented by the following general formula (II) are preferable.

O = P (OH) _m (OR) _3-m (I)
(In general formula (I), R is an alkyl group or an aryl group, and each may be the same or different. M is an integer of 0-2.)

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

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

In the general formula (I), R is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, more preferably an alkyl group having 2 to 25 carbon atoms. is there. M is preferably 1 and / or 2.
In the general formula (II), R ′ is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. Preferable specific examples of the phosphite represented by the general formula (II) include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis ( Mention may be made of 2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.

  The content of these phosphorus compounds is preferably 0.001 to 1 part by weight, particularly 0.005 to 0.5 part by weight, particularly 0.01 to 100 parts by weight of the total of component A and component B. It is preferable that it is -0.3 weight part.

In the aromatic polycarbonate resin composition of the present invention, the content ratio of the A component and the B component is 51 to 99 parts by weight, preferably 55 to 90 parts by weight, of the total of 100 parts by weight of the A and B components. More preferably, it is 60-85 weight part, B component is 1-49 weight part, Preferably it is 10-45 weight part, More preferably, it is 15-40 weight part.
When the A component is 51 parts by weight or more, impact resistance tends to be improved, and when it is less than 99 parts by weight, fluidity and chemical resistance tend to be improved.

The polycarbonate resin composition of this invention may contain other resin and various resin additives other than the said A and B component in the range which does not impair the objective of this invention as needed.
Examples of other resins include 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, mold release agents, dyes and pigments, heat stabilizers, reinforcing agents, flame retardants, impact resistance improvers, weather resistance improvers, antistatic agents, antifogging agents, and lubricants. -Antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, and the like. These may be used alone or in combination of two or more.

In the resin composition of the present invention, in addition to the components A and B, resins, additives, and the like can be appropriately selected from any conventionally known methods.
Specifically, for example, the components A and B 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, uniaxial kneading A resin composition can be produced by melt-kneading with an extruder, 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 and 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.
<A component>
PC-1: Bisphenol A type aromatic polycarbonate produced by an interfacial polymerization method (Iupilon S-3000FN, Mv22500, manufactured by Mitsubishi Engineering Plastics Co., Ltd., terminal hydroxyl group concentration 150 ppm)
PC-2: Bisphenol A type aromatic polycarbonate produced by an interfacial polymerization method (Iupilon E-2000FN, Mv28000, terminal hydroxyl group concentration 150 ppm, manufactured by Mitsubishi Engineering Plastics)

<B component>
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 a raw material supply line (1) from a slurry preparation tank in advance with an esterification rate of 99. % Was continuously fed to a reaction tank (A) for esterification having a screw type stirrer filled with polybutylene terephthalate oligomer at 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 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 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)
(Where η _sp = η / η ₀ −1, η is the polymer solution dropping time, η ₀ is the solvent dropping time, C is the polymer solution concentration (g / dL), and K _H is the Huggins constant. Yes 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
The esterification step in the reactor (A) was carried out in the same manner as PBT-1, and the polycondensation step was carried out using the step shown in FIG. The reaction conditions in the first polycondensation reaction tank (a) were the same as those of PBT-1, and the internal temperature of the second polycondensation reaction tank (d) was 241 ° C., the pressure was 150 Pa, the residence time was 70 minutes, and pellets were obtained. . 50 kg of this PBT pellet was subjected to solid-phase polymerization treatment at 195 ° C. under reduced pressure (0.133 kPa or less) in a double conical blender (with an internal volume of 100 L). When the intrinsic viscosity was reached, the polymerization was stopped by cooling. 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
In PBT-1, the slurry is supplied to 41 kg / h, the bottom component of the rectifying column (C) is supplied at 17.2 kg / h from the recirculation line (2), and from the catalyst supply line (3). 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 as a catalyst at 97 g / h (30 ppm relative to the theoretical polymer yield). Went.

  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 carried out in the same manner as 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 3 is referred to as PBT-3.

PBT-4: Production Example 4
The polycondensation step was carried out in the step shown in FIG. 2 and was carried out in the same manner as PBT-3 except that the third polycondensation reaction tank (k) was not used. 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
The esterification step in the reactor (A) was carried out in the same manner as 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 5 is referred to as PBT-5.

PBT-6: Production Example 6
The esterification step in the reactor (A) was carried out in the same manner as PBT-1, and the polycondensation step was carried out using the step shown in FIG. The addition method of magnesium acetate tetrahydrate and the reaction conditions in the first polycondensation reaction tank (a) are the same as in PBT-5, the internal temperature of the second polycondensation reaction tank (d) is 238 ° C., the pressure is 200 Pa, and the residence Pellets were obtained with a time of 140 minutes. The analysis values of the obtained PBT are collectively shown in Table 1. Hereinafter, the polybutylene terephthalate resin 6 obtained in Production Example is referred to as PBT-6.

PBT-7: Production Example 7
The esterification step in the reactor (A) was carried out in the same manner as PBT-1. In place of PBT-5 magnesium acetate tetrahydrate, lithium acetate dihydrate, pure water, and 1,4-butanediol were 2.5% by weight, 20% by weight, and 77.5% by weight, respectively. The solution is prepared in a preparation tank (not shown), and this solution is supplied to the 1,4-butanediol line (L8) through the supply line (L7). A predetermined amount was supplied to 4). The conditions for the first polycondensation reactor (a) were the same as those for PBT-5, the internal temperature of the second polycondensation reactor (d) was 241 ° C., and the internal temperature of the third polycondensation reactor (k) was 242. A polycondensation reaction was performed in the same manner as PBT-5 except that the temperature was changed to ° C. The analysis values of the obtained PBT are collectively shown in Table 1. Hereinafter, the polybutylene terephthalate resin obtained in Production Example 7 is referred to as PBT-7.

PBT-8: Production Example 8
The esterification step in the reactor (A) and the initial polycondensation step in the first polycondensation reaction tank (a) are carried out in the same manner as in PBT-1, and the pressure in the second polycondensation reactor (d) is 200 Pa, The same as PBT-1, except that the pressure of the triple condensation reactor (k) was 650 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 8 is referred to as PBT-8.

PBT-9: Production Example 9
The internal temperature of the first polycondensation reactor (a) is 247 ° C., the pressure is 6.0 kPa, the pressure of the second polycondensation reactor (d) is 250 Pa, and the internal temperature of the third polycondensation reactor (k) is 245. The procedure was the same as PBT-1, except that the temperature and the residence time were 70 minutes. The analysis values of the obtained PBT are collectively shown in Table 1. Hereinafter, the polybutylene terephthalate resin obtained in Production Example 9 is referred to as PBT-9.

PBT-10: Production Example 10
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 10 is referred to as PBT-10.

<Other ingredients>
Phosphorus compounds:
Chemical formula O = P (OH) _{n ′} (OC ₁₈ H ₃₇ ) _{3-n ′} (mixture of n ′ = 1 and 2)
“Adeka Stub AX-71” manufactured by Asahi Denka Kogyo Co., Ltd.

[Preparation of resin composition]
After the A component, B component and other components were uniformly mixed with a tumbler mixer in the proportions shown in Table 2, a twin screw extruder (manufactured by Nippon Steel Works, TEX30XCT, L / D = 42, barrel number 12) was used. The pellets of the resin composition were prepared by feeding to the extruder from the barrel 1 and melt-kneading at a cylinder temperature of 270 ° C. and a screw speed of 200 rpm.

[Preparation of test piece]
The pellets obtained by the above method were dried at 110 ° C. for 4 hours or more, and then a cylinder temperature of 270 ° C., a mold temperature of 80 ° C., a molding cycle of 55 using a M150AII-SJ type injection molding machine manufactured by Meiki Seisakusho. ASTM test pieces (normally molded products) were prepared under the conditions of seconds.
In addition, the retention molding was performed in one cycle of 2.5 minutes, and evaluation was performed for the retention molding products after the fifth shot. Further, 30 parts by weight of ASTM test pieces obtained by continuous molding in the above molding cycle 55 seconds (recycled raw material) and 70 parts by weight of resin composition pellets (virgin raw material) are uniformly distributed in a tumbler mixer. And dried at 110 ° C. for 4 hours or more, and then using a M150AII-SJ type injection molding machine manufactured by Meiki Seisakusho, under conditions of a cylinder temperature of 270 ° C., a mold temperature of 80 ° C., and a molding cycle of 55 seconds, ASTM test specimens were prepared. This operation was repeated twice to produce a recycled molded product (ASTM test piece).

[Evaluation methods]
(1) Fluidity (Q value):
Using a high load type flow tester, the flow rate Q value (unit: ml / s) per unit time of the composition was measured under the conditions of 280 ° C. and a load of 160 kgf / cm ² 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):
In accordance with ASTM D256, Izod impact strength (unit: J / m) was measured at 23 ° C. using a notched specimen having a thickness of 3.2 mm.
(3) Chemical resistance (breaking elongation retention):
A test chemical is applied to an ASTM tensile test piece (thickness: 3.2 mm) with a deformation rate of 1%, and the elongation at break after 48 hours (ratio with respect to the test chemical not applied) evaluated. Di (2-ethylhexyl) phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as a test chemical. The evaluation of chemical resistance was evaluated as ◯ when the breaking elongation retention was 75% or more, and x when the breaking elongation retention was less than 75%.
(4) 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 Type A test piece, and the number of times of failure was evaluated.

(5) Heat resistance (thermal deformation temperature: DTUL):
In accordance with ASTM D648, the heat distortion temperature (unit: ° C.) was measured at 0.45 MPa.
(6) Stability thermal stability (thermal deformation temperature and hue):
a. Thermal deformation temperature Based on ASTM D648, the thermal deformation temperature of the staying molded article was measured at 0.45 MPa and evaluated.
b. Hue As compared with the above-mentioned normal molded product, the retained molded product was evaluated as ◯ when there was no or almost no hue change, and x when the hue change was recognized.
(7) Recycling characteristics (heat distortion temperature and hue):
a. Thermal deformation temperature Based on ASTM D648, the thermal deformation temperature of the recycled molded product was measured and evaluated at 0.45 MPa.
b. Hue As compared with the normal molded product, the recycle molded product with almost no hue change was evaluated as ◯, and the one with hue change was evaluated as x.

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

From the results shown in Table 2, the following can be understood. The aromatic polycarbonate resin compositions described in Examples 1 to 7 of the present invention have an excellent balance of fluidity, impact resistance, chemical resistance, heat resistance, residence heat stability, and recycling characteristics. Conversely, the composition in Comparative Example 1 has a titanium atom content of the B component that is outside the scope of this patent, and compared with the compositions of Examples, fatigue characteristics, heat resistance, residence heat stability, and recycling characteristics Inferior to

  In addition, the composition of Comparative Example 2 has a terminal carboxy concentration of the B component outside the range specified in this patent, and is inferior in impact resistance and fatigue characteristics as compared with the compositions of Examples. And the composition in Comparative Example 3 has a titanium atom content of the B component and a terminal carboxy concentration outside the scope of this patent, and compared with the compositions of the Examples, impact resistance, fatigue characteristics, and stable heat retention Inferior in properties and recycling characteristics.

Explanatory drawing of an example of the esterification reaction process or transesterification reaction process employed in the present invention Explanatory drawing of an example of the polycondensation step employed in the present invention Explanatory drawing of an example of the polycondensation step employed in the present invention

Explanation of symbols

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, L5: Extraction lines L2, L4, 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, e, m: gear pump for extraction g: die head h: rotary cutter

Claims (9)

  An aromatic polycarbonate resin composition comprising an aromatic polycarbonate resin (component A) and a polybutylene terephthalate resin (component B), a total of 100 of the aromatic polycarbonate resin (component A) and the polybutylene terephthalate resin (component B) In the parts by weight, the aromatic polycarbonate resin (component A) is 51 to 99 parts by weight, the polybutylene terephthalate resin (component B) is 1 to 49 parts by weight, and the polybutylene terephthalate resin (component B) has a titanium compound content. Is an aromatic polycarbonate resin composition characterized by having a titanium atom of more than 1 ppm and 75 ppm or less and a terminal carboxyl group of 39 μeq / g or less.   The polybutylene terephthalate resin (component B) 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 exceeds 1 ppm in terms of metal atoms. The aromatic polycarbonate resin composition according to claim 1, wherein the aromatic polycarbonate resin composition is 50 ppm or less.   The aromatic polycarbonate resin composition according to claim 1 or 2, wherein the terminal methoxycarbonyl group concentration of the polybutylene terephthalate resin (component B) is 0.5 µeq / g or less.   The aromatic polycarbonate resin composition according to any one of claims 1 to 3, wherein the content of the titanium compound in the polybutylene terephthalate resin (component B) 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 4, wherein a terminal carboxyl group of the polybutylene terephthalate resin (component B) is 10 to 30 µeq / g.   The aromatic polycarbonate resin composition according to any one of claims 2 to 5, wherein the polybutylene terephthalate resin (component B) contains a magnesium compound as a group 2 metal compound.   The aromatic polycarbonate resin composition according to any one of claims 1 to 6, comprising 10 to 45 parts by weight of the B component with respect to 55 to 90 parts by weight of the A component.   A resin molded product obtained by molding the aromatic polycarbonate resin composition according to any one of claims 1 to 7. The resin molded product according to claim 8, wherein a part of the molding material is a recycled material.

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