JP2008285529A - Resin composition for producing coated part, and coated part - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin composition having excellent and balanced fluidity, rigidity, impact strength, fatigue resistance, weather resistance and coating workability. <P>SOLUTION: The resin composition for producing a coated part is an aromatic polycarbonate resin composition containing 51-99 pts.wt. of an aromatic polycarbonate resin (component A) and 1-49 pts.wt. of a polybutylene terephthalate resin (component B) and further containing 11-25 pts.wt. of a rubbery polymer (component C), 1-5 pts.wt. of titanium oxide (component D), 0.01-3 pts.wt. of an ultraviolet absorber (component E) and 0.001-1 pt.wt. of a phosphorus-based stabilizer (component F) based on 100 pts.wt. of the sum of the components A and B, wherein the weight ratio of the rubbery polymer (component C) to the titanium oxide (component D) is 5-10. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polycarbonate resin composition for producing a painted part (hereinafter sometimes simply referred to as “resin composition for producing a painted part”) and a painted part mainly composed of an aromatic polycarbonate resin and a polybutylene terephthalate resin. More particularly, the present invention relates to a resin composition for producing a coated part which is excellent in balance in terms of fluidity, rigidity, impact resistance, fatigue resistance, weather resistance, and paintability, and a painted part formed by coating and molding the resin composition.

  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 composed of an aromatic polycarbonate resin and a polybutylene terephthalate resin has the chemical resistance and molding processability (fluidity) that are the disadvantages of the aromatic polycarbonate resin, while taking advantage of the above-mentioned excellent features of the aromatic polycarbonate resin. It is an improved material and is used in vehicle interior / exterior parts, various housing members and a wide range of other fields.

  An aromatic polycarbonate resin composition (polymer alloy) mainly composed of an aromatic polycarbonate (PC) resin and a polybutylene terephthalate (PBT) resin is a polymer alloy having a micro-form of sea-island structure, and any resin is a sea phase. Depending on whether the (continuous layer) is formed, the characteristics are also greatly different. In the case where the aromatic polycarbonate resin constitutes a continuous layer (the content of the aromatic polycarbonate resin is higher than that of the polybutylene terephthalate resin), it is more resistant than the polymer alloy having a higher content of polybutylene terephthalate resin. While excellent in impact properties and dimensional characteristics, there is a problem that fluidity and fatigue resistance are low. And when such a resin composition is used for a large-sized exterior part for automobiles, etc., a material having a better balance in terms of fluidity, impact resistance and fatigue resistance has been demanded.

  Furthermore, in the case of resin-made coated parts, manufacturers often do not paint before shipment in order to meet the diversifying needs of customers, and paint according to customer requirements at dealers. For example, in the case of a vehicle such as a truck, unpainted parts may be discolored by exposure to sunlight between the time the vehicle is manufactured and before painting at a dealer. At the same time, a material excellent in weather resistance has been demanded.

  As means for solving the above problems, a resin composition has been proposed in which impact resistance is improved by blending a rubbery polymer with a polymer alloy mainly composed of an aromatic polycarbonate resin and a polybutylene terephthalate resin. (For example, refer to Patent Documents 1 and 2). Further, as a method for improving the mechanical strength by containing an impact strength improver, a thermoplastic resin composition comprising a polybutylene terephthalate resin having a specific terminal carboxyl group concentration and a polycarbonate resin has been proposed (for example, a patent). Reference 3). However, these prior arts only disclose a resin composition having excellent impact resistance obtained by blending a rubbery polymer with a polymer alloy composed of an aromatic polycarbonate resin and a polybutylene terephthalate resin. It did not disclose an excellent resin composition with a good balance of properties, rigidity, impact resistance, fatigue resistance, weather resistance, and paintability.

  Furthermore, mechanical properties, crystallization speed, hydrolysis resistance, comprising 5 to 100 parts by weight of polycarbonate resin and other components with respect to 100 parts by weight of polybutylene terephthalate resin having a titanium content of 33 ppm or less as titanium atoms. A resin composition having excellent properties has also been proposed (see, for example, Patent Document 4). However, this is a so-called polybutylene terephthalate resin composition with a high content of polybutylene terephthalate resin, so-called improvement in mechanical properties, crystallization speed, hydrolysis resistance, and so-called polycarbonate resin content. This is different from the technique for improving the polycarbonate resin composition. Furthermore, the above patent document did not disclose a resin composition having a good balance in terms of fluidity, rigidity, impact resistance, fatigue resistance, weather resistance, and paintability.

  Further, as an impact resistance improving resin composition that does not change color even when exposed to ultraviolet rays, the resin composition includes a polyester resin, a polycarbonate resin, an impact resistance improving agent, a hindered amine light stabilizer, a UV absorber, and a composition thereof. Products have also been proposed (see, for example, Patent Document 5). However, the above-mentioned patent documents do not disclose a resin composition excellent in balance with respect to fluidity, rigidity, impact resistance, fatigue resistance, weather resistance, and paintability.

JP 49-41442 A JP 58-117247 A JP 2004-18558 A JP 2004-307794 A JP 2003-160721 A

  An object of the present invention is to provide a resin composition for producing a coated part, which solves the above-mentioned drawbacks of the prior art and has a good balance of fluidity, rigidity, impact resistance, fatigue resistance, weather resistance, and paintability. There is.

  As a result of intensive research to achieve the above object, the present inventors have found that a polymer alloy of an aromatic polycarbonate resin and a polybutylene terephthalate resin having a large content of an aromatic polycarbonate resin, a rubbery polymer, an oxidation polymer By blending titanium, ultraviolet absorber and phosphorus stabilizer and limiting the weight ratio of rubbery polymer and titanium oxide to a specific ratio, fluidity, rigidity, impact resistance, fatigue resistance, weather resistance As a result, the present invention was completed.

  That is, the gist of the present invention is an aromatic polycarbonate resin composition containing 51 to 99 parts by weight of an aromatic polycarbonate resin (component A) and 1 to 49 parts by weight of a polybutylene terephthalate resin (component B). 11 to 25 parts by weight of rubber polymer (C component) and 1 to 5 parts by weight of titanium oxide (D component) with respect to 100 parts by weight of the total of resin (A component) and polybutylene terephthalate resin (B component) In addition, 0.01 to 3 parts by weight of an ultraviolet absorber (component E), 0.001 to 1 part by weight of a phosphorus stabilizer (component F), and a rubbery polymer (component C) and titanium oxide This is a resin composition for producing a painted part having a (D component) weight ratio of 5 to 10.

The aromatic polycarbonate resin composition of the present invention is a resin composition having an excellent balance of physical properties that simultaneously satisfies various physical properties such as fluidity, rigidity, impact resistance, fatigue resistance, weather resistance, and paintability.
The polycarbonate resin composition for manufacturing painted parts of the present invention having such features is widely used in electrical / electronic equipment parts, OA equipment, machine parts, vehicle parts, building members, various containers, leisure goods and miscellaneous goods. In particular, it can be expected to be applied to vehicle exterior / skin parts.

  More specific vehicle exterior / skin parts include outer door handles, bumpers, fenders, door panels, trunk lids, front panels, rear panels, roof panels, bonnets, pillars, side moldings, garnishes, wheel caps, hood bulges, fuel lids. , Various spoilers, motorbike cowls and the like.

  Hereinafter, the present invention will be described in more detail. In the present specification, “to” means that the numerical values described before and after that are included as the lower limit value and the upper limit value, and the “group” possessed by various compounds is within the scope of the present invention. It includes that it may have a substituent.

[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.

  Moreover, what is obtained by the conventionally well-known arbitrary manufacturing method can be used for the aromatic polycarbonate resin (A component) used for this invention. 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, etc. are used. Specifically, phosgene; diaryl carbonates such as diphenyl carbonate, ditolyl carbonate; dimethyl carbonate, diethyl carbonate, etc. 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 or the like, 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). And reacted 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). The addition timing of the molecular weight regulator may be appropriately selected and determined after the phosgenation reaction until 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.

Further, in the aromatic polycarbonate resin, the amount of terminal hydroxyl groups greatly affects the thermal stability, hydrolysis stability, color tone, etc. of the product polycarbonate. Therefore, the aromatic polycarbonate resin 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, for example, a sulfur-containing acidic compound or a derivative formed therefrom. The compound that neutralizes such a catalyst is preferably added in an amount of 0.5 to 10 equivalents, 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 14,000 to 30,000, still more preferably 15,000 to 25,000, and particularly preferably 16000 to 21,000. 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 Mv ^0.83 . Here, the intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity ηsp at each solution concentration [C] (g / dL).

  The terminal hydroxyl group concentration of the aromatic polycarbonate resin used in the present invention is usually 1000 ppm or less, preferably 700 ppm or less, more preferably 400 ppm or less, and particularly preferably 300 ppm or less. The lower limit is preferably 10 ppm or more, more preferably 20 ppm or more, further 30 ppm or more, and particularly preferably 40 ppm or more.

By setting the terminal hydroxyl group concentration to 10 ppm or more, a decrease in molecular weight can be suppressed, and the mechanical properties and fatigue properties of the resin composition tend to be further improved. Moreover, it is preferable for the terminal group hydroxyl group concentration to be 1000 ppm or less because the heat resistance and residence heat stability of the resin composition tend to be further improved.
The terminal hydroxyl group unit is the weight of the terminal hydroxyl group expressed in ppm with respect to the weight of the aromatic polycarbonate resin, and the measurement method is colorimetric determination (Macromol. Chem. 88 215) by the titanium tetrachloride / acetic acid method. (Method of (1965)).

  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 (hereinafter sometimes abbreviated as “component B”) used in the present invention is a polyester having a structure in which a terephthalic acid unit and a 1,4-butanediol unit are ester-bonded, and a dicarboxylic acid A polymer or copolymer in which 50 mol% or more of units consist of terephthalic acid units and 50 mol% or more of diol units consist of 1,4-butanediol units, more preferably polybutylene terephthalate resin (component B) The polybutylene terephthalate resin has a titanium compound content of more than 1 ppm as a titanium atom and 75 ppm or less and 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, Aromatic dicarboxylic acids such as 4,4′-diphenylsulfone dicarboxylic acid and 2,6-naphthalenedicarboxylic acid; fats such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid Cyclic dicarboxylic acids; aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. These dicarboxylic acid components can be introduced into the polymer skeleton as dicarboxylic acids, or using dicarboxylic acid derivatives such as dicarboxylic acid esters and dicarboxylic acid halides as raw materials.

  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 Aliphatic diols such as 1,6-hexanediol and 1,8-octanediol; 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1,4-cyclohexanedimethylol Alicyclic diols such as xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, and the like. This Can.

  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; tricarbaric 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 a 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 (component B) preferably 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 a metal in the polymer by a method such as wet ashing and using a method such as atomic emission, atomic absorption, Inductively Coupled Plasma (ICP).

  The lower limit of the titanium content is preferably 1 ppm, particularly 10 ppm, more preferably 20 ppm, particularly 25 ppm as a titanium atom, and the upper limit is preferably 75 ppm, particularly 50 ppm, particularly 45 ppm, as a titanium atom. . 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 deteriorated, which may be undesirable.

  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. In some cases, the mechanical properties and fatigue characteristics of the polymer alloy of the alloy are lowered, and further, the color tone and weather resistance are lowered.

  The polybutylene terephthalate resin (component B) used in the present invention preferably contains a specific amount of 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. By setting the content of the Group 1 metal compound and / or the Group 2 metal compound to 1 ppm or more, the mechanical properties and fatigue characteristics of the resin composition tend to improve, and the Group 1 metal compound and / or the Group 2 metal compound By making the content of less than 50 ppm, the mechanical properties, fatigue properties, and weather resistance of the resin composition tend to be improved.

  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 titanium compound as described above, but these compounds are those of the polybutylene terephthalate resin (Component B). A co-catalyst for a polycondensation catalyst or a titanium compound catalyst is preferred. There are no particular limitations on the Group 1 metal compound and / or Group 2 metal compound used as the polycondensation catalyst. 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 concentration of the terminal carboxyl group of the polybutylene terephthalate resin (component B) used in the present invention is preferably 39 μeq / g or less, more preferably 5 to 35 μeq / g, and particularly preferably 10 to 30 μeq / g. By setting the terminal carboxyl group to 39 μeq / g or less, it may be preferable from the viewpoint of mechanical properties and fatigue characteristics of the resin composition. Conversely, by setting the terminal carboxyl group concentration to 5 μeq / g or more, the resin composition May be preferable from the viewpoint of mechanical properties, fatigue properties, and weather resistance.
The terminal carboxyl group concentration of the polybutylene terephthalate resin is obtained by dissolving 0.5 g of polybutylene terephthalate resin in 25 mL of benzyl alcohol and titrating with 0.01 mol / L benzyl alcohol solution of sodium hydroxide. be able to.

  At the end of the polybutylene terephthalate resin, there may be a hydroxyl group and a vinyl group in addition to the carboxyl group, and a methoxycarbonyl group derived from the raw material may remain as the other, particularly when dimethyl terephthalate is used as the raw material. Many may remain. In addition, the terminal methoxycarbonyl group in polybutylene terephthalate resin causes toxic methanol, formaldehyde, formic acid, etc. to be generated due to heat 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 amount (concentration) of the terminal methoxycarbonyl group is preferably 0.5 μeq / g or less, more preferably 0.3 μeq / g or less, and further preferably 0.8. 2 μeq / g or less, particularly 0.1 μeq / g or less is preferable.

  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 will be deteriorated, and the terminal vinyl group concentration tends to further increase due to the heat history during molding. In the case of the manufacturing method, the color tone may be further deteriorated.

Each said terminal group density | concentration can be quantified by dissolving polybutylene terephthalate resin in the 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 deuterated 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, mechanical properties and fatigue properties of 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 of products, sprues, runners, etc., and pulverized products obtained from these 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 raw material supply or the discharge form of a polymer. 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. Further, in the present invention, from the viewpoint of productivity, stability of product quality, and the effect of the present invention, it is preferable to employ a method of continuously supplying raw materials and continuously performing an esterification reaction or a 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 portion of 1,4-butanediol is converted to terephthalic acid (or terephthalic acid) in the esterification reaction tank, preferably in the presence of a titanium catalyst. Terephthalic acid (or dialkyl terephthalate) and 1,4-butanediol are continuously esterified (or transesterified) while being fed to the esterification reactor (or transesterification reactor) independently of dialkyl). A process is preferably employed.

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

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

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

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

  Examples of the polycondensation catalyst for the polybutylene terephthalate resin (component B) used in the present invention include the above-mentioned titanium compounds, Group 1 metal compounds and / or Group 2 metal compounds (hereinafter referred to as “titanium catalyst” and “1 group”, respectively). In addition to “metal catalyst” and “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 Is mentioned.

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

  In the production of the polybutylene terephthalate resin (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 reaction aids such as phosphorus compounds such as esters and metal salts thereof.

  In addition, 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 separated from the terephthalic acid (or dialkyl terephthalate) in the reaction liquid phase part. It is preferable to supply directly to Here, the reaction liquid phase part indicates the liquid phase side of the gas-liquid interface in the esterification reaction tank or the 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 titanium catalyst can be supplied directly to the reaction liquid phase part of the esterification reaction tank or the transesterification reaction tank without being dissolved in the solvent or the like, but the supply amount is stabilized, and the reactor In order to reduce adverse effects such as heat denaturation from a heat medium jacket or the like, it is preferable to dilute with a solvent such as 1,4-butanediol. The concentration at this time is usually 0.01 to 20% by weight, particularly 0.05 to 10% by weight, particularly preferably 0.08 to 8% by weight, as the concentration of the titanium catalyst with respect to the whole solution. From the viewpoint of reducing foreign matter, the water concentration in the solution is usually 0.05 to 1.0% by weight, and the temperature during the preparation of the solution is usually 20 to 150 ° C., particularly from the viewpoint of preventing deactivation and aggregation. It is preferable that it is 30-100 degreeC, especially 40-80 degreeC. In addition, the catalyst solution is preferably mixed with separately supplied 1,4-butanediol and piping or the like and supplied to the esterification reaction tank or transesterification reaction tank from the viewpoints 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 and the titanium catalyst, or may be supplied independently.
Among these, from the viewpoint of the stability of the catalyst, it is preferable that the terephthalic acid or the titanium catalyst is supplied to the upper surface of the reaction liquid independently from the reaction liquid 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, etc., in water, a solvent such as 1,4-butanediol, and a copolymer component such as polytetramethylene ether glycol. It is preferable to melt | dissolve and supply as a solution, and the density | concentration in this case is the same as the above-mentioned solution density | concentration.

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

  Next, this oligomer is transferred to a polycondensation reaction tank and polycondensed in the presence of a polycondensation catalyst in one or a plurality of polycondensation reaction tanks. 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 the 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.

  Subsequently, this oligomer is transferred to a polycondensation reaction tank, and preferably continuously in the presence of a polycondensation reaction catalyst in one or a plurality of polycondensation reaction tanks, usually at 210 to 280 ° C., preferably 220 to 260. ℃, more preferably at 230-250 ℃, in at least one polycondensation reaction tank, usually 20 kPa or less, preferably 10 kPa or less, more preferably 5 kPa or less, with stirring, usually 2 to 15 The polycondensation reaction is performed for a time, preferably 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 transesterification reaction tank, any conventionally known one can be used, for example, any type of vertical stirring complete mixing tank, vertical heat convection mixing tank, tower type continuous reaction tank, etc. There may be. Also, a single tank may be a plurality of tanks in which the same kind or different kinds of tanks are connected 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. It is also possible to use a type that rotates at high speed.

  The form of stirring is not particularly limited, and in addition to the usual stirring method in which the reaction liquid in the reaction tank is directly stirred from the top, bottom, side, etc. of the reaction tank, a part of the reaction liquid is connected to the reactor by piping or the like. A method in which the reaction liquid is circulated 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, or a combination thereof. 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. It is also possible to use a type that rotates at high speed.

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

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

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

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

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

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

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

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

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

In FIG. 2, the oligomer supplied from the above-described extraction line (4) shown in FIG. 1 is polycondensed under reduced pressure in the first polycondensation reaction tank (a) to become a prepolymer, and then extracted. It supplies to a 2nd polycondensation reaction tank (d) through a gear pump (c) and an extraction line (L1).
If it is necessary to add Group 1 and / or Group 2 metal catalysts, these catalysts are diluted with a solvent such as 1,4-butanediol in a preparation tank (not shown) and adjusted to a predetermined concentration. Via (L7), it is connected to a 1,4-butanediol supply line (L8), further diluted with 1,4-butanediol, and then supplied to the oligomer extraction line (4). The same applies to FIG.

  In the second polycondensation reactor (d), polycondensation usually proceeds at a lower pressure than that of the first polycondensation reactor (a) to become a polymer. The polymer obtained 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 rotated with a rotary cutter (h ) To form pellets. Further, in FIG. 3, the polymer obtained in the second polycondensation reactor (d) is supplied to the third polycondensation reaction tank (k) via the extraction gear pump (e) and the extraction line (L3). To do. The third polycondensation reaction tank (k) is a horizontal reaction tank composed of a plurality of stirring blade blocks and equipped with a biaxial self-cleaning type stirring blade.

Usually, in the second polycondensation reaction tank (d), polycondensation proceeds at a lower pressure than in the first polycondensation reaction tank (a), and in the third polycondensation reaction tank (k), polycondensation proceeds further. It becomes a polymer.
The polymer obtained in the third condensation reactor (k) is withdrawn in the form of a melted strand from the die head (g) through the extraction gear pump (m) and the extraction line (L5) After being cooled, it is cut with a rotary cutter (h) into pellets.
Reference numerals (L2), (L4), and (L6) in FIGS. 2 and 3 are vent lines of the respective polycondensation reaction tanks (a), (d), and (k).

[3] Rubber polymer (component C)
The rubbery polymer used in the present invention has a glass transition temperature of 0 ° C. or lower, particularly −20 ° C. or lower, and is a polymer obtained by copolymerizing a rubbery polymer with a monomer component copolymerizable therewith. Is also included. As the component C used in the present invention, any conventionally known component that can be generally blended in a polycarbonate resin composition or the like to improve its mechanical properties can be used.

Examples of component C include polybutadiene, polyisoprene, diene copolymers (styrene / butadiene copolymers, acrylonitrile / butadiene copolymers, acrylic / butadiene rubbers, etc.), copolymers of ethylene and α-olefin ( Ethylene / propylene copolymer, ethylene / butene copolymer, ethylene / octene copolymer, etc.), copolymer of ethylene and unsaturated carboxylic acid ester (ethylene / methacrylate copolymer, ethylene / butyl acrylate copolymer) Etc.), copolymers of ethylene and aliphatic vinyl compounds, terpolymers of ethylene, propylene and nonconjugated dienes, acrylic rubber (polybutyl acrylate, poly (2-ethylhexyl acrylate), butyl acrylate / 2-ethylhexyl acrylate Polymers, etc.), Silico System Rubber (polyorganosiloxane rubber, polyorganosiloxane rubber and a polyalkyl (meth) IPN type composite rubber consisting of acrylate rubber), and the like.
These may be used alone or in combination of two or more. “(Meth) acrylate” means “acrylate” and “methacrylate”, and “(meth) acrylic acid” described later means “acrylic acid” and “methacrylic acid”.

  Moreover, as C component used for this invention, you may use the copolymer which monomer-component polymerized to the rubber-like polymer. Preferred examples of this monomer include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, and the like. Other monomer components include epoxy group-containing (meth) acrylic acid ester compounds such as glycidyl (meth) acrylate; maleimide compounds such as maleimide, N-methylmaleimide, N-phenylmaleimide; maleic acid, phthalic acid, itacon Examples include α, β-unsaturated carboxylic acid compounds such as acids and anhydrides thereof (eg, maleic anhydride). These monomer components may be used alone or in combination of two or more.

  The component C used in the present invention is preferably of the core / shell type graft copolymer type from the viewpoint of impact resistance. Among them, at least one selected from butadiene-containing rubber, butyl acrylate-containing rubber, and silicone rubber is used as a rubber polymer core layer, and at least one selected from acrylic acid ester, methacrylic acid ester, and aromatic vinyl compound around it. A core / shell type graft copolymer comprising a shell layer formed by copolymerizing the above monomer components is particularly preferred.

  More specifically, methyl methacrylate-butadiene-styrene polymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene polymer (MABS), methyl methacrylate-butadiene polymer (MB), methyl methacrylate-acrylic rubber polymer ( MA), methyl methacrylate-acrylic rubber-styrene polymer (MAS), methyl methacrylate-acrylic butadiene rubber copolymer, methyl methacrylate-acrylic butadiene rubber-styrene copolymer, methyl methacrylate- (acrylic silicone IPN (interpenetrating) polymer network) rubber) polymer and the like. Such rubbery polymers may be used alone or in combination of two or more.

  Specific examples of other rubbery polymers include polybutadiene rubber, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene / butylene-styrene block copolymer ( SEBS), styrene-ethylene / propylene-styrene block copolymer (SEPS), acrylonitrile-butadiene-styrene polymer (ABS), acrylonitrile-styrene-acrylic rubber polymer (ASA), acrylonitrile-ethylenepropylene rubber-styrene polymer (AES) etc. are mentioned.

[4] Titanium oxide (component D)
Various titanium oxides can be used as titanium oxide (D component) in the present invention. The particle size of titanium oxide (component D) is preferably 0.05 to 0.5 μm. When the particle diameter is less than 0.05 μm, the light shielding property and light reflectance are inferior, and when it exceeds 0.5 μm, the light shielding property and light reflectance are inferior, and the surface of the molded product is roughened or the impact strength is reduced. Cheap. The particle diameter of titanium oxide (D component) is more preferably 0.1 to 0.5 μm, and most preferably 0.15 to 0.35 μm.

  The titanium oxide (component D) is preferably titanium oxide produced by a chlorine method. Titanium oxide produced by the chlorine method is superior in terms of whiteness and the like as compared with titanium oxide produced by the sulfuric acid method. As the crystal form of titanium oxide (component D), rutile type titanium oxide is preferable, and is superior in terms of whiteness, light reflectance and weather resistance as compared with anatase type titanium oxide.

  Titanium oxide is generally surface-treated with an inorganic surface treatment agent (alumina and / or silica). Further, it is treated with an organic surface treatment agent. As the organic surface treatment agent, surface treatment is performed with an organosilane compound or an organosilicone compound having an alkoxy group, an epoxy group, an amino group, or a Si—H bond. Particularly preferred are silicone compounds having Si-H bonds.

[5] Ultraviolet absorber (E component)
Examples of the ultraviolet absorber (component E) used in the present invention include organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, triazine compounds, malonic acid ester compounds, cyanoacrylate compounds, benzoxazoline compounds, cerium oxide, and zinc oxide. Inorganic ultraviolet absorbers such as, for example, are preferably organic ultraviolet absorbers, more preferably benzotriazole compounds, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5. -[(Hexyl) oxy] -phenol, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol 2,2 ′-(1,4-phenylene) bis [4H-3,1-benzoxazin-4-one], [(4-methoxyphenyl) -me Tylene] -propanedioic acid-dimethyl ester, and particularly preferred is a benzotriazole-based ultraviolet absorber represented by the following general formula (1).

(Wherein, X is a phenyl group, a hydroxyl group or a phenyl group substituted with an alkyl group having 1 to 10 carbon atoms, R ₁ to R ₄ is a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms)

  Specific examples of the benzotriazole ultraviolet absorber include, for example, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, Examples include 2- (2′-hydroxy-5-octylphenyl) benzotriazole.

  Among these, in the present invention, 2- (5-methyl-2-hydroxyphenyl) benzotriazole represented by the following formula (d-1) and 2- (5-methyl-2-hydroxyphenyl) benzotriazole represented by the following formula (d-2) are particularly preferred. (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole is preferred. Specific product names of formulas (d-1) and (d-2) include Tinuvin P and Tinuvin 326 manufactured by Ciba Specialty, respectively.

  In the present invention, a hindered amine weather resistance stabilizer is used in addition to the E component benzotriazole ultraviolet absorber. The amine compound usually tends to promote hydrolysis of the aromatic polycarbonate resin and its use is not preferred. In the present invention, the hindered amine weather resistance having a specific structure represented by the following general formula (2) is used. When the stabilizer is used in combination with the above benzotriazole-based compound, a special effect is exhibited.

(However, R < ₅ > -R < ₈ > shows a hydrogen atom or a methyl group in a formula)

  The hindered amine-type weather resistance stabilizer in the present invention is a compound having a structure represented by the general formula (2), and the weather resistance can be further improved by using it together with the component (E). Specific examples thereof include those shown in the following formulas (e-1) and (e-2). The trade names of the formulas (e-1) and (e-2) are Sanol LS-2626 manufactured by Sankyo Co., Ltd. and Tinuvin 622LD (molecular weight 3100-4000) manufactured by Ciba Specialty, respectively.

[6] Phosphorus stabilizer (component F)
In the present invention, a phosphorus-based stabilizer (F component) is used to improve heat resistance and residence heat stability. Any conventionally known phosphorous stabilizer (F component) can be used. Specifically, phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, phosphorus oxo acid such as polyphosphoric acid, acidic pyrophosphoric acid metal salt such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, acidic calcium pyrophosphate, potassium phosphate , Sodium phosphate, cesium phosphate, zinc phosphate and other group 1 or group 2B metal phosphates, organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, and the like.
Among these, an organic phosphate compound represented by the following general formula (I) and / or an organic phosphite compound represented by the following general formula (II) is preferred, and more preferably represented by the following general formula (I). An organic phosphate compound.

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’はアルキル基又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 ′ is an alkyl group or an aryl group, and each 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 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.

  In the resin composition for producing a painted part of the present invention, the content ratio of the A component to the F component constituting the resin component is 51 to 99 parts by weight of an aromatic polycarbonate resin (A component), polybutylene terephthalate resin (B component) 1 A resin composition containing ˜49 parts by weight, wherein the rubbery polymer (C component) is 11 to 25 parts by weight and the titanium oxide (D component) is 1 with respect to 100 parts by weight of the total of the A component and the B component. -5 parts by weight, UV absorber (E component) 0.01-3 parts by weight, phosphorus stabilizer (F component) 0.001-1 part by weight, and rubbery polymer (C component) ) And titanium oxide (component D) in a weight ratio of 5 to 10.

In the resin composition for producing a painted part according to the present invention, among the total 100 parts by weight of the A component and the B component, the A component is preferably 55 to 90 parts by weight, particularly 60 to 85 parts by weight. Among these, 10 to 45 parts by weight, particularly 15 to 40 parts by weight is preferable.
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 component C is preferably 12 to 24 parts by weight, particularly 14 to 21 parts by weight, with respect to 100 parts by weight of the total of the components A and B. When the C component is 11 parts by weight or more, impact resistance is improved, and when it is 25 parts by weight or more, rigidity, fatigue characteristics, and heat resistance tend to be lowered.
The D component is preferably 1.5 to 4 parts by weight with respect to 100 parts by weight of the total of the A and B components. When the D component is 1 part by weight or more, the weather resistance is good, and when it exceeds 4 parts by weight, the impact resistance is lowered.
Moreover, it is preferable that the weight ratio of a rubber-like polymer (C component) and titanium oxide (D component) is 5.5-9. If the ratio of the C component to the D component is less than 5, the impact resistance is insufficient, and if it exceeds 10, the weather resistance is lowered.

The E component is preferably 0.03 to 2 parts by weight with respect to a total of 100 parts by weight of the A and B components. If the E component is less than 0.01 parts by weight, the weather resistance is insufficient, and if it exceeds 3 parts by weight, mold deposits are likely to occur, the paintability is lowered, and the residence heat stability and impact resistance are also lowered.
Furthermore, the resin composition of the present invention contains 0.01 to 3 parts by weight of a hindered amine-based weathering stabilizer in addition to the ultraviolet absorber of the E component with respect to a total of 100 parts by weight of the A and B components. It is preferable to do.
Especially, it is preferable to mix | blend 0.03-2 weight part with respect to a total of 100 weight part of A component and B component of a hindered amine type weather resistance stabilizer. When the blending ratio of the hindered amine-based weather resistance stabilizer is less than 0.01 parts by weight, the weather resistance is insufficient, and when it exceeds 3 parts by weight, mold deposit is likely to occur, the paintability is lowered, and the residence heat stability and impact resistance are reduced. Also decreases.

  The F component is preferably contained in an amount of 0.003 to 0.5 parts by weight with respect to a total of 100 parts by weight of the A and B components. If the F component is less than 0.001 part by weight, the effect of improving the thermal stability of the resin composition is small, and if it exceeds 1 part by weight, mold deposits are likely to occur and the paintability also deteriorates.

The resin composition of the present invention may contain other resins and various resin additives in addition to the above-described components A to F as long as the purpose of the present invention is not impaired as required.
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 / pigments, reinforcing agents, flame retardants, antistatic agents, antifogging agents, lubricants / antiblocking agents, fluidity improvers, plasticizers, dispersants. And antibacterial agents. These may be used alone or in combination of two or more.

The resin composition of the present invention can be produced by appropriately selecting a conventionally known arbitrary method for resins, additives, and the like in addition to the components A to F.
Specifically, for example, the A to F components and additive components blended as necessary are mixed in advance using various mixers such as a tumbler and a Henschel mixer, and then Banbury mixer, roll, Brabender, single-screw kneading extrusion The resin composition can be produced by melt-kneading with a machine, a twin-screw kneading extruder, a kneader or the like. Alternatively, 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 insulation 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.
The painted component according to the present invention is obtained by painting a molded product produced from a resin composition as described above. Examples of the type of paint used for painting include urethane-based (one-liquid curing type, 2 Liquid curing type), acrylic urethane type, epoxy type, vinyl chloride-vinyl acetate copolymer type, acrylic type, acrylic alkyd type, aminoalkyd type paint, and the like. Examples of the coating method include spray spraying, brush coating, and dipping method.

In addition, in the present invention, from the viewpoint of reducing environmental burdens such as waste reduction and cost reduction, when manufacturing a molded product from a resin composition, non-conforming product, sprue, runner, used product, etc. are recycled. The raw material can be mixed with the virgin material for recycling, so-called material recycling. In this case, it is preferable to use the recycled raw material because it can be used after being pulverized, since it can reduce problems when producing a molded product.
The content ratio of the recycled material is preferably 70% by weight or less, more preferably 50% by weight or less, and further preferably 30% by weight or less, out of a total of 100% by weight of the recycled material and the virgin material.

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

In obtaining each resin composition of Examples and Comparative Examples, the following raw materials were prepared.
<Aromatic polycarbonate resin: Component A>
PC-1: Bisphenol A type aromatic polycarbonate produced by an interfacial polymerization method (“Iupilon S-3000” manufactured by Mitsubishi Engineering Plastics, viscosity average molecular weight 22500, terminal hydroxyl group concentration = 150 ppm)
PC-2: Bisphenol A type aromatic polycarbonate produced by an interfacial polymerization method (“Iupilon H-3000” manufactured by Mitsubishi Engineering Plastics, viscosity average molecular weight 19000, terminal hydroxyl group concentration = 150 ppm)

<Polybutylene terephthalate resin: Component B>
PBT-1: Production Example 1
Through the esterification step shown in FIG. 1 and the polycondensation step shown in FIG. 3, a polybutylene terephthalate resin was produced in the following manner. First, a 60 ° C. slurry mixed at a ratio of 1.80 moles of 1,4-butanediol with respect to 1.00 moles of terephthalic acid is passed through the raw material supply line (1) from the slurry preparation tank in advance with an esterification rate of 99%. To a reaction vessel (A) for esterification having a screw type stirrer filled with the polybutylene terephthalate oligomer was continuously fed at 41.0 kg / h.
At the same time, the bottom component of the rectification column (C) at 185 ° C. is fed at 17.2 kg / h from the recirculation line (2), and 6. 5% of tetrabutyl titanate at 65 ° C. is used as the catalyst from the catalyst feed line (3). A 0 wt% 1,4-butanediol solution was fed at 97 g / h (30 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) And 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 rectification 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 2.1 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 130 Pa, the liquid level is controlled so that the residence time is 90 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 240 ° C., the pressure was 130 Pa, the residence time was 60 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 polymer solution having a concentration of 1.0 g / dL and the number of falling seconds of the solvent alone were measured and obtained from the following formula.
IV = ((1 + 4K _H η _sp ) ^0.5 −1) / (2K _H C)
(Where η _sp = n / n ₀ −1, n is the polymer solution falling seconds, n ₀ is the solvent dropping seconds, C is the polymer solution concentration (g / dL), and K _H is the Huggins constant. 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 polycondensation step is carried out in the step shown in FIG. 2, and the slurry is supplied at 41 kg / h in PBT-1, and the bottom component of the rectification column (C) is supplied from the recirculation line (2) to 17. The catalyst was fed at a rate of 2 kg / h, and a 6.0 wt% 1,4-butanediol solution of tetrabutyl titanate at 65 ° C. was fed as a catalyst from the catalyst feed line (3) at 97 g / h (30 ppm relative to the theoretical polymer yield). The esterification reaction was carried out in the same manner as PBT-1.
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 third polycondensation reaction tank (k) is The procedure was the same as PBT-1, except that it 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 2 is referred to as PBT-2.

PBT-3: Production Example 3
The esterification step in the reactor (A) was carried out in the same manner as PBT-1. After 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, 20% by weight, It prepared in the preparation tank (not shown) so that it might become 75 weight%. The temperature at this time was 25 ° C. This solution was supplied to the 1,4-butanediol line (L8) through the supply line (L7), and a predetermined amount was supplied to the oligomer extraction line (4) as a solution having a lower concentration.
The internal temperature of the first polycondensation reactor (a) is 246 ° C., the pressure is 2.4 kPa, and the residence time is 120 minutes. The internal temperature of the second polycondensation reactor (d) is 239 ° C., the pressure is 150 Pa, and the residence time is 130 minutes. The internal temperature of the third polycondensation reactor (k) was 238 ° C., the pressure was 130 Pa, and the residence time was 70 minutes. The analysis values of the obtained PBT are collectively shown in Table 1. Hereinafter, the polybutylene terephthalate resin obtained in Production Example 3 is referred to as PBT-3.

PBT-4: Production Example 4
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 those of PBT-3, the internal temperature of the second polycondensation reaction tank (d) is 238 ° C., the pressure is 200 Pa, 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 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. In place of PBT-3 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 for PBT-3, 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-3 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 5 is referred to as PBT-5.

PBT-6:
PBT-6, DURANEX 2002 (trade name) manufactured by Wintech Polymer Co., Ltd., intrinsic viscosity IV is 1.03 dL / g, titanium atom content is 78 ppm, terminal carboxyl group concentration is 54 μeq / g, terminal methoxycarbonyl group Polybutylene terephthalate having a concentration of 2 μeq / g was used.

<Rubber polymer: Component C>
Core / shell type graft copolymer consisting of polybutadiene (core) / alkyl acrylate / alkyl methacrylate copolymer (shell) ("EXL2603" manufactured by Rohm and Haas Japan)
<Titanium oxide: D component>
Rutile-type titanium oxide produced by the chlorine method, treated with silica alumina (inorganic treatment) and methylhydrogenpolysiloxane (organosilicone compound) (“Taipek PC-3” manufactured by Ishihara Sangyo Co., Ltd.), particle size 0.21 μm
<Ultraviolet absorber: E component>
Benzotriazole ultraviolet absorber: 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole (“Tinuvin 326” manufactured by Ciba Specialty)

<Phosphorus stabilizer: F component>
F-1:
Organic phosphate compound represented by the chemical formula O = P (OH) _{n ′} (OC ₁₈ H ₃₇ ) _{3-n ′} (mixture of n ′ = 1 and 2), “Adeka Stab AX-71” manufactured by Asahi Denka Kogyo Co., Ltd.
F-2:
Distearyl pentaerythritol diphosphite, “ADK STAB PEP-8” manufactured by Asahi Denka Kogyo Co., Ltd.
<Other ingredients>
Hindered amine weathering stabilizer: 1- [2- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3- (3,5-di-tert -Butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-tetramethylpiperidine, “Sanol LS-2626” manufactured by Sankyo Co., Ltd.

[Preparation of resin composition]
After the A to F components and other components were uniformly mixed at a ratio shown in Table 2, using a tumbler mixer, 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 at a cylinder temperature of 270 ° C. and a screw speed of 200 rpm, and melt-kneading.

[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. An ASTM test piece was prepared under the condition of seconds.

[Evaluation methods]
(1) Fluidity (Q value)
Using an elevated flow tester, the flow rate Q value (unit: cc / 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) Rigidity (flexural modulus)
In accordance with ASTM D790, measurement was performed at 23 ° C. using a test piece having a thickness of 6.4 mm.

(3) 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.
(4) Weather resistance (anti-fading acceleration test)
Using a sunshine weather tester from Suga Test Instruments Co., Ltd. in accordance with JIS D0205, a flat molded product with a thickness of 3.2 mm is treated for 240 hours under conditions of a black panel temperature of 63 ° C. and a rain spray of 12 minutes / 60 minutes. did. The hue before and after the treatment was measured with a color difference meter (model: SE-2000) manufactured by Nippon Denshoku Industries Co., Ltd. according to ASTM-E1925 to determine the hue change ΔE. The smaller the value of △ E, the harder it is to discolor.

(5) Fatigue properties (bending fatigue failure)
In accordance with ASTM D671, a test was performed at 23 ° C. and an actual stress of 14 MPa using a Type 1 test piece, and the number of times of failure was evaluated.
(6) Paintability (coating adhesion test)
Dainippon Paint Co., Ltd. Urethane paint (trade name: V-top two-component white paint) main agent and curing agent are weighed and mixed at a weight ratio of 4: 1, and the total of the main agent and curing agent is 100 parts by weight. The paint thinner was diluted with 40 parts by weight. This paint dilution was sprayed onto a 3.2 mm thick flat plate molded product to a coating thickness of 30 μm, and after 30 minutes of writing at 100 ° C., a painted part was obtained. . On the painted surface of this painted part, 11 cuts were orthogonally crossed with a cutter knife at 1 mm intervals to form 100 gobangs, and Nichiban cellophane tape was adhered to it, and then it was peeled off in a perpendicular direction. . The number of eyes that were not peeled off at this time was used as a numerator, and the number of first formed Gobang eyes (here, 100) was evaluated as a denominator. 100/100 is desirable.
(7) Impact resistance after painting (surface impact strength at low temperature and high speed)
5m / sec using a high speed puncture impact tester (trade name: Hydroshot) manufactured by Shimadzu Corporation in accordance with ASTM D-3763 while maintaining the same painted part as in (6) at an ambient temperature of −30 ° C. The destructive test was carried out at a constant hitting speed. The fracture energy value was calculated from the displacement and load curve until fracture. The unit of fracture energy is indicated by J (joule).

[Examples 1 to 10, Comparative Examples 1 to 6]
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 composition for producing coated parts described in Examples 1 to 10 of the present invention has a balance of fluidity, impact resistance (with or without coating), rigidity, weather resistance, fatigue characteristics, and paintability. It is an excellent material.
On the other hand, since the composition of Comparative Example 1 does not contain an ultraviolet absorber (E component), the weather resistance is inferior compared to the Examples. The compositions of Comparative Examples 2 and 3 have a rubbery polymer (component C) content outside the scope of the present invention, and are particularly inferior in impact resistance. Furthermore, the compositions of Comparative Examples 5 and 6 have a rubbery polymer (component C) content outside the scope of the present invention, and the weight ratio with titanium oxide (component D) is also outside the range. Therefore, in Comparative Example 5, the impact resistance is inferior, and in Comparative Example 6, the weather resistance is inferior.
In the composition of Comparative Example 4, the weight ratio of the rubber polymer (C component) and titanium oxide (D component) is outside the range of the present invention, and the weather resistance is higher than that of the composition of the example. Is inferior.

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

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 : Extraction line L5: Extraction line L2: Vent line L4: Vent line L6: Vent line L7: Group 1 / Group 2 metal compound catalyst supply line L8: 1,4-butanediol supply line a: First polycondensation reaction Tank d: Second polycondensation reaction tank k: Third polycondensation reaction tank c: Extraction gear pump e: Extraction gear pump m: Extraction gear pump g: Die head h: Rotary cutter

Claims (15)

  An aromatic polycarbonate resin composition comprising 51 to 99 parts by weight of an aromatic polycarbonate resin (component A) and 1 to 49 parts by weight of a polybutylene terephthalate resin (component B), wherein the aromatic polycarbonate resin (component A) and polybutylene 11 to 25 parts by weight of rubbery polymer (C component), 1 to 5 parts by weight of titanium oxide (D component), and UV absorber (E component) with respect to 100 parts by weight of the total terephthalate resin (B component) In an amount of 0.01 to 3 parts by weight, and a phosphorus stabilizer (F component) in an amount of 0.001 to 1 part by weight, and the weight ratio of the rubber polymer (C component) to titanium oxide (D component) is The resin composition for coating parts manufacture which is 5-10.   2. The coating according to claim 1, wherein the content of the titanium compound in the polybutylene terephthalate resin (component B) is more than 1 ppm as a titanium atom and 75 ppm or less, and the terminal carboxyl group concentration is 39 μeq / g or less. Resin composition for manufacturing parts.   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 resin composition for producing a painted part according to claim 1, wherein the resin composition is 50 ppm or less.   4. The resin composition for producing a painted part according to claim 1, wherein the polybutylene terephthalate resin (component B) has a terminal methoxycarbonyl group concentration of 0.5 μeq / g or less.     5. The resin composition for producing a coated part according to claim 1, 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 resin composition for producing a coated part according to any one of claims 1 to 5, wherein the terminal carboxyl group concentration of the polybutylene terephthalate resin (component B) is 10 to 30 µeq / g.   The polybutylene terephthalate resin (component B) contains a magnesium compound as a group 2 metal compound, the resin composition for producing a painted part according to any one of claims 3 to 6.   The coating according to any one of claims 1 to 7, comprising 10 to 45 parts by weight of a polybutylene terephthalate resin (B component) with respect to 55 to 90 parts by weight of the aromatic polycarbonate resin (A component). Resin composition for manufacturing parts.   9. The resin composition for producing a painted part according to claim 1, wherein the rubber polymer (component C) is a core / shell type graft copolymer.   The content of the rubber polymer (C component) is 15 to 20 parts by weight with respect to 100 parts by weight in total of the polycarbonate resin (A component) and the polybutylene terephthalate resin (B component). The resin composition for coating parts manufacture in any one of Claims 1 thru | or 9.   The resin composition for producing a coated part according to any one of claims 1 to 10, wherein the ultraviolet absorber (component E) is a benzotriazole ultraviolet absorber.   The hindered amine-based weather resistance stabilizer is contained in an amount of 0.01 to 3 parts by weight with respect to a total of 100 parts by weight of the polycarbonate resin (component A) and the polybutylene terephthalate resin (component B). 11. The resin composition for producing a painted part according to any one of 11 above. The resin composition for producing a coated part according to any one of claims 1 to 12, wherein the phosphorus-based heat stabilizer (F component) is an organic phosphate compound represented by the following general formula (I).
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.)   The viscosity average molecular weight [Mv] of aromatic polycarbonate resin (A component) is 15000-25000, The resin composition for coating component manufacture in any one of Claims 1 thru | or 13 characterized by the above-mentioned.   A painted part obtained by coating a molded product obtained by molding the resin composition for producing a painted part according to claim 1.

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