JP2007161840A - Polyethylene terephthalate resin composition, and resin molded product and laminated product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polybutylene terephthalate resin composition giving resin molded products excellent in mechanical strength and heat resistance and metal laminated products excellent in specular clarity, surface smoothness and metal layer adhesion, and suppressed in degradation of these characteristics even under high temperature environment, to provide resin molded products and resin-metal laminated products, obtained by molding the composition. <P>SOLUTION: The polybutylene terephthalate resin composition comprises, based on 100 pts.wt. (A) polybutylene terephthalate resin, 5-80 pts.wt. (B) polyethylene terephthalate resin and 0-80 pts.wt. (C) fine particulate filler, wherein the (A) polybutylene terephthalate resin contains (a) titanium compound, (b) a group 1 metal compound and/or a group 2 metal compound, (a) titanium compound content is ≥10 ppm but ≤80 ppm expressed in terms of titanium atom, and the content of (b) the group 1 metal compound and/or the group 2 metal compound is ≥1 ppm but ≤50 ppm expressed in terms of the metal atom. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polyester resin composition, a resin molded body obtained by molding the polyester resin composition, and a laminate in which a metal layer is provided on the surface of the resin molded body. More specifically, it is possible to provide a light reflector or the like which is excellent in so-called direct metal layer forming ability by providing a metal layer on the surface of a resin molded body by vapor deposition or the like, and has a good surface appearance such as mirror sharpness and surface smoothness. The present invention relates to a polybutylene terephthalate resin, a resin molded body obtained by molding the polybutylene terephthalate resin, and a laminate in which a metal layer is provided on the surface of a resin molded product.

  Light reflectors incorporated in housings, reflectors, extensions, home appliance lighting fixtures, etc. in automotive lamps have high brightness, smoothness, and uniform reflection to improve the directionality and reflectivity of the lamp light source. The rate and further high heat resistance are required. In general, such a light reflector has a metal (sheet metal) itself, a bulk molding compound (BMC), a sheet molding compound (SMC), etc. on the surface of a thermosetting resin by metal plating, vapor deposition, coating, etc. A resin / metal laminate (hereinafter sometimes simply referred to as “laminate”) provided with a metal thin film layer has been used.

  This light reflector is often required to have a complicated shape. For example, a metal reflector has a problem that workability is poor, and it is heavy and difficult to handle. On the other hand, the laminate described above has excellent characteristics such as heat resistance, rigidity, and dimensional stability, but the molding cycle is long, burrs are generated during molding, and monomers are volatilized during molding. As a result, there is a problem that problems may occur in the work environment. For this reason, there is no such problem, and with the enhancement of functionality and diversification of the design of these light reflectors, a resin molded body formed by molding a thermoplastic resin, which is excellent in productivity, is used as a base. A laminate having a metal layer on the surface has been studied.

  Such a light reflector made of a thermoplastic resin substrate has, for example, excellent mechanical properties, electrical properties, other physical and chemical properties, and good workability as the substrate. Thermoplastic polyester resins, particularly polybutylene terephthalate resins, are being studied. For example, a polybutylene terephthalate resin alone, a mixture with a polyethylene terephthalate resin or the like, and a resin composition in which a reinforcing material is added and mixed are being studied.

In general, polybutylene terephthalate resin has a problem that since it has a high crystallization speed, it solidifies quickly in a mold and it is difficult to obtain good mirror transfer. In particular, in the case of a polybutylene terephthalate resin composition to which an inorganic filler such as talc or mica is added in order to impart heat resistance, the relief of these fillers becomes significant.
For such a problem, for example, a method has been proposed in which a metal layer is formed by vacuum deposition or the like after a pretreatment (undercoating) such as an undercoat is performed on a resin molded body to form a light reflector ( For example, see Patent Document 1).

However, since undercoating such as an undercoat greatly increases the cost, it is desired to obtain a light reflector having a high luminance feeling without undercoating. In order for the reflector provided with a light reflecting layer on one surface of the molded body without undercoating to achieve high brightness and uniform reflectance, the resin molded body itself has good surface smoothness, and It needs to have high gloss and brightness. However, this requires the surface smoothness of the molding die to be remarkably improved, and there has been a problem that the mold release at the time of taking out the molded product is lowered and the molding cycle is lowered. Therefore, it has been required to improve both moldability and mold release properties and to maintain the surface brightness of the resin molded body.

  In response to this, a method has been proposed in which an amorphous polymer is added to polybutylene terephthalate resin, the crystallization speed of the material is lowered to improve the mold transferability, and the filler is prevented from being raised (for example, Patent Document 2). Further, as a molding method, a method for improving fluidity by increasing the resin temperature (see, for example, Patent Document 3), or a method for increasing mold temperature by delaying the solidification rate to improve mold transferability (for example, Patent Document 4). Etc.) have been proposed.

  However, even with these methods, the appearance of the molded product is improved, but an increase in the resin temperature and mold temperature increases the generation of volatile components at the time of molding, thereby deteriorating the working environment. Furthermore, since such volatile matter causes a haze-like appearance defect on the surface of the molded body, it is difficult to obtain a good molded product continuously, and new mold polishing, wiping, etc. There has been a problem of requiring appropriate measures. In addition, when exposed to a high temperature atmosphere, the metal surface is violated and clouding occurs.

  In addition, such amorphous polymers have low heat resistance and generally poor compatibility with polybutylene terephthalate resins. Therefore, the surface property and brightness sensation caused by the amorphous polymer under high temperature conditions such as molding. There was a problem of causing a drop in Furthermore, when the light reflector is used, there is a problem that the heat resistance level is not sufficient.

For this, (A) 5 to 80 parts by weight of polyethylene terephthalate resin and (C) average primary particle size with respect to 100 parts by weight of polybutylene terephthalate resin having a terminal carboxyl group amount of 50 meq / kg or less. There has been proposed a light reflector in which a resin molded article obtained by molding a resin composition containing 2 to 50 parts by weight of a non-fibrous inorganic filler of 10 μm or less is used as a base and a metal layer is provided on at least a part of the base ( For example, see Patent Document 7). However, even with this method, it is difficult to satisfy mechanical strength, heat resistance (thermal deformation temperature), etc. when the thickness is reduced in response to the recent demand for thinner light reflectors. There was a problem.
JP-A-6-203613 Japanese Patent Laid-Open No. 11-293099 JP 2002-88235 A Japanese Patent Laid-Open No. 11-241005 Japanese Patent Laid-Open No. 2005-41977 JP-A-2005-146103 JP 2000-35509 A

  In this way, the laminate of resin and metal used as a light reflector is excellent in mechanical strength, heat resistance, specular sharpness, and surface smoothness, particularly when volatile matter is generated when exposed to a high temperature atmosphere. There is a demand for a laminate that suppresses deformation, maintains high reflectivity, and has excellent adhesion to a metal layer, a resin molded body that serves as the base, and a polybutylene terephthalate resin composition that forms the laminate. It was.

  As a result of intensive studies to solve the above problems, the present inventors have found that a specific polyester resin, specifically, a polybutylene terephthalate resin composition containing a specific polybutylene terephthalate resin and a specific amount of a specific inorganic filler. However, it has been found that heat resistance and mechanical strength are improved and generation of volatile components when exposed to a high temperature atmosphere is suppressed. The present inventors have found that the resin / metal laminate formed by molding the polybutylene terephthalate resin composition is suppressed in deformation even under a high temperature atmosphere and realizes a high brightness feeling, thereby completing the present invention.

  That is, the gist of the present invention includes (B) 5 to 80 parts by weight of a polyethylene terephthalate resin and (C) 0 to 80 parts by weight of a fine powder filler with respect to 100 parts by weight of (A) polybutylene terephthalate resin, (A) The polybutylene terephthalate resin contains (a) a titanium compound and (b) a Group 1 metal compound and / or a Group 2 metal compound, and (a) the content of the titanium compound is 10 ppm or more in terms of titanium atoms. A polybutylene terephthalate resin composition, wherein the content of the group 1 metal compound and / or the group 2 metal compound is 80 ppm or less in terms of metal atoms, and (b) It exists in the resin molded product formed and the laminated body which used this resin molded object as a base | substrate, and provided the metal layer on the surface.

  The polybutylene terephthalate resin composition of the present invention is excellent in mechanical strength and heat resistance when formed into a resin molded body, and also has a mirror surface sharpness, surface smoothness, and metal layer adhesion when formed into a laminate with a metal. In addition, it has excellent characteristics that these characteristic deteriorations are suppressed even in a high temperature environment. And by such a characteristic, the light reflector which has the outstanding characteristic used for the housing in a lamp | ramp for motor vehicles, a reflector, an extension, a household appliance lighting device etc. can be provided with sufficient productivity.

Hereinafter, the present invention will be described in detail.
(A) Polybutylene terephthalate resin (A) Polybutylene terephthalate resin (hereinafter sometimes abbreviated as “PBT”) used in the present invention is an ester-linked terephthalic acid unit and 1,4-butanediol unit. A polymer having a structure in which 50 mol% or more of dicarboxylic acid units are composed of terephthalic acid units and 50 mol% or more of diol components are composed of 1,4-butanediol units.

  If the terephthalic acid unit or the 1,4-butanediol unit is too low, for example, if it is less than 50 mol%, the crystallization rate of PBT may decrease, and the moldability of the resulting polybutylene terephthalate resin may decrease. Therefore, the proportion of terephthalic acid units in all dicarboxylic acid units is usually 70 mol% or more, preferably 80 mol% or more, more preferably 95 mol% or more, and particularly preferably 98% or more. The proportion of 1,4 butanediol units is usually 70 mol% or more, preferably 80 mol% or more, more preferably 95 mol% or more, and particularly preferably 98% or more.

In the dicarboxylic acid component which is a raw material of (A) PBT used in the present invention, there is no particular limitation on the dicarboxylic acid component other than terephthalic acid. 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 a dicarboxylic acid or using a dicarboxylic acid derivative such as a dicarboxylic acid ester or a dicarboxylic acid halide as a raw material.

Moreover, in the diol component which is a raw material of (A) PBT used for this invention, there is no restriction | limiting in particular as diol components other than 1, 4- butanediol. 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; Cited The

  Further, (A) PBT used in the present invention includes lactic acid, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, p-β-hydroxyethoxybenzoic acid and the like. Hydroxycarboxylic acids; monofunctional components such as alkoxycarboxylic acid, stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t-butylbenzoic acid, benzoylbenzoic acid; tricarbaric acid, trimellitic acid, trimesic acid, pyromellitic acid, A copolymer obtained by copolymerizing trifunctional or more polyfunctional components such as gallic acid, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, and the like can also be used.

  (A) PBT used in the present invention contains (a) a titanium compound and (b) a Group 1 metal compound and / or a Group 2 metal compound, and (a) the content of the titanium compound is in terms of titanium atoms. 10 ppm to 80 ppm, and (b) the content of the Group 1 metal compound and / or the Group 2 metal compound is 1 ppm to 50 ppm in terms of metal atoms.

  (A) PBT used in the present invention is a polycondensation of an oligomer obtained by an esterification reaction (or transesterification reaction) between 1,4-butanediol and terephthalic acid (or dialkyl terephthalate). By using (a) a titanium compound and (b) a group 1 metal compound and / or a group 2 metal compound as a catalyst (polycondensation catalyst) used in the polycondensation, (A) (a ) And (b) are preferable because the dispersibility can be improved.

These polycondensation catalysts can be used at any time. Specifically, examples of the usage method include the following methods (1) to (4). Hereinafter, (a) a titanium compound may be referred to as a titanium catalyst, and (b) a group 1 metal compound and a group 2 metal compound may be referred to as a group 1 metal catalyst and a group 2 metal catalyst, respectively.
(1) A method of using both (a) and (b) in the esterification reaction (or transesterification reaction) and bringing them into the polycondensation reaction.
(2) A method in which (a) and (b) are partially used in the esterification reaction (or transesterification reaction) and added at the start of the polycondensation reaction or during the reaction.
(3) A method in which one of the catalysts (a) and (b) is used in the esterification reaction (or transesterification reaction), and the other is added at the start of the polycondensation reaction or during the reaction.
(4) A method in which neither (a) nor (b) is used in the esterification reaction (or transesterification reaction), and both are added at the start of the polycondensation reaction.

  The (a) titanium compound used in the present invention 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 (b) Group 1 metal compound and / or Group 2 metal compound used in the present invention is not particularly limited. Specifically, for example, the Group 1 metal compound may be hydroxylated with lithium, sodium, potassium, rubidium, or cesium. Compounds; oxides; alcoholates; various organic acid salts such as acetates, phosphates, carbonates, etc., and examples of group 2 metal compounds include beryllium, magnesium, calcium, strontium, Various compounds such as barium hydroxides; oxides; alcoholates; various organic acid salts such as acetates, phosphates and carbonates; 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 content of (a) titanium compound in (A) PBT used in the present invention is 10 ppm or more and 80 ppm or less in terms of titanium atom. When there is too much content of this titanium compound, the color tone and hydrolysis resistance of (A) PBT may fall, and the solution haze and foreign material by deactivation of a titanium catalyst may increase. On the other hand, if the amount is too small, the polymerizability of (A) PBT is lowered. Therefore, the content of the (a) titanium compound is preferably 70 ppm or less, particularly 60 ppm or less, more preferably 50 ppm or less, and particularly preferably 40 ppm or less, and the lower limit thereof is 15 ppm or more, especially 20 ppm or more, and particularly preferably 30 ppm or more. .

  In (A) PBT used in the present invention, the content of (b) Group 1 metal compound and / or Group 2 metal compound is 1 ppm or more and 50 ppm or less in terms of each metal atom. When there is too much content of this 1st group metal compound and / or 2nd group metal compound, the moldability of the PBT composition of this invention and the heat resistance of the resin molded product obtained may fall. On the other hand, even if the amount is too small, the surface appearance of the molded product may deteriorate. Therefore, the content of (b) Group 1 metal compound and / or Group 2 metal compound is 40 ppm or less, preferably 30 ppm or less, more preferably 20 ppm or less, particularly preferably 15 ppm or less, and the lower limit thereof is 3 ppm or more, especially 5 ppm or more. In particular, it is preferably 10 ppm or more. The metal content such as titanium atom can be measured using a method such as atomic emission, atomic absorption, Inductively Coupled Plasma (ICP) after recovering the metal in the polymer by a method such as wet ashing.

  Examples of the polycondensation catalyst for (A) PBT used in the present invention include the titanium compounds as described above and (b) Group 1 metal compounds and / or Group 2 metal compounds. Examples of other polycondensation catalysts include: Tin and its compound are mentioned. Tin is usually used as a tin compound, specifically, for example, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, cyclohexahexylditin oxide, didodecyltin oxide, triethyltin hydroxide, Triphenyltin hydroxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, tributyltin chloride, dibutyltin sulfide, butylhydroxytin oxide, methylstannic acid, ethylstannic acid, butylstannic acid, etc. Can be mentioned.

  However, since tin and tin compounds generally deteriorate the color tone of (A) PBT, the content of tin compounds in (A) PBT used in the present invention is preferably low and preferably not contained. 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 (A) PBT used in the present invention, in addition to the titanium catalyst, group 1 metal catalyst and group 2 metal catalyst, antimony compounds such as antimony trioxide; germanium such as germanium dioxide and germanium tetroxide. Reaction aids such as compounds; manganese compounds; zinc compounds; zirconium compounds; cobalt compounds; phosphorous compounds such as orthophosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, and their esters and metal salts;

The terminal carboxyl group concentration of (A) PBT used in the present invention is arbitrary, but a lower one is preferable. If it exceeds 60 μeq / g, gas is likely to be generated during melt molding of the resin composition. However, since the production of polyalkylene terephthalate resin having an excessively low terminal carboxyl concentration is remarkably low in productivity, that of (A) PBT used in the present invention is specifically 60 μeq / g or less, particularly 30 μeq / g or less. It is preferably 5 to 25 μeq / g, more preferably 5 to 20 μeq / g.
The terminal carboxyl group concentration in the present invention was measured by titration using a benzyl alcohol solution having a sodium hydroxide concentration of 0.01 mol / liter, in which 0.5 g of polyalkylene terephthalate was dissolved in 25 ml of benzyl alcohol. . As a method for adjusting the terminal carboxyl group concentration, any conventionally known method such as a method for adjusting polymerization conditions such as a raw material charge ratio at the time of polymerization, a polymerization temperature, a pressure reducing method, a method for reacting a terminal blocking agent, etc. is appropriately used. , Apply.

  Next, the manufacturing method of (A) PBT used for this invention is demonstrated. The method for producing (A) PBT used in the present invention is arbitrary. Generally, depending on the raw materials used, a method using a dicarboxylic acid as a main raw material (direct polymerization method) and a method using a dicarboxylic acid dialkyl ester as a main raw material (Transesterification method). The former has a difference in that water is mainly produced in the initial esterification reaction, and the latter mainly produces alcohol in the initial transesterification reaction.

  In addition, the (A) PBT production method used in the present invention is generally divided into batches according to the raw material supply or the form of extraction of the polybutylene terephthalate resin as the produced polymer (method of extracting the produced (molten) polymer from a reaction vessel or the like) The law is broadly divided into law and continuous law. The initial esterification reaction or transesterification reaction is performed in a continuous operation, and the subsequent polycondensation is performed in a batch operation, or the initial esterification reaction or transesterification reaction is performed in a batch operation, and the subsequent polycondensation is performed in a continuous operation. The method of performing is known.

  As the method for producing (A) PBT used in the present invention, it is preferable to use a direct polymerization method from the viewpoint of the superiority of the raw material basic unit, the ease of processing of by-products, and the quality of the obtained (A) PBT. It is preferable to use a so-called continuous method in which an esterification reaction and a polycondensation reaction are continuously performed in terms of stability and energy efficiency in production.

  The above-mentioned Group 1 metal catalyst and / or Group 2 metal catalyst used in the production of (A) PBT used in the present invention can be supplied to the esterification reaction tank or transesterification reaction tank. There is no restriction | limiting, You may supply to the reaction liquid upper surface from the reaction liquid phase part of these reaction tanks, and you may supply directly to a reaction liquid phase part. Moreover, in this case, it may be supplied together with the raw material terephthalic acid or the titanium catalyst, or may be supplied independently. Among these, from the viewpoint of the stability of the catalyst, it is preferable to supply the terephthalic acid and the titanium catalyst independently from the terephthalic acid and the titanium catalyst and to the upper surface of the reaction liquid from the reaction gas phase.

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

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

  As a specific example of the method for producing (A) PBT used in the present invention, for example, in the case of a continuous esterification method using a direct polymerization method, the following method may be used. A dicarboxylic acid component mainly composed of terephthalic acid, which is a raw material, and a diol component mainly composed of 1,4-butanediol 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 and a Group 1 metal catalyst and / or a Group 2 metal catalyst, the temperature condition is usually 180 to 260 ° C, preferably 200 to 245 ° C, more preferably 210 to 235 ° C. The pressure (indicating absolute pressure; hereinafter the same) conditions are usually 10 to 133 kPa, preferably 13 to 101 kPa, more preferably 60 to 90 kPa, and usually 0.5 to 10 hours. Preferably, the esterification reaction is continuously performed for 1 to 6 hours.

  Any conventionally known esterification reaction tank or transesterification reaction tank can be used. Specifically, for example, a vertical stirring complete mixing tank, a vertical heat convection mixing tank, a tower-type continuous reaction tank, and the like can be mentioned. These may be a single tank or a plurality of reaction tanks in which the same or different reaction tanks are connected in series or in parallel. Among them, it is preferable to use a reaction tank having a stirrer. As a stirrer, in addition to a normal stirrer including a power unit, a bearing, a shaft, a stirring blade, etc., a turbine stator type high-speed rotary stirrer, a disc mill stirrer, You may use what can rotate at high speed, such as a rotor mill type stirrer.

  Next, the obtained oligomer as the esterification reaction product (or transesterification reaction product) is transferred to a polycondensation reaction tank. Although the esterification rate of this oligomer is arbitrary, it is usually 90% or more, preferably 95% or more, and the number average molecular weight is usually 300 to 3000, preferably 500 to 1500.

  The form of the polycondensation reaction tank is arbitrary, and examples thereof include a vertical stirring complete mixing tank, a vertical heat convection mixing tank, a tower-type continuous reaction tank, and the like, and these may be used in combination. Among these, at least one polycondensation reaction tank preferably has a stirrer, and the stirrer is the same as the esterification reaction layer described above.

  The form of stirring is not particularly limited, and in addition to the usual stirring method in which the reaction solution in the reaction tank is directly stirred from the top, bottom, side, etc. of the reaction tank, a part of the reaction solution is connected to the outside of the reactor by piping or the like. It is also possible to use a method in which the reaction solution is circulated by taking it out and stirred with a line mixer or the like, and further, a horizontal reactor having a rotating shaft in the horizontal direction and excellent in self-cleaning property may be used.

The polycondensation reaction is performed in the presence of a titanium catalyst and a group 1 metal catalyst and / or a group 2 metal catalyst. The reaction temperature is usually 210 to 280 ° C, preferably 220 to 250 ° C, particularly preferably 230 to 245 ° C. For example, when using several reaction tanks, it is preferable that the temperature of the at least 1 reaction tank is 230-240 degreeC. The reaction is preferably performed under stirring conditions. The polycondensation reaction time is usually 1 to 12 hours, preferably 3 to 10 hours. The pressure condition in the reaction atmosphere is usually 27 kPa or less, preferably 20 kPa or less, and particularly preferably 13 kPa or less. For example, when a plurality of reaction vessels are used, the pressure in at least one of the reaction vessels is usually 1.3 kPa or less, particularly 0.5 kPa or less, particularly 0.3 kPa or less in order to suppress coloring and deterioration of the product. It is preferable to be under a high vacuum.

  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.

  Furthermore, the PBT polycondensation reaction step is to once produce a PBT having a relatively small molecular weight by melt polycondensation, for example, an intrinsic viscosity of about 0.1 to 0.9, and then at a temperature below the melting point of the PBT. Solid phase polycondensation (solid phase polymerization) may be performed.

  Although there is no restriction | limiting in the intrinsic viscosity of PBT of this invention, it is 0 as a value measured at the temperature of 30 degreeC using the mixed solvent of 1,1,2,2-tetrachloroethane / phenol = 1/1 (weight ratio). It is preferably 7 to 3, more preferably 0.8 to 1.5, and particularly preferably 0.8 to 1.2. When the intrinsic viscosity is 0.7 or more, mechanical properties tend to be improved, and when the intrinsic viscosity is 3 or less, molding processability tends to be improved. In the present invention, two or more types of intrinsic viscosity PBT may be used in combination.

(B) Polyethylene terephthalate resin In the present invention, the (B) polyethylene terephthalate resin is combined with (A) polybutylene terephthalate resin at a specific ratio to form the resin layered product and laminate of the present invention as a metal layer. The surface smoothness, brightness, etc. can be improved. Since the polyethylene terephthalate resin has a slower crystallization speed than the polybutylene terephthalate resin, the addition of the terephthalate resin has an effect of improving the mold transferability as a resin composition. In addition, it is effective in suppressing the surface smoothness, the decrease in luminance, the deformation, and the like that occur when the light reflector is placed under a high temperature such as light or heat.

The polyethylene terephthalate resin (B) used in the present invention is a polymer obtained by polycondensation reaction of, for example, terephthalic acid or an ester-forming derivative thereof with an alkylene glycol having 2 carbon atoms or an ester-forming derivative thereof, and is a homopolymer. Alternatively, a copolymer containing 70% by weight or more of this polyethylene terephthalate may be used.
Monomers to be copolymerized include dibasic acid components other than terephthalic acid and lower alcohol esters thereof, and aliphatic and aromatic polyvalents such as isophthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid and succinic acid Examples include basic acids or ester-forming derivatives thereof. Examples of glycol components other than ethylene glycol include ordinary alkylene glycols such as diethylene glycol, propylene glycol, trimethylene glycol, hexamethylene glycol, neopentyl glycol, cyclohexane dimethanol, and 1,3-octanediol. Alkylene glycols; alkylene oxide adduct alcohols such as ethylene oxide 2-mole adducts of bisphenol A and propylene oxide 3-mole adducts of bisphenol A; polyhydroxy compounds such as glycerin and pentaerythritol or ester-forming derivatives thereof; It is done.

The polyethylene terephthalate resin (B) used in the present invention may be modified or unmodified. Examples of the modified polyethylene terephthalate resin include modified polyethylene terephthalate copolymers such as those modified with isophthalic acid, and the degree of modification is usually 5-40 mol% modified with isophthalic acid relative to the polyethylene terephthalate resin.
The polyethylene terephthalate resin (B) used in the present invention is preferably an unmodified polyethylene terephthalate resin from the viewpoint of obtaining a light reflector having good surface properties and high brightness. In addition, the intrinsic viscosity of the polyethylene terephthalate resin (B) used in the present invention is usually preferably 0.5 to 1 because of its influence on fluidity and appearance.

  In the present invention, it is important that the content of the polyethylene terephthalate resin (B) is 5 to 80 parts by weight with respect to 100 parts by weight of the component (A). If the content of the polyethylene terephthalate resin (B) is too small, good mold transferability cannot be obtained, and it becomes difficult to obtain a light reflector having good brightness and surface properties. On the other hand, if the amount is too large, not only the mold release property is lowered and the molding cycle needs to be lengthened, but also the appearance defect, brightness, and surface property due to the generated gas are lowered. Therefore, the content of the polyethylene terephthalate resin (B) in the present invention is preferably 10 to 60 parts by weight with respect to 100 parts by weight of the component (A).

(C) Fine powder filler As the (C) fine powder filler used in the present invention, any conventionally known filler can be used. Specific examples of the fine powder filler include silica, kaolin, calcined kaolin, zeolite, quartz, talc, mica, clay, hydrotalcite, mica, graphite, glass beads, calcium carbonate, calcium sulfate, barium carbonate, sulfuric acid. Examples include barium, magnesium carbonate, magnesium sulfate, calcium silicate, titanium oxide, zinc oxide, magnesium oxide, silicon oxide, calcium titanate, magnesium titanate, and barium titanate, and these can be used in combination of two or more. . These fine powder fillers may be subjected to a surface treatment as necessary. The average particle size of the fine powder filler may be appropriately selected and determined, but from the viewpoint of improving the surface smoothness of the resin molded article using the polybutylene terephthalate resin composition of the present invention, it is determined by a precipitation method. The obtained particle diameter is preferably 20 μm or less, and usually the lower limit is 0.1 μm.

  The content of the fine powder filler used in the present invention may be appropriately selected and determined, but is usually 1 to 80 parts by weight with respect to 100 parts by weight of component (A). By containing 1 part by weight or more, the trapping performance of volatile components generated during molding is improved, and when the content is 80 parts by weight or less, the surface property deterioration due to the rising of the filler on the surface of the molded product can be suppressed. Especially, it is preferable that content of (C) fine powder filler shall be 30-60 weight part with respect to 100 weight part of (A) component.

(D) Release agent In the present invention, (D) a release agent can be further used. As the (D) mold release agent used in the present invention, any conventionally known plastic mold release agent can be used. Of these, fatty acid ester compounds are preferred because they are less likely to inhibit metal film adhesion. Examples of fatty acid ester compounds include glycerin fatty acid esters, sorbitan fatty acid esters, pentaerythritol fatty acid esters, and partially saponified products thereof. These can use 1 type (s) or 2 or more types in arbitrary ratios.

  The content of the release agent in the present invention may be appropriately selected and determined, but is usually 0.05 to 4 parts by weight with respect to 100 parts by weight of component (A). When the blending amount is 0.05 parts by weight or more, the surface property of the resin molded product obtained tends to be good, and when it is 4 parts by weight or less, the resin composition of the present invention is produced. Maintains kneading workability and improves the surface quality of the molded product. For example, when aluminum is deposited on the surface of the molded product, the unreacted release agent is prevented from being raised, and the molded product surface is prevented from being clouded. I can do it. The compounding amount of the release agent is preferably 0.07 to 2 parts by weight.

Further, in the present invention, the thermal stability at the time of molding of the resin composition substrate constituting the light reflector is improved, and particularly when continuously injection molded, gas generated from the obtained resin molded product, low molecular weight An antioxidant and a heat stabilizer can be further added for the purpose of suppressing a decrease in appearance and brightness due to the influence of components, exudates and the like.
As the antioxidant / heat stabilizer that can be used in the present invention, any conventionally known antioxidants can be used. Specifically, for example, it is preferably composed of one or a combination of two or more selected from hindered phenols, thioethers, and organophosphorus compounds, and these additions are stable in the heat of melting at the time of extrusion or in a molding machine. It is useful for continuous production of molded products with good appearance and surface smoothness with little appearance of surface haze due to gas adhesion, and light reflectors under high temperature conditions. It is particularly useful for suppressing the generation of gas and decomposition products generated from the resin and maintaining good appearance and surface smoothness.

In addition, the polybutylene terephthalate resin composition of the present invention is within a range not impairing the object of the present invention, such as polycarbonate resin, other thermoplastic resins and any conventionally known additives such as ultraviolet absorbers, fibrous reinforcing agents, A lubricant, a flame retardant, an antistatic agent, a colorant, a pigment and the like can be contained.
The polyester resin composition of the present invention can be obtained by molding the polybutylene terephthalate resin composition of the present invention by any conventionally known resin molding method. Among these, the use of the injection molding method is preferable because the feature of the present invention that is a feature of the present invention, that is, a resin molded product excellent in productivity and surface properties becomes remarkable.
The shape of the resin molding of the present invention is arbitrary, and for example, it can be an arbitrary shape according to a desired final product. Among them, a resin molded body on a thin, substantially flat plate such as a light reflection plate, in particular, a surface having a thickness of 0.5 to 10 mm, a main plane being substantially rectangular, and having a maximum area (main plane) is 0.0001. When the flat molded body of ˜1 m ² is obtained, the effect of the present invention is remarkable, which is preferable.

  The laminate of the present invention is a resin / metal laminate in which a metal layer is provided on at least a part of the above-mentioned polybutylene terephthalate resin molding. Specifically, the laminate of the present invention can be obtained, for example, by metal vapor deposition on at least one main plane of the surface of a flat polyester resin molded body. The method for providing the metal layer is arbitrary, and specifically, any conventionally known method such as electroless plating using a plating bath or a so-called metal vapor deposition method such as MOCVD can be used.

  Examples of the metal to be provided include chromium, nickel, and aluminum. In particular, when the laminate of the present invention is used as a reflector for various lamps for automobiles or home appliance lighting equipment, it is preferable to use aluminum as the metal vapor deposition because it can realize a sense of brightness and uniform reflectance. The surface of the molded product in the present invention is smooth and good, and an effect is obtained that a good gloss can be obtained even if metal deposition is directly performed on the molded product without performing primer treatment. In addition, in order to raise adhesive force, you may wash | clean and degrease the molded object surface before providing a metal layer.

  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 these examples and comparative examples, the following components were used.
(Resin and components used in Examples and Comparative Examples)
(A) PBT production method (A-1 to A-8)

(A-1) :
Using the esterification step shown in FIG. 1 and the polycondensation step shown in FIG. 2, PBT was produced by the following method. First, 1,4-butanediol 1.8 to 1.00 mol of terephthalic acid.
The slurry at 60 ° C. mixed at a ratio of 0 mol is passed through the raw material supply line 1 from the slurry preparation tank to the reaction tank A for esterification having a screw type stirrer filled with a PBT oligomer having an esterification rate of 99% in advance. , 41 kg / h continuously.
At the same time, the bottom component of the rectifying column C at 185 ° C. (98% by weight or more is 1,4-butanediol) is supplied at 20 kg / h from the recirculation line 2 and the catalyst at 65 ° C. is supplied from the titanium catalyst supply line 3 as a catalyst. A 6.0 wt% 1,4-butanediol solution of tetrabutyl titanate was fed at 99 g / h (30 ppm relative to the theoretical polymer yield). The water content in this catalyst solution was 0.2% by weight. A 6.0 wt% 1,4-butanediol solution of magnesium acetate tetrahydrate at 65 ° C. was fed at 62 g / h (15 ppm based on the theoretical polymer yield) as a catalyst from the Group 2 metal catalyst supply line 15. The water content in this catalyst solution was 10.0% by weight.

  The internal temperature of the reaction tank A is 230 ° C., the pressure is 78 kPa, and water to be generated, tetrahydrofuran and excess 1,4-butanediol are distilled from the distillation line 5. Separated into boiling components. The high-boiling component at the bottom of the column after the system is stabilized is 98% by weight or more of 1,4-butanediol, and a part of the high-boiling component through the extraction line 8 so that the liquid level of the rectifying column C is constant. 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 in the tank F was constant.

  A certain amount of the oligomer generated in the reaction tank A was extracted from the extraction line 4 using the pump B, and the liquid level was controlled so that the average residence time of the liquid in the reaction tank A was 2.5 hr. The oligomer extracted from the extraction line 4 was continuously supplied to the first polycondensation reaction tank a shown in FIG. After the system was stabilized, the esterification rate of the oligomer collected at the outlet of the reaction tank A was 96.5%.

  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, tetrahydrofuran 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 240 ° C., the pressure is 130 Pa, the liquid level is controlled so that the residence time is 85 minutes, and water is supplied from a vent line L4 connected to a decompressor (not shown). Further, the polycondensation reaction was advanced while extracting tetrahydrofuran and 1,4-butanediol. The obtained polymer was continuously extracted in a strand form from the die head g via the extraction line L3 by the extraction gear pump e, and was cut by the rotary cutter h. The analytical values of the obtained PBT are shown in Table 1.

(A-2) :
In (A-1), the residence time of the second polycondensation reaction tank d is set to 60 minutes, and the obtained polymer chip is 195 ° C. under reduced pressure (0.133 kPa or less) in a double conical blender (with an internal volume of 100 liters). ) A solid state polymerization treatment for 5 hours was performed. The intrinsic viscosity of the polymer subjected to the solid phase polymerization treatment was 0.85 dL / g, and the terminal carboxyl group concentration was 5.1 μeq / g. The analytical values of the obtained PBT are shown in Table 1.

(A-3) :
In (A-1), the supply amounts of tetrabutyl titanate and magnesium acetate tetrahydrate are adjusted so that the contents of titanium and magnesium in the polymer are as shown in Table 1, and in the second polycondensation reaction tank d. The procedure was the same as (A-1) except that the residence time was 75 minutes. The analytical values of the obtained PBT are shown in Table 1.

(A-4) :
In (A-1), the supply amounts of tetrabutyl titanate and magnesium acetate tetrahydrate are adjusted so that the contents of titanium and magnesium in the polymer are as shown in Table 1, and the temperature of the second polycondensation reaction tank d Was performed in the same manner as (A-1) except that the temperature was 244 ° C. and the residence time was 75 minutes. The analytical values of the obtained PBT are shown in Table 1.

(A-5) :
In (A-1), lithium acetate dihydrate is used in place of magnesium acetate tetrahydrate, the supply amount is adjusted so that the titanium and lithium contents in the polymer are as shown in Table 1, and the second The same procedure as (A-1) was performed except that the temperature of the polycondensation reaction tank d was 244 ° C. and the residence time was 70 minutes. The analytical values of the obtained PBT are shown in Table 1.

(A-6) :
In (A-1), magnesium acetate tetrahydrate is not used, and the supply amount of tetrabutyl titanate is adjusted so that the titanium content in the polymer is as shown in Table 2. Was carried out in the same manner as (A-1) except that the residence time of was changed to 105 minutes. The analytical values of the obtained PBT are shown in Table 1.

(A-7) :
In (A-1), the supply amount of tetrabutyl titanate and magnesium acetate tetrahydrate is adjusted so that the titanium and magnesium contents in the polymer are as shown in Table 1, and the second polycondensation reaction tank d is retained. The procedure was the same as (A-1) except that the time was 75 minutes. The analytical values of the obtained PBT are shown in Table 1.

(A-8) :
In (A-1), the feed amounts of tetrabutyl titanate and magnesium acetate tetrahydrate are adjusted so that the contents of titanium and magnesium in the polymer are as shown in Table 1, and the second polycondensation reaction tank (d) Was carried out in the same manner as (A-1) except that the residence time was 90 minutes. The analytical values of the obtained PBT are shown in Table 1.
Evaluation method of PBT characteristics

(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) Terminal carboxyl group concentration:
0.5 g of PBT or oligomer was dissolved in 25 ml of benzyl alcohol, and titrated using a 0.01 mol / L benzyl alcohol solution of sodium hydroxide.

(3) Intrinsic viscosity (IV):
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 = η / η ₀ −1, η is the polymer solution dropping time, η ₀ is the solvent dropping time, C is the polymer solution concentration (g / dL), and K _H is the Huggins constant. Yes, 0.33.
)

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

(5) Pellet color tone:
A color difference meter (Z-300A type) manufactured by Nippon Denshoku Co., Ltd. was used, and the b value in the L, a, b color system was evaluated. A lower value indicates less yellowing and a better color tone.

[Polyethylene terephthalate resin]
(B) Polyethylene terephthalate: manufactured by Mitsubishi Chemical Corporation, GS385, [η] = 0.65.

[Fine powder filler]
(C1) Inorganic filler-1 (talc, Hayashi Kasei, Talkan PK-C, particle diameter 11 μm)
(C2) Inorganic filler-2 (Mica, manufactured by Yamaguchi Mica, A-21, particle size 23 μm)
(The particle diameter is a value measured by the sedimentation method.)

[Release agent]
(D-1) Pentaerythritol distearate: Product name Unistar H-476D manufactured by NOF Corporation
(D-2) Polyethylene wax: Mitsui Petrochemical HW100P

The test method of the present invention was performed according to the method described below.
(1) Light reflector appearance:
Using a 75 ton injection molding machine, molding was performed at a molding temperature of 250 ° C., a mirror surface mold having a molded product shape of 100 mm × 100 mm × 3 mm, and a mold temperature of 80 ° C. The molded article was subjected to aluminum vapor deposition without applying a primer treatment to obtain a light reflector. Deposition conditions are as follows: Argon gas at a pressure of 3 Pa is converted into a plasma with a direct current of 500 V, and after processing the molded product for 5 minutes, the inside of the deposition apparatus is reduced to 1 × 10 ⁻² Pa, and aluminum is deposited at a rate of 1 nm / sec. Vapor deposition was performed with a thickness of 100 nm. The obtained light reflector is heat-treated using a hot air dryer under the conditions of 160 ° C. × 24 Hr (when fine powder filler is contained) or 180 ° C. × 24 Hr (when fine powder filler is not desired). The appearance before and after was visually evaluated according to the following criteria.
1: It has a high brightness feeling and the fluorescent lamp clearly appears without distortion.
2: Has a sense of brightness and reflects a fluorescent lamp.
3: Although there is a feeling of brightness, the fluorescent lamp appears slightly distorted.
4: The surface is rough and the fluorescent light appears to wave.

(2) Tape peelability:
The aluminum-deposited sample was heat-treated in a hot air dryer under the conditions of 160 ° C. × 24 Hr (when fine powder filler was not included) or 180 ° C. × 24 Hr (when fine powder filler was included), and then aluminum was deposited and obtained. The metal surface of the laminate was scratched with a knife, an adhesive tape was attached from above, and the adhesiveness when the adhesive tape was removed was evaluated.
A: Almost no peeling of the aluminum deposited film is observed.
○: Some peeling of the aluminum deposited film is observed.
X: Peeling of the aluminum vapor deposition film is remarkable.

(3) Thermal deformation temperature:
The heat distortion temperature was measured using an ISO test piece. The specimen was annealed at 160 ° C. for 1 hour and then measured according to ISO75. The load was measured at 0.45 MPa.

(4) Charpy impact strength:
Charpy impact strength was measured according to ISO179 using an ISO test piece.

[Examples 1 to 9 and Comparative Examples 1 to 6]
After sufficiently dry blending at the ratios shown in Tables 2 and 3, pelletization was carried out at an extrusion rate of 15 Kg / hr using a twin screw extruder set at 250 ° C. In Example 9, extruded pellets were similarly obtained by adding 608 ppm of magnesium stearate (25 ppm as metallic magnesium) to the composition of Comparative Example 4.
The obtained pellets were dried at 120 ° C. for 6 hours before injection molding, using an injection molding machine with a clamping force of 75 tons, a molding temperature of 250 ° C., and using a mirror mold with a molded product shape of 100 mm × 100 mm × 3 mm. Molding was performed at a mold temperature of 80 ° C. The mold release property at the time of injection molding was good, and the molded product could be taken out without resistance. The molded product was subjected to aluminum deposition without being subjected to primer treatment, and then the above-described evaluation was performed. Further, an ISO test piece was molded at a molding temperature of 250 ° C. and a mold temperature of 80 ° C. with the same injection molding machine, and the thermal deformation temperature and Charpy impact strength were measured. The results are shown in Table 2 and Table 3.

  Example 9 in Table 3 above is a result of evaluating pellets obtained by extrusion in the same manner after adding 608 ppm of magnesium stearate (25 ppm as metallic magnesium) to the resin composition of Comparative Example 4.

From Tables 2 and 3, the following can be seen. In other words, the examples have superior impact strength and heat distortion temperature compared to the comparative examples, the surface appearance of the sample when exposed to a high temperature atmosphere, the tape peelability are good, and the light reflector has good characteristics. is doing.
Moreover, in the Example shown by Table 3, the characteristic as a light reflector is better than a comparative example. Furthermore, in the present invention, even if a release agent is contained, it is useful for smoothly performing mold release at the time of molding, and does not promote peeling of the deposited film even at a high temperature, which is preferable. .

  From the above results, the resin molded body formed by molding the resin composition of the present invention and the light reflector obtained therefrom have excellent surface appearance such as specular sharpness, and thus are excellent in direct metal vapor deposition. Since these characteristics are not impaired even in a high temperature environment, it can be expected to be suitably used as a housing, a reflector, an extension, a home appliance lighting device, or the like in an automobile lamp.

(A) Explanatory drawing of an example of esterification (or transesterification) reaction process in PBT production (A) Explanatory drawing of an example of a polycondensation process in PBT production

Explanation of symbols

1: Raw material supply line 2: Recirculation line 3: Titanium 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
15: 2A group metal catalyst supply line A: Reaction tank B: Extraction pump C: Rectification tower D: Pump E: Pump F: Tank G: Capacitor L1: Extraction line L2: Vent line L3: Extraction line L4: Vent line a: first polycondensation reaction tank c: extraction gear pump d: second polycondensation reaction tank e: extraction gear pump g: dice head h: rotary cutter

Claims (7)

  (A) 100 parts by weight of polybutylene terephthalate resin, (B) 5 to 80 parts by weight of polyethylene terephthalate resin, (C) 0 to 80 parts by weight of fine powder filler, and (A) the polybutylene terephthalate resin is (A) a titanium compound and (b) a Group 1 metal compound and / or a Group 2 metal compound, (a) the content of the titanium compound is 10 ppm to 80 ppm in terms of titanium atom, (b) The polybutylene terephthalate resin composition, wherein the content of the Group 1 metal compound and / or the Group 2 metal compound is 1 ppm to 50 ppm in terms of metal atoms.   2. The polycondensation catalyst for producing (A) polybutylene terephthalate resin, wherein (a) the titanium compound and (b) the Group 1 metal compound and / or the Group 2 metal compound are (1). Polybutylene terephthalate resin composition.   (B) The polybutylene terephthalate resin composition according to claim 1 or 2, wherein the Group 1 metal compound or Group 2 metal compound is a magnesium compound.   The polybutylene terephthalate resin composition according to any one of claims 1 to 3, wherein (C) the fine powder filler is a fine powder filler having an average particle diameter of 20 µm or less.   The polybutylene according to any one of claims 1 to 4, further comprising 0.05 to 4 parts by weight of (D) a fatty acid ester compound with respect to 100 parts by weight of (A) polybutylene terephthalate resin. A terephthalate resin composition.   A polybutylene terephthalate resin molded product obtained by molding the (A) polybutylene terephthalate resin composition according to any one of claims 1 to 5. The laminated body which provides a metal layer in at least one part on the polybutylene terephthalate resin molding of Claim 6.

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