WO2004060961A1 - Polybutylene terephthalate and method for production thereof, and composition comprising the same and film - Google Patents

Abstract

A polybutylene terephthalate (PBT) which contains titanium and has a titanium content of 33 ppm or less; and a composition comprising the polybutylene terephthalate. In a preferred embodiment, the polybutylene terephthalate exhibits a crystallization temperature in the course of the decrease of temperature of 170 to 190°C, has a concentration of a terminal vinyl group of 0.1 to 10 μeq/g, exhibits a haze of its specific solution of 10 % or less, exhibits an increase of the concentration of a terminal carboxyl group of 0.1 to 30 μeq/g after being heat-treated under specific conditions, and contains foreign particles having a size of 5 μm or larger in an amount of 50 pieces/10 g-polymer or less. The PBT and a composition comprising the PBT are excellent in color tone, hydrolysis resistance, heat stability, transparency and processability, and is reduced in the content of foreign matter, and thus can be suitably used for a film, a monofilament, a fiber, an electric or electronic part, an automobile part or the like.

Description

 Technical Field

 The present invention relates to a polybutylene terephthalate, a method for producing the same, and a composition thereof.

Objects and films. Specifically, the present invention relates to a color tone, hydrolysis resistance, and heat Yasuda

Polybutylene terephthalate excellent in qualitative properties, transparency, moldability and reduced in foreign matter, which can be suitably used for films, monofilaments, fibers, electric and electronic parts, automobile parts, etc. It relates to compositions and films. Background art

 Typical edges among thermoplastic polyester resins:

Certain polybutylene terephthalates have excellent moldability, mechanical properties, heat resistance, chemical resistance, fragrance retention, and other excellent physical and chemical properties. Widely used for injection molding products such as precision instrument parts. In recent years, it has been widely used in the fields of films, sheets, monofilaments, and fibers, taking advantage of its excellent properties.

 In general, it is known that the higher the concentration of the terminal lipoxyl group, the worse the hydrolysis resistance of the polyester becomes (for example, a saturated polyester resin, published by Nikkan Kogyo Shinbunsha on Feb. 22, 1989). Handbook, pp. 192-193), polybutylene terephthalate also has a higher terminal lipoxyl group concentration, the higher the rate of hydrolysis reaction under moist heat, the lower the molecular weight due to hydrolysis, and consequently the mechanical properties. A major problem is that it causes a decrease.

Furthermore, normal melt molding is performed at a temperature higher than the melting point of polybutylene terephthalate. Therefore, there is a problem that the concentration of the terminal lipoxyl group increases again during molding, and the hydrolysis resistance further deteriorates when the product becomes a molded product.

 In order to solve the above-mentioned problems, it is widely practiced to once solidify the polybutylene terephthalate obtained by melt polymerization, and to carry out solid-state polymerization at a temperature lower than its melting point to reduce the terminal carboxyl group concentration. (For example, Japanese Patent Application Laid-Open No. 9-31616). However, as described above, in conventional polybutylene terephthalate, even if the concentration of terminal lipoxyl groups is reduced by solid-phase polymerization, the concentration of terminal lipoxyl groups increases again during molding, resulting in a molded product. At this point, there is a problem that the effect of solid phase polymerization is reduced.

 On the other hand, especially for applications such as films, sheets, monofilaments, and fibers, their commercial value is greatly affected by foreign matter, haze, coloring, etc. Therefore, reduction and improvement of these are strongly demanded. Foreign matter and haze in polybutylene terephthalate are considered to be caused by degraded resin, which is generally referred to as "Jakemeji", as well as deactivated substances and aggregated substances of metal compounds added as a catalyst.

 Therefore, the reaction for the continuous esterification of terephthalic acid and 1,4-butanediol is divided into two stages.In the first stage of the esterification reaction, only the organotin compound is added, and in the second stage of the esterification reaction. A method has been proposed in which an organic titanium compound is added to reduce foreign substances and haze derived from the catalyst (for example, Japanese Patent Application Laid-Open No. 10-330468).

However, since the metal concentration in the finally obtained polybutylene terephthalate is high, the effect of reducing foreign substances and haze is limited, and there is a problem that these metal compounds cause deterioration of polymer color tone and heat resistance. (See Patent Document 4). Further, the above-mentioned increase in the concentration of the terminal lipoxyl group at the time of melting is accelerated by the use of a metal compound as a catalyst, so that there is also a disadvantage that hydrolysis resistance is deteriorated as a result. '' Brief description of the drawings FIG. 1 is a diagram illustrating an example of an esterification reaction step or a transesterification reaction step employed in the present invention.

 FIG. 2 is an explanatory diagram of another example of the esterification reaction step or transesterification reaction step employed in the present invention.

 FIG. 3 is an explanatory diagram of another example of the esterification reaction step or transesterification reaction step employed in the present invention.

 FIG. 4 is an explanatory diagram of another example of the esterification reaction step or transesterification reaction step employed in the present invention.

 FIG. 5 is an explanatory diagram of another example of the esterification reaction step or transesterification reaction step employed in the present invention.

 FIG. 6 is an explanatory diagram of an example of the polycondensation step employed in the present invention.

 FIG. 7 is an explanatory diagram of another example of the polycondensation step employed in the present invention.

 FIG. 8 is an explanatory diagram of another example of the polycondensation step employed in the present invention.

 FIG. 9 is an explanatory diagram of another example of the polycondensation step employed in the present invention. Disclosure of the invention

 The present invention has been made in view of the above circumstances, and has as its object to improve the color tone, hydrolysis resistance, heat stability, transparency, and moldability, and furthermore, to reduce the amount of foreign matter, to obtain a film or monofilament. Polybutylene terephthalate, a method for producing the same, and a polybutylene terephthalate composition and a film containing the polybutylene terephthalate and having various functions, which can be suitably used for fibers, electric and electronic parts, and automobile parts. To provide.

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, if the esterification or transesterification reaction is performed under specific conditions, the use amount of the catalyst is increased because the efficiency of use of the catalyst is improved. It has been found that a novel polybutylene terephthalate can be obtained which can be remarkably reduced, and as a result, the content of the catalyst is remarkably low, thereby easily solving the above-mentioned problems. Also, esterification or esterification under certain conditions It has been found that by performing a steal exchange reaction, the conversion rate can be increased, foreign substances can be reduced, and side reactions can be suppressed.

 The present invention has been completed based on the above findings, and the first gist of the present invention is to provide a polybutylene terephthalate characterized by containing titanium and having an amount of 33 ppm or less as a titanium atom. Be on the rate.

 A second gist of the present invention is a polybutylene terephthalate having a step of performing an esterification reaction by continuously supplying terephthalic acid and 1,4-butanediol in the presence of a titanium catalyst in an esterification reaction tank. In the method for producing 1,4-butanediol, at least a part of 1,4-butanediol is supplied to an esterification reactor independently of terephthalic acid, and 1,4-butanediol is supplied to an esterification reactor independently of terephthalic acid. 10% by weight or more of the titanium catalyst is supplied to the liquid phase of the reaction liquid, and 10% by weight or more of the titanium catalyst is supplied to the liquid phase of the reaction liquid independently of terephthalic acid. It is in the manufacturing method.

 A third gist of the present invention is a polybutylene having a step of performing a transesterification reaction by continuously supplying a dialkyl terephthalate and 1,4-butanediol in a transesterification reaction tank in the presence of a titanium catalyst. In the method for producing terephthalate, at least a portion of 1,4-butanediol is supplied to a transesterification reactor independently of dialkyl terephthalate, and supplied to a transesterification reactor independently of dialkyl terephthalate. A polybutanediol, wherein at least 10% by weight of monobutanediol is supplied to the reaction liquid phase, and at least 10% by weight of the titanium catalyst is supplied to the reaction liquid phase independently of terephthalic acid. It lies in the method of manufacturing butylene terephthalate.

The fourth gist of the present invention is a process of continuously performing an esterification reaction of terephthalic acid and an excess of 1,4-butanediol with respect to terephthalic acid in the presence of a titanium catalyst in an esterification reaction tank. In the method for producing polybutylene terephthalate having the following formula, the molar ratio of terephthalic acid and 1,4-butanediol supplied to the esterification reactor per unit time (moles of 1,4-butanediol / terephthalic acid) (Molar number of acid) is controlled to be constant.

 The fifth gist of the present invention is that, in a transesterification reaction tank, dialkyl terephthalate and an excess of 1,4-butanediol relative to dialkyl terephthalate are continuously esterified in the presence of a titanium catalyst. In a process for producing polybutylene terephthalate having a step of performing an exchange reaction, the molar ratio of dialkyl terephthalate and 1,4-butanediol supplied to a transesterification reactor per unit time (1,4-butanediol (Moles / moles of terephthalic acid) is controlled to be constant.

 The sixth gist of the present invention is that the polybutylene terephthalate according to the first gist, a phenolic antioxidant (B 1), a zeolite antioxidant (B 2), and a phosphorus antioxidant (B 3) And a heat-resistant polybutylene terephthalate composition comprising at least one antioxidant selected from the group consisting of:

 A seventh aspect of the present invention is based on 100 parts by weight of the polybutylene terephthalate according to the first aspect, wherein a fatty acid residue having 12 to 36 carbon atoms and an alcohol residue having 1 to 36 carbon atoms are used. A releasing agent selected from the group consisting of a fatty acid ester (C 1) and a paraffin wax and a polyethylene wax (C 2) (C) in an amount of 0.01 to 2 parts by weight. It is present in the butylene terephthalate composition.

 According to an eighth aspect of the present invention, there is provided the polybutylene terephthalate according to the first aspect, in which the reinforcing filler (D) is contained in an amount of 0 to 200 parts by weight and the epoxy compound (E) is added in an amount of 100 to 100 parts by weight. 20 parts by weight of a hydrolysis-resistant polybutylene terephthalate composition.

According to a ninth aspect of the present invention, the polybutylene terephthalate according to the first aspect has a weight ratio of 100 to 100 parts by weight, and the impact modifier (F) has a content of 0.5 to 40 parts by weight and a reinforcing filler (D). 0 to 200 parts by weight of an impact-resistant polybutylene terephthalate composition. According to a tenth aspect of the present invention, a brominated aromatic compound-based flame retardant (G) is used in an amount of 3 to 50 parts by weight, based on 100 parts by weight of the polybutylene terephthalate according to the first aspect. A flame retardant polybutylene terephthalate composition comprising 1 to 30 parts by weight, an anti-dripping agent (I) 0 to 15 parts by weight and a reinforcing filler (D) 0 to 200 parts by weight. Exists.

 The eleventh aspect of the present invention is based on a total of 100 parts by weight of 50 to 95 parts by weight of the polybutylene terephthalate according to the first aspect and 5 to 50 parts by weight of the polyphenylene ether resin (J). Compatibilizer (K) 0.05 to 10 parts by weight, at least one compound selected from phosphate ester or phosphonitrile (L) 2 to 45 parts by weight, reinforcing filler (D) 0 to 200 parts by weight, an anti-dripping agent (I) 0 to 15 parts by weight, melamine cyanurate (M) 0 to 45 parts by weight and a metal borate (N) 0 to 50 parts by weight. It is a non-hazardous flame retardant polybutylene terephthalate composition.

 The 12th gist of the present invention is that the polybutylene terephthalate according to the 1st gist is 100 parts by weight, the polycarbonate resin (O) is 5 to 100 parts by weight, and the organic phosphorus compound (P) is 0.01. 1 to 1 part by weight, a reinforcing filler (D) 0 to 200 parts by weight, and an impact modifier (F) 0 to 50 parts by weight in a polybutylene terephthalate composition.

 A thirteenth aspect of the present invention resides in that 100 to 100 parts by weight of the polybutylene terephthalate according to the first aspect, 5 to 100 parts by weight of an aromatic polyester resin (Q) other than polybutylene terephthalate and reinforced filling Material (D) The polybutylene terephthalate composition contains 0 to 200 parts by weight.

According to a fourteenth aspect of the present invention, the polystyrene resin (R) is 5 to 100 parts by weight, the maleic anhydride-modified polystyrene resin (S) is 100 parts by weight of the polybutylene terephthalate according to the first aspect. Or a polycarbonate resin (0) 0 to 40 parts by weight and a reinforcing filler (D) 0 to 200 parts by weight. A fifteenth aspect of the present invention resides in a film comprising a polybutylene terephthalate containing titanium and having an amount of 33 ppm or less as a titanium atom.

 The 16th gist of the present invention is that 1 to 99% by weight of polybutylene terephthalate and 1 to 99% by weight of polybutylene terephthalate containing titanium and having an amount of 33 ppm or less as a titanium atom (but not both). (Total amount of 100% by weight).

 A seventeenth aspect of the present invention is to provide an aromatic polyester obtained by copolymerizing 1 to 99% by weight of polybutylene terephthalate containing titanium and having an amount of 33 ppm or less as a titanium atom and polytetramethylene glycol. 1 to 99% by weight (the total of both is 100% by weight). BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The polybutylene terephthalate (hereinafter abbreviated as PBT) of the present invention has a structure in which terephthalic acid units and 1,4-butanediol units are ester-bonded, and 50 mol% or more of dicarboxylic acid units is terephthalic acid. A macromolecule consisting of 1,4-butanediol units in which 50% or more of the diol component is composed of diol units. The proportion of terephthalic acid units in all dicarboxylic acid units is preferably at least 70 mol%, more preferably at least 80 mol%, particularly preferably at least 95 mol%, and The proportion of 4-butanediol units is preferably at least 70 mol%, more preferably at least 80 mol%, particularly preferably at least 95 mol%. If the content of terephthalic acid units or 1,4-butanediol units is less than 50 mol%, the crystallization speed of PBT will decrease, leading to deterioration in moldability.

In the present invention, the dicarboxylic acid component other than terephthalic acid is not particularly limited. For example, phthalic acid, isophthalic acid, 4,4 ′ diphenyldicarboxylic acid, 4, 4 ′ —Diphenyl ether dicarboxylic acid, 4, 4'-benzophenone dicarboxylic acid, 4, 4 'diphenoxyethane dicarboxylic acid, 4, 4' diphenyl sulfone dicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, etc. Aromatic dicarboxylic acids, 1,

Alicyclic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid, and aliphatic dicarboxylic acids such as malonic acid, succinic acid, daltaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. I can do it. These dicarboxylic acid components can be introduced into the polymer skeleton as a dicarboxylic acid or a dicarboxylic acid derivative such as dicarboxylic acid ester or dicarboxylic acid octalide as a raw material.

 In the present invention, diol components other than 1,4-butanediol are not particularly limited, and include, for example, ethylene glycol, diethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, polypropylene glycol, Aliphatic diols such as polytetramethylene glycol, dibutylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,2-cyclohexanediol, Alicyclic diols such as 1,4-cyclohexanediol, 1,1-cyclohexane dimethylol, 1,4-cyclohexane dimethylol, xylylene glycol, 4,4'-dihydroxybiphenyl, 2,2- Bis (4-hydroxyphenyl) propane, bis (4-hydroxy And aromatic diols such as phenyl) sulfone.

In the present invention, further, hydroxycarboxylic acids such as lactic acid, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, p-3-hydroxyethoxybenzoic acid, and alkoxycarboxylic acids Monofunctional components such as acid, stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t-butyl benzoic acid, benzoyl benzoic acid, etc., tricarboxylic acid, trimellitic acid, trimesic acid, pyromellitic acid, gallic acid, G Trifunctional or higher polyfunctional components such as rimethylolethane, trimethylolpropane, glycerol, and pentaerythritol can be used as copolymer components. '

 The PBT of the present invention is obtained by using a titanium catalyst as a catalyst in the esterification reaction (or transesterification reaction) between 1,4-butanediol and terephthalic acid (or dialkyl terephthalate).

 As the titanium catalyst, a titanium compound is usually used. Specific examples thereof include an inorganic titanium compound such as titanium oxide and titanium tetrachloride, a titanium alcohol such as tetramethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate; Titanium phenolate such as enil titanate and the like can be mentioned. Of these, tetraalkyl alkyl ether is preferred, and tetrabutyl titanate is more preferred.

 In addition to titanium, tin may be used as a catalyst. Tin is usually used as a tin compound, and specific examples thereof include dibutyltin oxide, methylphenyltin suloxide, tetraethyltin, hexethyl stannuloxide, cyclohexahexyldisuloxide, and the like. Didodecyl sulphoxide, triethyltin hydroxide, triphenyltin octahydroxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, triptyltin chloride, dibutyltin sulfide, butylhydroxyl Examples include sutoxide, methylstannic acid, ethylstannic acid, and butylstannic acid.

In addition, in addition to titanium, magnesium compounds such as magnesium acetate, magnesium hydroxide, magnesium carbonate, magnesium oxide, magnesium alkoxide, magnesium hydrogen phosphate, calcium acetate, calcium hydroxide, calcium carbonate, calcium oxide, In addition to calcium compounds such as calcium alkoxide and calcium hydrogen phosphate, antimony compounds such as antimony trioxide, germanium compounds such as germanium dioxide and germanium tetroxide, manganese compounds, Using reaction compounds such as zinc compounds, zirconium compounds, cobalt compounds, orthophosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, phosphorus compounds such as esters and metal salts thereof, sodium hydroxide, sodium benzoate, etc. Is also good.

 When the esterification reaction (or transesterification reaction) consists of a plurality of tanks, the above-mentioned catalyst and reaction aid may be added in portions, or may be added in the subsequent polycondensation reaction.

 The PBT of the present invention is characterized by containing titanium and having an amount of 33 ppm or less as a titanium atom. The above values are the weight ratio of atoms to PBT. In the present invention, the lower limit of the above-mentioned titanium content is usually l ppm, preferably 3 ppm, more preferably 5 ppm, particularly preferably 8 ppm, and still more preferably 15 ppm. The upper limit for the titanium content is preferably 30 ppm, more preferably 27 ppm. If the titanium content is more than 33 ppm, the color tone, hydrolysis resistance, transparency, moldability, etc. will deteriorate, and moreover, foreign matter tends to increase.If it is less than 1 ppm, the polymerizability will deteriorate. Sometimes.

 In the present invention, a tin catalyst can be used together with a titanium catalyst. In general, tin catalysts have a lower catalytic activity than titanium catalysts, so it is necessary to increase the amount of tin catalyst compared to titanium catalysts. However, too much tin catalyst can lead to color degradation and tin is toxic. Therefore, the amount of the tin catalyst used is usually 100 ppm or less, preferably 50 ppm or less, more preferably 20 ppm or less, and the most preferred embodiment is that no tin catalyst is used. The content of titanium atoms, etc. can be determined using methods such as atomic emission, atomic absorption, and Induced Coupled Plasma (ICP) after recovering the metals in the polymer by wet ashing or other methods. Can be measured.

The PBT of the present invention has an intrinsic viscosity of usually 0.60 to 2.00 dL / g, preferably 0.65 to 1.50 dLZg, and more preferably 0.75 to 1.30 dLZg. If the intrinsic viscosity is less than 0.60 dLZg, the mechanical strength of the molded product will be insufficient, and if it exceeds 2.00 dLZg, the melt viscosity will be high and the fluidity will deteriorate, and Shape properties tend to deteriorate. The above intrinsic viscosity is a value measured at 30 ° C using a mixed solvent of phenolnotetrachloroethane (weight ratio 1/1).

 In the present invention, two or more PBTs having different intrinsic viscosities may be used in combination. In this case, the intrinsic viscosity of the plurality of PBTs to be used is preferably in the range of 0.60 to 2.00 dL / g, and the intrinsic viscosity of the composition is also in the above range. Preferably, there is. For example, a PBT (A1) having an intrinsic viscosity of 0.60 to 0.90 dL / g and a PBT (A2) having an intrinsic viscosity of 0.91 to 1.50 dL / g in a weight ratio of 5:95 to It is good to mix 95: 5. The terminal lipoxyl group concentration of the PBT of the present invention is usually 0.1 to 35 / ie ciZg, preferably 1 to 25 ^ eqZg, more preferably 1 to 20 eqZg, and particularly preferably 1 to 15 eqZg. It is said. If the terminal carboxyl group concentration is too high, the hydrolysis resistance of PBT deteriorates.

 It is preferable that the terminal lipoxyl group concentration be lower as the molecular weight becomes smaller and the molecular weight becomes lower and the molecular weight is more susceptible to the decrease in molecular weight due to hydrolysis. That is, it is recommended to satisfy the following equation (1-1). It is preferably Formula (1-2), more preferably (1-3), and particularly preferably Formula (1-4).

20 X I V + 6 ≥ [COOH] ≥ 20 X I V-12 (I-1)

20 X I V + 4 ≥ [COOH] ≥ 20 X I V- 12 (1-2)

20 X I V + 2 ≥ [COOH] ≥ 20 X I V- 12 (1-3)

20 X I V ≥ [COOH] ≥ 20 X I V-12 (1-4)

(Here, [COOH] is the concentration of terminal lipoxyl group (unit is zeq / g), [COOH]> 0, and IV is the intrinsic viscosity.) Also, lower the terminal lipoxyl group concentration of PBT. However, if the temperature rises due to heat during kneading or molding, not only does the hydrolysis resistance of the product deteriorate, but also gas such as tetrahydrofuran is generated. Therefore, nitrogen, helium, argon, etc. When heat treatment is performed at 245 ° C for 40 minutes in an inert gas atmosphere, the concentration of lipoxyl group at the terminal end excluding the hydrolysis reaction is usually 1 to 30 eqZg, preferably l to 10 e. qL / g, more preferably 1 to 8 eq / g. In general, the lower the content of the catalytic substance, and the higher the molecular weight, the smaller the increase in the terminal lipoxyl group concentration when heat is applied.

 In the above evaluation method, the temperature and time are specified because if the temperature is too low or the time is too short, the rate of increase in the terminal lipoxyl group concentration is too small, and if the temperature is too low or too short, the evaluation is too large. It is to be accurate. Another reason is that if the evaluation is performed at an extremely high temperature, side reactions other than the generation of a terminal lipoxyl group will occur at the same time, and the evaluation will be inaccurate. Under the heat treatment conditions, the decrease in the number average molecular weight due to a reaction other than the hydrolysis reaction caused by the water contained in the PBT can be ignored, and the increase in the terminal lipoxyl group concentration due to the hydrolysis reaction is the same as before and after the heat treatment. Can be considered to be almost the same as the increase in the terminal hydroxyl group concentration of the compound. Therefore, the increase in the terminal lipoxyl group concentration due to the thermal decomposition reaction other than the hydrolysis reaction, which is a problem during kneading and molding, is expressed by the following formula (II). You can ask.

Δ AV (d) = AAV (t) -AAV (h) = AAV (t) -ΔΟΗ Οθθ where AAV (d) is the amount of change in terminal lipoxyl group concentration due to the thermal decomposition reaction,

ΔAV (t) is the total change in terminal lipoxyl group concentration before and after heat treatment, ΔΑν (h) is the change in terminal lipoxyl group concentration due to hydrolysis reaction, and ΔOH is the change in terminal hydroxyl group concentration before and after heat treatment. Represent. From the viewpoint of the reliability of the thermal decomposition reaction evaluation, it is preferable that the hydrolysis reaction is small, so that the water content of PBT used for the heat treatment is usually recommended to be 300 ppm or less. The concentration of terminal hydroxyl groups before and after the heat treatment can be determined by NMR.

The terminal lipoxyl group concentration of PBT can be determined by dissolving PBT in an organic solvent and titrating it with an alkaline solution such as sodium hydroxide solution. Can be.

In addition, the terminal vinyl group concentration of the PBT of the present invention is usually 15 ^ eqZg or less, preferably 0.1 to 10 ^ eq_Zg, more preferably:! 88 zeq / g, particularly preferably 1-5 eci / g. When the terminal vinyl group concentration is too high, it causes deterioration of color tone and solid phase polymerization. When manufacturing high molecular weight PBT or low catalyst concentration PBT without reducing productivity, it is generally necessary to raise the polymerization temperature or increase the reaction time. The vinyl group concentration tends to increase. The terminal vinyl group concentration can be quantified by dissolving PBT in bichloroform form Z hexafluoroisopropanol = 7/3 (volume ratio) and measuring ^J H -N.

 At the end of PBT, in addition to the hydroxyl group, propyloxyl group, and vinyl group, a methoxycarbonyl group derived from the raw material may remain, especially when dimethyl terephthalate is used as the raw material. There is. By the way, the methoxycarbonyl terminal generates methanol, formaldehyde, and formic acid by heat due to solid-state polymerization, kneading, molding, and the like, and these toxicity is a problem particularly when used for food. Formic acid also damages metal forming equipment and vacuum equipment. Therefore, the concentration of the terminal methoxycarbonyl group in the present invention is generally 0.5 β e QZg or less, preferably 0.1 S / xe qZg or less, more preferably 0.2 β e Q / g or less, and particularly preferably 0.1 L or less. ^ e ciZg or less.

 The concentration of each of the above terminal groups other than the terminal lipoxyl group can be determined by dissolving PBT in a mixed solvent of formaldehyde / hexafluoroisopropanol = 7/3 (volume ratio) and measuring iH-NMR. It can be quantified. At this time, a very small amount of a basic component such as heavy pyridine or the like may be added to prevent overlap with the solvent signal.

The cooling crystallization temperature of the PBT of the present invention is usually from 170 to 200, preferably from 172-195 ° C, and more preferably from 170 to 190 ° C. In the present invention, the cooling crystallization temperature refers to a temperature lowering from a molten state of a resin using a differential scanning calorimeter. This is the temperature of the exothermic peak due to crystallization that appears when cooled at a rate of 20 ° C / min. The cooling crystallization temperature corresponds to the crystallization speed. The higher the cooling crystallization temperature, the faster the crystallization speed, so that the cooling time during injection molding can be shortened and the productivity can be increased. If the crystallization temperature is low, crystallization takes a long time during injection molding, and the cooling time after injection molding must be extended, which tends to extend the molding cycle and reduce productivity.

 Although the solution haze of the PBT of the present invention is not particularly limited, it is usually 10% or less as a solution haze when measuring 2.7 g of PBT dissolved in 20 mL of a phenol Z tetrachloroethane mixed solvent (3/2 by weight). It is preferably at most 5%, more preferably at most 3%, particularly preferably at most 1%. If the solution haze is high, the transparency tends to deteriorate and the amount of foreign substances tends to increase. Therefore, in applications where transparency is required, such as films, monofilaments and fibers, the commercial value is significantly reduced. Solution haze tends to increase with high catalyst content or high catalyst deactivation.

 Further, the foreign matter having a length of 5 zm or more contained in the PBT of the present invention is usually 60 particles / 10 g or less. In particular, in applications in which foreign matter in the raw material PBT resin such as films, monofilaments, and filaments greatly affects product quality, the number is preferably 50 or less, more preferably 40 or less, and particularly preferably 30 or less. The amount of the above foreign substances can be determined, for example, by dissolving 10 g of PBT at a concentration of 20% by weight in a mixed solvent of hexafluoroisopropanol / chloroform = 2/3 (volume ratio), After filtration through a fluoroethylene membrane filter, the filter is sufficiently washed with the mixed solvent, and the amount of foreign substances remaining on the filter can be determined by observing with an optical microscope and counting.

Next, the method for producing the PBT of the present invention will be described. Production methods of PBT are broadly classified into so-called direct polymerization methods using dicarboxylic acid as a main raw material and transesterification methods using dialkyl dialkyl sulfonate as a main raw material. The former produces water during the initial esterification reaction, and the latter produces water during the initial transesterification reaction. There is a difference that alcohol is produced.

 In addition, PBT production methods are broadly classified into a batch method and a continuous method based on the raw material supply or polymer delivery form. The initial esterification reaction or transesterification reaction is performed in a continuous operation, and the subsequent polycondensation is performed in a batch operation, or conversely, the initial esterification reaction or transesterification reaction is performed in a batch operation and the subsequent polymerization is performed. There is also a method in which the condensation is performed in a continuous operation.

 In the present invention, a direct polymerization method is preferred from the viewpoints of availability of raw materials, easy processing of distillate, height of raw material unit, and improvement effect of the present invention. Further, in the present invention, from the viewpoints of productivity and product quality stability and the improvement effect of the present invention, a method of continuously supplying raw materials and continuously performing an esterification reaction or a transesterification reaction is adopted. . In the present invention, a so-called continuous method in which a polycondensation reaction following an esterification reaction or a transesterification reaction is also continuously performed is preferable. In the present invention, at least a part of 1,4-butanediol is esterified independently of terephthalic acid (or dialkyl terephthalate) in an esterification reaction tank (or a transesterification reaction tank) in the presence of a titanium catalyst. A step of continuously esterifying (or transesterifying) terephthalic acid (or dialkyl terephthalate) with 1,4-butanediol while supplying the mixture to the esterification reactor (or transesterification reactor) is preferably employed.

 That is, in the present invention, in order to reduce haze and foreign substances derived from the catalyst and not to decrease the catalytic activity, 1,4-butanediol supplied together with terephthalic acid or dialkyl terephthalate as a raw material slurry or solution is Separately, 1,4-butanediol is supplied to an esterification reactor or a transesterification reactor independently of terephthalic acid or dialkyl terephthalate. Hereinafter, the 1,4-butanediol may be referred to as “separately supplied 1,4-butanediol”.

The above-mentioned “separate 1,4-butanediol” can be treated with fresh 1,4-butanediol that is unrelated to the process. In addition, "Separate supply 1, 4 The “tandiol” is obtained by collecting 1,4-butanediol distilled from the esterification or transesterification reaction tank with a condenser or the like, or as it is, or temporarily holding it in a tank or the like and refluxing it to the reaction tank. Impurities can be separated and purified to provide 1,4-butanediol with increased purity. Hereinafter, the “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 use of resources and simplicity of equipment, it is preferable to assign “recycled 1,4-butanediol” to “separate 1,4-butanediol”.

 In general, 1,4-butanediol distilled from an esterification reactor or a transesterification reactor contains components such as water, alcohol, tetrahydrofuran, and dihydrofuran in addition to the 1,4-butanediol component. In. Therefore, the 1,4-butanediol distilled out above should be separated and purified from components such as water, alcohol and tetrahydrofuran after being collected with a condenser or while collecting, and returned to the reaction tank. Is preferred.

 In the present invention, it is preferable that 10% by weight or more of the “separately supplied 1,4-butanediol” is directly returned to the liquid phase of the reaction liquid. Here, the liquid phase of the reaction liquid refers to the liquid phase side of the gas-liquid interface in the esterification reaction tank or the transesterification reaction tank. This means that “separate supply 1,4-butanediol” is directly supplied to the liquid phase without passing through the gas phase. The proportion returned directly to the liquid phase of the reaction liquid is preferably at least 30% by weight, more preferably at least 50% by weight, particularly preferably at least 80% by weight, most preferably at least 90% by weight. When the amount of “separately supplied 1,4-butanediol” that is returned directly to the liquid phase of the reaction liquid is small, foreign substances tend to increase.

The temperature of the “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 200 ° C.). 0 to: L 90 ° C If the temperature of “separate feed 1,4-butanediol” is too high, the amount of tetrahydrofuran by-product tends to increase, and if it is too low, the heat load Increased Energy loss.

 Further, in the present invention, in order to reduce haze and foreign substances derived from the catalyst and not to lower the catalytic activity, 10% by weight or more of the titanium catalyst used in the esterification reaction (or the transesterification reaction) is terephthalic acid ( Or dialkyl terephthalate) is preferably supplied directly to the liquid phase of the reaction liquid. Here, the liquid phase of the reaction liquid refers to 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 liquid phase of the reaction liquid means using a pipe or the like. This indicates that the catalyst is supplied directly to the liquid phase without passing through the gas phase of the reactor. The proportion of the titanium catalyst added directly to the liquid phase of the reaction solution is preferably at least 30% by weight, more preferably at least 50% by weight, particularly preferably at least 80% by weight, most preferably at least 90% by weight. It is.

 The above titanium catalyst can be supplied directly to the liquid phase of the reaction solution in the esterification reaction tank or transesterification reaction tank without dissolving or dissolving it in a solvent, etc. In order to reduce adverse effects such as denaturation due to heat from the heat medium jacket of the vessel, it is preferable to dilute with a solvent such as 1,4-butanediol. The concentration at this time is usually from 0.1 to 20% by weight, preferably from 0.05 to 10% by weight, more preferably from 0.08 to 8% by weight, as the concentration of the titanium catalyst with respect to the whole solution. . In addition, from the viewpoint of reducing foreign matter, the water concentration in the solution is usually set to 0.5 to 1.0% by weight. The temperature at the time of preparing the solution is usually 20 to 150 ° C, preferably 30 to 100 ° C, more preferably 40 to 80 ° C, from the viewpoint of preventing deactivation and aggregation. You. Also, the catalyst solution is preferably mixed with “separate supply 1,4-butanediol” via a pipe or the like and supplied to the esterification reaction tank or transesterification reaction tank from the viewpoints of deterioration prevention, precipitation prevention, and foreign matter control. .

An example of a continuous method employing a direct polymerization method is as follows. That is, 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 a single or a plurality of esters are formed. In the reaction tank, in the presence of titanium catalyst, usually 180 to 260 ° C, preferably 200-245 ° C, more preferably 210-235 ° C, also usually 10-133 kPa, preferably 13-: L 01 kPa, more preferably 60-90 kP Under the pressure of a, the esterification reaction is continuously performed usually for 5 to 10 hours, preferably 1 to 6 hours, and the obtained oligomer as an esterification reaction product is transferred to a polycondensation reaction tank, In a plurality of polycondensation reactors, preferably continuously, in the presence of a polycondensation catalyst, usually at a temperature of 210-280 ° C, preferably 220-265 ° C, usually no more than 27 kPa, preferably The polycondensation reaction is carried out under a reduced pressure of 20 kPa or less, more preferably 13 kPa or less, and usually for 2 to 12 hours, preferably 3 to 10 hours under stirring. The polymer obtained by the polycondensation reaction is usually transferred from the bottom of the polycondensation reaction tank to a polymer extraction die, extracted in a strand form, cut with a cutter with or after cooling with water, and pelletized. It is a granular material such as a chip.

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

BM / TM = 1.1 to 4.5 (mo1 / mo1) (III)

 (However, BM is the number of moles of 1,4-butanediol supplied from the outside to the esterification reactor per unit time, and TM is the mole of terephthalic acid supplied from the outside to the esterification reactor per unit time.) If the above BMZTM value is less than 1.1, conversion rate will decrease or the catalyst will be deactivated. If it is greater than 4.5, not only will the thermal efficiency decrease, but also tetrahydrofuran, etc. By-products tend to increase. The value of BM / TM is preferably 1.5 to 4.0, more preferably 2.0 to 3.8, and particularly preferably 2.7 to 3.5.

An example of a continuous method employing the transesterification method is as follows. That is, in one or more transesterification reactors in the presence of a titanium catalyst, typically 110 ~ 260 ° C, preferably 140-245 ° C, more preferably 180-220 ° C, and usually 10-133 kPa, preferably 13-120 kPa, more preferably 60-101 kPa. The ester exchange reaction is continuously performed under pressure, usually for 5 to 5 hours, preferably 1 to 3 hours, and the obtained transesterification reaction product is transferred to a polycondensation reaction tank as an oligomer. In the polycondensation reactor, preferably continuously, in the presence of a polycondensation reaction catalyst, usually at a temperature of 210-280 ° C, preferably 220-265 ° C, usually no more than 27 kPa, preferably The polycondensation reaction is carried out under a reduced pressure of 20 kPa or less, more preferably 13 kPa or less, and usually for 2 to 12 hours, preferably 3 to 10 hours under stirring.

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

BM / DM = 1. ~ 2.5 (mo 1 / mo 1) (IV)

 (However, BM is the number of moles of 1,4-butanediol supplied externally to the transesterification reactor per unit time, and DM is the dialkyl terephthalate supplied externally to the transesterification reactor per unit time. If the above BM / DM value is less than 1.1, the conversion and catalyst activity will decrease. If it exceeds 2.5, not only will the thermal efficiency decrease, but also By-products such as tetrahydrofuran tend to increase. The value of BMZDM is preferably from 1.1 to; 1.8, more preferably from 1.2 to 1.5.

The above-mentioned "1,4-butanediol supplied to the esterification (transesterification) reaction tank from the outside" refers to 1,4-butanediol supplied together with terephthalic acid or dialkyl terephthalate as a raw material slurry or solution. In addition, 1,4-butanediol, which is supplied independently, and 1,4-butanediol used as a catalyst solvent, etc. It is. 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 to shorten the reaction time. The boiling point of 1,4-butanediol depends on the pressure of the reaction, but it is 230 ° C at 110.lkPa (atmospheric pressure) and 205 ° C at 50 kPa.

 In the process for producing PBT of the present invention, when a terephthalic acid or a dialkyl terephthalate and an excess 1,4-butanediol are continuously esterified or transesterified with these, per unit time By controlling the molar ratio of terephthalic acid or dialkyl terephthalate, which is supplied to a reaction tank (esterification or transesterification reaction tank) from the outside to 1,4-butanediol, to a constant value, It is preferable for maintaining and stabilizing the rate or transesterification rate, further reducing foreign matter, and stabilizing the amount of foreign matter.

 In the present invention, the method of controlling the molar ratio of terephthalic acid or dialkyl terephthalate and 1,4-butanediol supplied to the reaction vessel per unit time to be constant is, for example, when terephthalic acid is used as a raw material. The raw material slurry consisting of terephthalic acid and 1,4-butanediol is fixed at a certain molar ratio and supplied in a fixed amount. If the catalyst is composed of a 1,4-butanediol solution, its concentration And the supply amount is also constant, and at the same time, a certain amount of “separate supply 1,4-butanediol” is supplied to the esterification reaction tank.

Under conditions such as high temperature and reduced pressure, the amount of 1,4-butanediol gas generated from the esterification reactor fluctuates greatly. In particular, “separate 1,4-butanediol” is converted from “recycled 1,4-butanediol” When constituted, the 1,4-butanediol obtained by condensing it also fluctuates with a slight time delay from the above fluctuations in gas generation. In a preferred embodiment of the present invention, also in this case, the supply amount of recirculated 1,4-butanediol supplied to the esterification reaction tank is controlled to be constant without changing, and terephthalic acid supplied to the esterification reaction tank is controlled. Control the molar ratio of acid and 1,4-butanediol (BM / TM) so that it does not change. At this time, as in the case of the general reflux control, the liquid amount of the aggregated 1,4-butanediol is adjusted. Controlling the supply amount of recirculated 1,4-heptanediol to keep it constant will cause fluctuations in the conversion (esterification rate), and in some cases, fluctuations in the 1,4-butanediol gas generation and coagulation Due to the phase difference of the liquid volume fluctuation of 1,4-butanediol, the fluctuation is amplified and the quality becomes unstable.

 Also, when the molar ratio of the raw material terephthalic acid or dialkyl terephthalate to 1,4-butanediol excluding “separately supplied 1,4-butanediol” is constant, for example, terephthalic acid and 1,4-butanediol Even when the molar ratio of the diol raw material slurry is constant, when the supply amount is changed, that is, when the production amount is changed, the esterification reaction tank or ester is changed according to the change. "Separately supplied 1,4-butanediol" so that the molar ratio (BM / TM or BMZDM) of terephthalic acid or dialkyl terephthalate and 1,4-butanediol supplied to the exchange reaction tank is constant. There is also a method of changing the amount. Unless the amount of “separate 1,4-butanediol” is increased by increasing the supply amount of terephthalic acid component, B MZTM or B MZDM decreases, resulting in a decrease in conversion. On the other hand, if the amount of the terephthalic acid component is not reduced and the amount of the “separate 1,4-butanediol” is not reduced, the BMZTM or B MZDM will increase and the conversion will increase, but there will be additional This leads to increased reaction and energy loss.

 When changing the supply amount of the terephthalic acid component, while controlling the supply amount of “separate supply 1,4-butanediol” so as to keep the BM No TM or B MZDM constant, at the same time, as described above, It is preferable to control the supply amount of “separate supply 1,4-butanediol” so that it does not fluctuate due to the short-term 1,4-butanediol gas generation amount.

As the esterification reaction tank or the transesterification reaction tank, known ones can be used, and any type such as a vertical stirring complete mixing tank, a vertical thermal convection type mixing tank, and a tower-type continuous reaction tank may be used. In addition, a single tank or a plurality of tanks in which the same or different tanks are arranged in series may be used. Among them, a reaction tank having a stirring device is preferable. In addition to the usual type consisting of a power unit, bearings, shafts, and stirring blades, a type that rotates at high speed, such as a turbine stirrer type high-speed rotary stirrer, a disk mill type stirrer, and a rotor mill type stirrer, is also used. You can do it.

 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 upper, lower, and lateral portions of the reaction tank, a part of the reaction solution is piped into the reactor. It is also possible to adopt a method in which the reaction solution is circulated by taking it out of the reactor and stirring with a line mixer or the like.

 Known types of stirring blades can be selected, and specific examples include propeller blades, screw blades, turbine blades, fan turbine blades, disk turbine blades, faudler blades, full zone blades, and max blended blades. .

 In the production of PBT, usually, a plurality of reaction vessels are used, preferably 2 to 5 reaction vessels are used, and the molecular weight is sequentially increased. Usually, an initial esterification or transesterification reaction is followed by a polycondensation reaction.

 In the polycondensation reaction step of PBT, a single reaction vessel or a plurality of reaction vessels may be used, but preferably, a plurality of reaction vessels are used. The form of the reaction tank may be any type such as a vertical stirring complete mixing tank, a vertical thermal convection type mixing tank, a tower type continuous reaction tank, and the like, or a combination thereof. Among them, a reaction tank having a stirring device is preferable. As the stirring device, in addition to a normal type including a power unit, a bearing, a shaft, and a stirring blade, a high-speed rotary stirrer with a turbine stay, an overnight type, and a disk mill-type stirrer A type that rotates at high speed such as a rotor mill type stirrer can also be used.

The form of stirring is not particularly limited, and in addition to the usual stirring method in which the reaction solution in the reaction tank is directly stirred from the upper, lower, and lateral portions of the reaction tank, a part of the reaction solution is piped into the reactor. It is also possible to adopt a method in which the reaction solution is circulated by taking it out of the reactor and stirring it with a line mixer or the like. In particular, it is recommended that at least one of the polycondensation reactors be a horizontal reactor with a horizontal axis of rotation and excellent surface renewal and self-cleaning properties. There is no limitation on the rotation direction of the stirring device of the horizontal reactor, When there are two stirring shafts, the rotation directions of the shafts are preferably in different directions, and more preferably, the rotation direction is such that the upper part is stretched and the lower part is involved in the polymer.

 In addition, in order to suppress coloring and deterioration, and to suppress an increase in the number of terminals such as a beer group, in at least one reaction tank, usually 1.3 kPa or less, preferably 0.5 kPa or less, more preferably 0.5 kPa or less. Under high vacuum below 3 kPa, typically 225-255. The temperature is preferably 230 to 250 ° C, more preferably 233 to 245 ° C.

 Further, in the polycondensation reaction step of PBT, once a PBT having a relatively small molecular weight, for example, an intrinsic viscosity of about 0.1 to 1.0 dLZg is produced by melt polycondensation, the PBT melting point is continuously determined. Solid-state polycondensation (solid-state polymerization) can be performed at the following temperatures.

 By performing solid-phase polymerization, the number of lipoxyl groups at the terminal of the obtained PBT can be reduced, so that the effects of the present invention such as improvement in hydrolysis resistance become more remarkable.

 In the PBT of the present invention, the foreign matter derived from the catalyst is significantly reduced, so that the foreign matter does not need to be removed. However, by installing a filter in the flow path between the polymer precursor and the polymer, the quality is further improved. Is obtained. In the present invention, for the above-mentioned reason, when a filter having the same opening as that used in a conventional PBT manufacturing facility is used, it is possible to extend the life until replacement. If the life until replacement is set to be the same, a filter with a smaller opening can be installed.

If the filter is installed too upstream in the manufacturing process, it will not be possible to remove foreign substances generated on the downstream side, and if the viscosity on the downstream side is high, the pressure loss at the filter will increase and the flow rate will be maintained. In order to achieve this, it is necessary to increase the size of the filter, to increase the size of the filter, and to increase the size of the filter and other equipment such as piping. Becomes inevitable. Therefore, the installation position of the filter depends on the intrinsic viscosity of PBT or its precursor. Usually, a position of 0.1 to 1.2 dL / g, preferably 0.2 to 1.2 OdLZg, and more preferably 0.5 to 0.9 dLZg is selected.

 The filter medium constituting the filter may be any of a metal wind, a laminated metal mesh, a metal nonwoven fabric, a porous metal plate, and the like. From the viewpoint of filtration accuracy, a laminated metal mesh or a metal nonwoven fabric is preferable. Preferably, the opening is fixed by sintering. The shape of the filter may be any type such as a basket type, a disk type, a leaf disk type, a tube type, a flat cylindrical evening, and a pleated cylindrical type. In order to prevent the operation of the plant from being affected, it is preferable to install a plurality of filters and use them by switching, or to install an auto screen changer or the like. Although the absolute filtration accuracy of the filter is not particularly limited, it is generally 0.5 to 200 am, preferably 1 to 100 m, more preferably 5 to 50 m, and particularly preferably 10 to 30 xm. If the absolute filtration accuracy is too high, the effect of reducing foreign substances in the product will be lost, and if it is too low, productivity will decrease and the frequency of filter replacement will increase.

 Hereinafter, a preferred embodiment of a method for manufacturing a PBT will be described with reference to the accompanying drawings. FIG. 1 is an explanatory view of an example of the esterification reaction step or transesterification reaction step employed in the present invention, and FIGS. 2 to 5 are diagrams of another example of the esterification reaction step or ester exchange reaction step employed in the present invention. FIG. 6 is an explanatory view of an example of the polycondensation step employed in the present invention, and FIGS. 7 to 9 are explanatory views of another example of the 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 a slurry form from a raw material supply line (1). You. In the case of terephthalic acid dialkyl ester, it is usually supplied to the reaction tank (A) without being mixed with 1,4-butanediol. On the other hand, the titanium catalyst is preferably made into a solution of 1,4-butanediol in a catalyst preparation tank (not shown), and then supplied to the catalyst supply line (3). In Figure 1, recirculation 1, (4) An embodiment is shown in which a catalyst supply line (3) is connected to a butanediol recirculation line (2), and both are mixed and then supplied to the liquid phase portion of the reaction tank (A).

 The gas distilled from the reaction tank (A) passes through the distillation line (5) and is separated into high-boiling components and low-boiling components in the rectification column (C). Usually, the main component of the high-boiling component is 1,4-butyldiol, and the main component of the low-boiling component is water and tetrahydrofuran for the direct polymerization method, and alcohol, tetrahydrofuran, and water for the transesterification method. It is.

 The high-boiling components separated in the rectification column (C) are extracted from the extraction line (6), pass through the pump (D), and partly circulate from the recirculation line (2) to the reaction tank (A). And a part is returned from the circulation line (7) to the rectification column (C). The surplus is extracted outside through 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), passed through the condensate line (10), and stored in the tank (F). Is temporarily stored. Part of the light-boiling components collected in the tank (F) is returned to the rectification column (C) via the extraction line (11), the pump (E) and the circulation line (12), and the remainder is It is extracted outside through the extraction line (13). The condenser (G) is connected to an exhaust device (not shown) via a vent line (14). The oligomer generated in the reaction tank (A) is extracted via the extraction pump (B) and the 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. Further, the raw material supply line (1) may be connected to the liquid phase of the reaction tank (A).

 The process shown in Fig. 2 is different from the process shown in Fig. 1 in that the rectification tower (C) is equipped with a repoiler (H), and the supply line (15 ) Is provided. The installation of the repoiler (H) facilitates the operation control of the rectification tower (C).

The process shown in Fig. 3 differs from the process shown in Fig. 1 in that a bypass line (16) branched from the circulation line (7) is connected to the gas phase of the reaction tank (A). You. Therefore, in the case of the process shown in FIG. 3, a part of the recirculated 1,4-butanediol returns to the reaction solution via the gas phase of the reaction tank (A).

 The process shown in FIG. 4 is different from the process shown in FIG. 1 in that a flow control valve (J) and a flow control valve (K) are provided in the recirculation line (2) and the extraction line (8), respectively. Further, to detect the liquid level of the rectification tower (C) and adjust the opening of the flow control valve (K) based on the detection signal to adjust the liquid level of the rectification tower (C) to a constant level. In that a control device (L) is provided. The liquid level at the bottom of the rectification column (C) is

Although the temperature fluctuates slightly due to fluctuations in the temperature in (A), fluctuations in the amount of distilled gas divided by the composition of the distillate gas, fluctuations in the supply of raw materials, and fluctuations in the temperature of the rectification tower (C), the process shown in Fig. For example, due to fluctuations in the liquid level at the bottom of the rectification column (C), the amount extracted from the extraction line (8) is adjusted, and the amount of recirculation from the recirculation line (2) is maintained constant . The process shown in FIG. 5 is different from the process shown in FIG. 2 in that the recirculation line (2) and the extraction line (8) are provided with a flow control valve (J) and a flow control valve (K), respectively. , Withdrawal line (6) and circulation line (7) for high boiling component tanks respectively

(N) and a reboiler (M) are provided. A supply line (15) is provided at a position downstream of the reboiler (H) of the circulation line (7).

A control device (L) that detects the liquid level of (N) and adjusts the opening of the flow control valve (K) based on the detection signal to maintain the liquid level of the high boiling component tank (N) constant. ) Is provided. The process shown in FIG. 5 has the same improvement effect as the process shown in FIG. The process shown in Fig. 5 clarifies that a signal based on the liquid level fluctuation of the high boiling component tank (N) can be used as an input signal to the controller (L).

In FIG. 6, the oligomer supplied from the extraction line (4) shown in FIGS. 1 to 5 is polycondensed under reduced pressure in the first polycondensation reaction tank (a) to form a prepolymer, It is supplied to the second polycondensation reaction tank (d) via the extraction gear pump (c) and the extraction line (L1). In the second polycondensation reaction tank (d), the polycondensation usually proceeds further at a lower pressure than in the first polycondensation reaction tank (a) to form a polymer. The resulting polymer Is extracted from the die head (g) through the extraction gear pump (e) and the extraction line (L3) in the form of a molten strand, cooled with water, etc. And cut into pellets. The symbol (L2) is the vent line of the first polycondensation reaction tank (a), and the symbol (L4) is the vent line of the second polycondensation reaction tank (d). The process shown in FIG. 7 is different from the process shown in FIG. 6 in that a filter (f) is provided in the flow path of the extraction line (L3).

 The process shown in FIG. 8 is different from the process shown in FIG. 6 in that a third polycondensation reaction tank (k) is provided after the second polycondensation reaction tank (d). 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. The polymer introduced from the second polycondensation reaction tank (d) to the third polycondensation reaction tank (k) through the extraction line (L3) is further subjected to polycondensation here, and then the extraction gear pump (M) and the melted strand from the die head (g) through the extraction line (L5), cooled with water, etc., cut with a rotary cutter (h), and pelletized. Become. The symbol (L 6) is the vent line of the third polycondensation reaction tank (k).

 The process shown in Fig. 9 differs from the process shown in Fig. 8 in that a filter is installed in the middle of the extraction line (L3) between the second polycondensation reaction tank (d) and the third polycondensation reaction tank (k). The difference is that (f) is equipped.

 <General composition containing the above polybutylene terephthalate>

 The PBT of the present invention includes 2,6-di-tert-butyl-4-octylphenol, pentaerythristyl-tetrakis [3- (3 ', 5'_t-butyl-4'-hydroxyphenyl) propionate] and the like. Phenolic compounds, thioether compounds such as dilauryl-1,3,3'-thiodipropionate, pen-erythrityl-tetrakis (3-lauryl thiodipropionate), triphenyl phosphite, tris (nonylphenyl) phosphite, tris ( Antioxidants, such as phosphorus compounds such as 2,4-Gt-butylphenylphosphite, paraffin wax,

, Polyethylene wax, montanic acid or montanic acid Long-chain fatty acids such as esters, esters thereof, and release agents such as silicone oil may be added.

 The PBT of the present invention may contain a reinforcing filler. The reinforcing filler is not particularly limited, but examples thereof include inorganic fibers such as glass fiber, carbon fiber, silica-alumina fiber, zirconia fiber, boron fiber, boron nitride fiber, potassium silicon nitride potassium fiber, and metal fiber. And organic fibers such as fibers, aromatic polyamide fibers and fluororesin fibers. These reinforcing fillers can be used in combination of two or more. Among the above reinforcing fillers, inorganic fillers, particularly glass fibers, are preferably used.

 When the reinforcing filler is an inorganic fiber or an organic fiber, the average fiber diameter is not particularly limited, but is usually l to 100 im, preferably 2 to 50 m, more preferably 3 to 30 / zm, and particularly preferably. Is 5-20 m. The average fiber length is not particularly limited, but is usually 0.1 to 20 mm, preferably 1 to 10 mm. The reinforcing filler is preferably used after surface treatment with a sizing agent or a surface treatment agent in order to improve interfacial adhesion with PBT. Examples of the sizing agent or the surface treatment agent include functional compounds such as an epoxy compound, an acrylic compound, an isocyanate compound, a silane compound, and a titanate compound. The reinforcing filler can be surface-treated in advance with a sizing agent or a surface treatment agent, or can be surface-treated by adding a sizing agent or a surface treatment agent when preparing a PBT composition. . The amount of the reinforcing filler to be added is usually 150 parts by weight or less, preferably 5 to 100 parts by weight, based on 100 parts by weight of the PBT resin.

The PBT of the present invention may contain other fillers together with the reinforcing filler. Other fillers to be blended include, for example, plate-like inorganic fillers, ceramic beads, asbestos, wollastonite, talc, clay, my power, zeolite, power orient, potassium titanate, barium sulfate, titanium oxide, oxide Examples include silicon, aluminum oxide, and magnesium hydroxide. By blending the plate-like inorganic filler, the anisotropy and warpage of the molded article can be reduced. Plate-like inorganic filler Examples thereof include glass flakes, mica, and metal foil. Among these, glass flake is preferably used.

 A flame retardant can be added to the PBT of the present invention in order to impart flame retardancy. The flame retardant is not particularly restricted but includes, for example, organic halogen compounds, antimony compounds, phosphorus compounds, other organic flame retardants, inorganic flame retardants and the like. Examples of the organic halogen compound include brominated polycarbonate, brominated oxy resin, brominated phenoxy resin, brominated polyphenylene ether resin, brominated polystyrene resin, brominated bisphenol A, poly (pentabromobenzyl acrylate), and the like. Is mentioned. Examples of the antimony compound include antimony trioxide, antimony pentoxide, and sodium antimonate. Examples of the phosphorus compound include a phosphoric acid ester, polyphosphoric acid, ammonium polyphosphate, and red phosphorus. Examples of other organic flame retardants include nitrogen compounds such as melamine and cyanuric acid. Other inorganic flame retardants include, for example, aluminum hydroxide, magnesium hydroxide, silicon compounds, boron compounds and the like.

 The PBT of the present invention may contain conventional additives and the like, if necessary. Such additives are not particularly limited, and include, for example, stabilizers such as antioxidants and heat stabilizers, as well as lubricants, fillers, release agents, catalyst deactivators, nucleating agents, and crystallization accelerators. And the like. These additives can be added during or after the polymerization. Examples of the crystal nucleating agent include talc, kaolin, boron nitride, and the like. Examples of the above-mentioned filler include layered silicate, zeolite, silica, and the like. d Furthermore, in order to provide the desired performance to PBT, ultraviolet absorbers, stabilizers such as weathering stabilizers, coloring agents such as dyes and pigments, antistatic agents, foaming agents, plasticizers, impact modifiers, etc. Can be blended.

The PBT of the present invention may include polyethylene, polypropylene, polystyrene, polyacrylonitrile, polymethacrylate, ABS resin, polyacrylonitrile, polyamide, polyphenylene sulfide, polyethylene, if necessary. Thermoplastic resins such as terephthalate, liquid crystal polyester, polyacetal, and polyphenylene oxide, and thermosetting resins such as phenolic resin, melamine resin, silicone resin, and epoxy resin can be blended. These thermoplastic resins and thermosetting resins can be used in combination of two or more. The method of compounding the above-mentioned various additives and resins is not particularly limited, but it is preferable to use a single-screw or twin-screw extruder having equipment capable of devolatilizing from the vent opening as a kneader. Each component, including additional components, can be fed to the kneader at once or can be fed sequentially. Also, two or more components selected from each component, including additional components, can be mixed in advance.

<Specific composition containing the above polybutylene terephthalate>

 As described above, the PBT of the present invention can be used as a general resin composition by an ordinary method in the resin field, and furthermore, the PBT of the present invention can be used in combination with a specific additive in various ways. It can be used as a specific polybutylene terephthalate composition having a function. Hereinafter, these resin compositions will be described. (Heat-resistant PBT composition)

The heat-resistant PBT composition of the present invention is a group consisting of the above-mentioned PBT (A), a phenolic antioxidant (B 1), a zeolite antioxidant (B 2) and a phosphorus antioxidant (B 3). It is characterized by containing one or more antioxidants selected from the group consisting of: The phenolic antioxidant (B 1) used in the present invention means a phenolic antioxidant having a phenolic hydroxyl group. Among them, the hindered phenolic antioxidant is a phenolic hydroxyl group to which a phenolic hydroxyl group is bonded. Means an antioxidant in which one or two carbon atoms adjacent to a carbon atom of the aromatic ring have been substituted with a substituent having 4 or more carbon atoms. The substituent having 4 or more carbon atoms may be bonded to a carbon atom of the aromatic ring by a carbon-carbon bond, or may be bonded via an atom other than carbon. Specific examples of the phenolic antioxidant (B 1) used in the present invention include p-cyclohexylphenol, 31-t-butyl-4-methoxyphenol, 4,4′-isopropylidenediphenol, 1, 1-bis (4-hydro Non-hindered phenolic antioxidants, such as cyclohexane) cyclohexane, etc., 2-t-butyl-4-methoxyphenol, 2,6-di-t-butyl-p-cresol, 2,4,6-tri-t- Butylphenol, 4-hydroxymethyl-2,6-di-t-butylphenol, styrenated phenol, 2,5-di-t-butylhydroquinone, octadecyl-3- (3-, 3-di-t-butyl-4 Hydroxyphenyl) propionate, triethylene glycol bis

[3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis [3- (3,5-di-t-butyl-4 monohydroxyphenyl) ) Propionate], pentaerythryl 1 rutetrakis

[3- (3,5-di-t-butyl-1-hydroxyphenyl) propionate], 2,2'-methylenebis (4-methyl-6_t_butylphenol), 2,2'-methylenebis (6-t —Butyl-4-ethylfurenol), 2,2′-methylenbis [4-methyl-6- (1,3,5-trimethylhexyl) phenol], 4,4′-methylenebis (2,6-di-t— Butylphenol), 4,4'-butylidenebis (3_methyl_6-t-butylphenol), 2,6-bis (2-1-hydroxy-3-t-butyl-1-5-methylbenzyl) _4_methylphenol, 1 , 1,3-Tris [2-methyl-4-hydroxy-5-t-butylphenyl] butane, 1,3,5-trimethylyl 2,4,6-tris [3,5-di-t-butyl-4-hydroxy Benzyl] benzene, tris (3,5-di-t-butyl 4-hydroxybenzyl) Socyanurate, Tris [3- (3,5-di-t-butyl-1-hydroxyphenyl) propionyloxexetyl] isocyanurate, 4,4'-thiopis (3-methyl-1-t-butylphenol) Hindered phenols such as 2,2'-thiobis (4-methyl-6-t-butylphenol), 4,4'-thiopis (2-methyl-6-t-butylphenol), and thiobis (β-naphthol) And antioxidants. In particular, a hindered phenol-based antioxidant can be suitably used as a radical trapping agent because it tends to itself become a stable radical. Hindered fenor The molecular weight of the toluene-based antioxidant is usually at least 200, preferably at least 500, and the upper limit is usually at most 300.

 The zeotype antioxidant (B 2) used in the present invention means an antioxidant having no zirconium atom without a phenolic hydroxy group. Specific examples of the zirconium-based antioxidants (B 2) include didodecylthiodipropionate, ditetradecylthiodipropionate, dioctadecylthiodipropionate, and pen erythritol tetrakis (3-dodecylthiopropionate). Nate), thiobis (N-phenyl) 3-naphthylamine, 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, tetramethylthiuram monosulfide, tetramethylthiuram disulphide, nickel dibutyldithiocarbamate, nickel Isopropyl xanthate, trilauryl trithiophosphite and the like. In particular, a thioether-based antioxidant having a thioether structure can be suitably used because it receives and reduces oxygen from an oxidized substance. The molecular weight of the zirconium antioxidant is usually at least 200, preferably at least 500, and the upper limit is usually at least 300.

The phosphorus-based antioxidant (B 3) used in the present invention means a phosphorus-containing antioxidant having neither a phenolic hydroxyl group nor an iodine atom. The phosphorus antioxidant (B 3) is preferably an antioxidant having a P (OR) ₃ structure. Here, R is an alkyl group, an alkylene group, an aryl group, an arylene group, etc., three R may be the same or different, and two R may form a ring structure. Examples of such phosphorus-based antioxidants include triphenylphosphite, diphenyldecylphosphite, phenyldiisodecylphosphite, tri (nonylphenyl) phosphite, and bis (2,4-dibutylbutylphenyl) pen. Erythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pen and erythritol diphosphite.

In the heat-resistant PBT composition of the present invention, the phenolic antioxidant (B 1) The content is usually 001 to 2 parts by weight, preferably 0.003 to 1 part by weight, based on 100 parts by weight of PBT. If the content of the phenolic antioxidant is less than 0.001 part by weight, the antioxidant effect may not be sufficiently exhibited, and if it exceeds 2 parts by weight, the oxidative heat stability may deteriorate, Decomposition of the resin may occur during kneading.

 In the heat-resistant PBT composition of the present invention, the zeolite-based antioxidant (B2) and the phosphorus- or phosphorus-based antioxidant (B3) improve the heat aging resistance of the resin composition, and improve the color tone, tensile strength and elongation. It has the effect of improving the retention such as degree.

 In the heat-resistant PBT composition of the present invention, the content of the zeolite antioxidant (B2) and the content of the phosphorus antioxidant (B3) are usually 0.001-1. 9 parts by weight, preferably 0.003 to 1 part by weight. If the content of each antioxidant is less than 0.001 parts by weight, the above effects may not be sufficiently exerted.If the content is more than 1.9 parts by weight, the oxidation heat stability may deteriorate, Decomposition of the resin may occur during melt-kneading.

 When the heat-resistant PBT composition of the present invention contains a phenolic antioxidant (B1), a zeolite antioxidant (B2), and / or a phosphorus-based antioxidant (B3), The ratio of the zirconium antioxidant and / or the phosphorus antioxidant to 1 part by weight of the antioxidant is usually 2 to 5 parts by weight. When the ratio of the zirconium antioxidant and the Z or phosphorus antioxidant is less than 0.2 part by weight or more than 5 parts by weight, the effect of improving the heat aging resistance may be reduced.

 In the heat-resistant PBT composition of the present invention, when a phenolic antioxidant and a zeolite antioxidant and a phosphorus or phosphorus antioxidant are contained, the total content of the antioxidant is based on 100 parts by weight of PBT. Usually less than 2 parts by weight. If the total content of the antioxidants exceeds 2 parts by weight, the oxidative heat stability may be deteriorated, or the resin may be decomposed during melt-kneading.

(Good release PBT composition) The good releasable PBT composition of the present invention comprises a fatty acid residue having 12 to 36 carbon atoms and an alcohol residue having 1 to 36 carbon atoms with respect to 100 parts by weight of the PBT (A). Fatty acid ester (C 1), paraffin wax and polyethylene wax

(C2) 0.01 to 2 parts by weight of a release agent selected from the group of (C2).

 The fatty acid forming the fatty acid ester (C 1) used in the present invention must be a fatty acid ester comprising a fatty acid residue having 12 to 36 carbon atoms and an alcohol residue having 1 to 36 carbon atoms. And preferably a fatty acid ester comprising a fatty acid residue having 16 to 32 carbon atoms and an alcohol residue having 1 to 36 carbon atoms, and more preferably a fatty acid residue having 16 to 32 carbon atoms and 1 to carbon atoms. It is a fatty acid ester consisting of 20 alcohol residues.

 Specific examples of fatty acids that form fatty acid esters (C 1) include lauric acid, myristic acid, palmitic acid, stearic acid, araquinic acid, behenic acid, lignoceric acid, serotinic acid, montanic acid, melisic acid, and raccelic acid. Are mentioned. When the fatty acid residue has less than 12 carbon atoms, the releasability is low, and the fatty acid residue is easily volatilized, which may cause mold contamination. If the fatty acid residue has more than 36 carbon atoms, the effect of improving the releasability may not be sufficiently exhibited.

As the alcohol forming the fatty acid ester (C 1), a monohydric alcohol, a dihydric alcohol and a trihydric or higher polyhydric alcohol can be used. Specific examples of such alcohols include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, cyclohexanol, heptanol, octanol, lauryl alcohol, and stearyl alcohol. Monohydric alcohols, such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, and other dihydric alcohols, Trihydric alcohols such as serine and trimethylolpropane; and tetrahydric alcohols such as pentaerythritol and erythritol. Carbon number of alcohol residue If it exceeds 36, the effect of improving the releasability may not be sufficiently exhibited. Examples of the method for producing the fatty acid ester (C 1) include a method in which a fatty acid and an alcohol are used as raw materials and esterification is performed in the presence of an acid catalyst such as sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, and the like. When the alcohol forming the fatty acid ester is a high-boiling alcohol, a transesterification method can be employed between the lower alkyl ester of the fatty acid and the high-boiling alcohol.

 Specific examples of the fatty acid ester (C 1) include methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl behenate, methyl montanate, isopropyl myristate, isopropyl palmitate, and laurin. Butyl acid, butyl stearate, octyl palmitate, octyl stearate, lauryl laurate, stearyl stearate, ethylene glycol dilaurate, ethylene glycol dipalmitate, ethylene blender distearate, ethylene glycol dimontanate, Propylene glycol monolaurate, propylene glycol monostearate, 1,3-propanediol dilaurate, 1,3-propanediol distearate, 1,3-propanediol Ludimontane, 1,4-butanediol diureate, 1,4-butanediol distearate, 1,4-butanediol dimontanate, glycerin monopalmitate, glycerin monostearate, glycerin monomontane, Glycerin dipalmitate, glycerin distearate, glycerin dioleate, glycerin tristearate, glycerin trioleate, pen erythritol monopalmitate, pen erythritol monostearate, pentaerythritol dipalmitate, penta erythritol Erythritol distearate, pentaerythritol tripalmitate, pentaerythritol tristearate, erythritol tristearate, erythritol tetrastearate, etc.

The molecular weight of (C 2) is usually 3 00-5000, preferably 500-3000. If the molecular weight is less than 300, it will easily evaporate from the vacuum vent during compounding, making it difficult to exert its effect, and wax will easily bleed out during molding, causing mold fouling. On the other hand, when the molecular weight exceeds 5,000, the effect as a release agent is reduced without bleeding out.

 In the good releasable PBT composition of the present invention, the content of the fatty acid ester (C1) is usually 0.01 to 2 parts by weight, preferably 0.1 to 1 part by weight based on 100 parts by weight of PBT. . When the content of the fatty acid ester (C1) is less than 0.01 parts by weight, the effect of improving the releasability (the effect of shortening the molding cycle) may not be sufficiently exhibited. The effect of improving the releasability corresponding to the increase of the ester cannot be obtained, but rather the strength and the heat resistance may decrease.

 In the good release PBT composition of the present invention, the content of paraffin wax or polyethylene wax (C2) is usually from 01 to 2 parts by weight, preferably from 0.1 to 1 part by weight, based on 100 parts by weight of PBT. Department. If the content of paraffin wax or polyethylene wax (C2) is less than 0.01 parts by weight, the effect of improving releasability (the effect of shortening the molding cycle) may not be sufficiently exhibited, and if it exceeds 2 parts by weight. Does not provide the effect of improving the releasability corresponding to the increase in paraffin wax or polyethylene wax, but rather may lower the strength and heat resistance.

 (Hydrolysis-resistant PBT composition)

 The hydrolysis-resistant PBT composition of the present invention contains 0.01 to 20 parts by weight of an epoxy compound (E) and 0 to 200 parts by weight of a reinforcing filler (D) based on 100 parts by weight of the above-mentioned PBT (A). It is characterized by doing.

The epoxy compound (E) used in the present invention may be monofunctional, difunctional, trifunctional or polyfunctional, or may be a mixture of two or more of these. In particular, a bifunctional, trifunctional, or polyfunctional epoxy compound, that is, a compound having two or more epoxy groups in one molecule is preferable. Epoxy compound (E) is composed of alcohol, phenolic compound or carboxylic acid and Any of a glycidyl compound and an alicyclic epoxy compound obtained from the reaction with drin may be used.

 Specific examples of the epoxy compound (E) include methyldaricidyl ether, petylglycidylether, 2-ethylhexyldaricidyl ether, decylglycidylether, stearylglycidylether, phenyldaricidyl ether, butylphenyl Daricidyl ethers such as dalicidyl ether and arylglycidyl ether; neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, propylene glycol diglycidyl ether, bisphenol A diglycidyl ether, etc. Diglycidyl ethers; fatty acid glycidyl esters such as daricidyl benzoate and sorbic acid dalycidyl ester; diglycidyl ester adipate; diglycidyl terephthalate Ester, diglycidyl esters such as orthophthalic acid diglycidyl ester le; 3, 4 _ epoxy cyclohexane Kishirumechiru 3, 4 etc. alicyclic diepoxy compounds such as hexyl Cal Po carboxylate and the like into single epoxycycloalkyl. Among them, dalicidyl ether compounds obtained by the reaction of bisphenol A with epichlorohydrin, particularly bisphenol A diglycidyl ether, are preferred.

 Examples of the type of the reinforcing filler (D) used in the present invention include glass fiber, carbon fiber, silica / alumina fiber, zirconia fiber, boron fiber, boron nitride fiber, potassium silicon titanate fiber, and metal. Examples include inorganic fibers such as fibers, and organic fibers such as aromatic polyamide fibers and fluororesin fibers. One of these reinforcing fillers may be used alone, or two or more of them may be used in combination. Of these, inorganic fillers are preferably used, and glass fiber is particularly preferably used.

When the reinforcing filler (D) is an inorganic fiber or an organic fiber, its average fiber diameter is usually 1 to 100 m, preferably 2 to 50 m, more preferably 3 to 30 ^ m, and particularly preferably. 5 to 20 xm. The average fiber length is usually 0.1 to 20. mm, preferably 1 to: I 0 mm.

 The reinforcing filler (D) is preferably used after surface treatment with a sizing agent or a surface treatment agent in order to improve interfacial adhesion with PBT. Examples of the sizing agent or the surface treatment agent include functional compounds such as an epoxy compound, an acrylic compound, an isocyanate compound, a silane compound, and a titanate compound. The reinforcing filler (D) can be surface-treated in advance with a sizing agent or a surface treatment agent, and the surface treatment should be performed by adding a sizing agent or a surface treatment agent when preparing the PBT composition. Can also be.

 Examples of the glass fiber used in the present invention include various glass fibers such as E glass, C glass, A glass, S glass, and S-2 glass. Among these, E-glass fiberglass, which has a low alkali content and good electrical properties, is preferred.

 The average fiber diameter of the glass fibers is usually 1 to 100 / m, preferably 2 to 50m, more preferably 3 to 30m, and particularly preferably 5 to 20 / im. Glass fibers with an average fiber diameter of less than 1 m are not easy to manufacture and may increase costs. Glass fibers having an average fiber diameter of more than 100 zm may decrease the tensile strength of the glass fibers. The average fiber length of the glass fibers is usually from l to 20 mm, preferably from 1 to 10 mm. If the average fiber length is less than 0.1 mm, the reinforcing effect of the glass fiber may not be sufficiently exhibited.If the average fiber length exceeds 2 Omm, melt kneading with PBT or molding of the PBT composition May be difficult.

 The glass fiber is preferably glass fiber that has been treated with a surface treatment agent. By treating the surface of the glass fiber with the surface treatment agent, strong adhesion or bonding occurs at the interface between the PBT and the glass fiber, and the stress is transmitted from the PBT to the glass fiber, thereby exhibiting the reinforcing effect of the glass fiber.

Examples of the surface treatment agent to be used include, for example, chlorosilane-based compounds such as vinyltrichlorosilane and methylvinyldichlorosilane, vinyltrimethoxysilane, Vinyltriethoxysilane, biertriacetoxysilane, methacryloxy

4-epoxycyclohexyl) Epoxysilane-based compounds such as ethyltrimethoxysilane and glycidoxypropyltrimethoxysilane, acryl-based compounds, isocyanate-based compounds, titanate-based compounds, and epoxy-based compounds.

 Further, the glass fiber is preferably a glass fiber that has been treated with a sizing agent. By treating the glass fiber with a sizing agent, the workability of handling the glass fiber can be improved and the glass fiber can be prevented from being damaged. Examples of the sizing agent used include resin emulsions such as vinyl acetate resin, ethylene-vinyl acetate copolymer, acrylic resin, epoxy resin, polyurethane resin, and polyester resin.

 In the hydrolysis-resistant PBT composition of the present invention, the content of the epoxy compound (E) is usually 0.01 to 20 parts by weight, preferably 0.03 to 10 parts by weight, based on 100 parts by weight of PBT. When the content of the epoxy compound (E) is less than 0.01 part by weight, there is almost no effect of improving the hydrolysis resistance, and when the content exceeds 20 parts by weight, other mechanical properties are degraded or the melting heat is stabilized. Or worse.

 In the hydrolysis-resistant PBT composition of the present invention, the content of the reinforcing filler (D) is usually 0 to 200 parts by weight, preferably 0 to 150 parts by weight, based on 100 parts by weight of PBT. When the content of the reinforcing filler (D) is more than 200 parts by weight, there is a possibility that melt-kneading and molding of the resin composition become difficult.

 (Impact PBT composition)

 The impact-resistant PBT composition of the present invention comprises, based on 100 parts by weight of the above-mentioned PBT (A), 0.5 to 40 parts by weight of an impact resistance improving material (F) and 0 to 200 parts by weight of a reinforcing filler (D). Parts.

The impact modifier (F) used in the present invention is used to improve impact values such as Izod impact value, Charpy impact value, and surface impact value. Rubber, butadiene rubber, silicone rubber and the like. In particular, acrylic rubber is preferable. Acrylic rubber is a rubber-like elastic material obtained by polymerization of acrylate or copolymerization based on acrylate, and a typical example is acrylate with a small amount of acrylate such as butyl acrylate. A rubber-like polymer obtained by graft-polymerizing a graft-polymerizable monomer such as methyl methacrylate with a polymer obtained by polymerizing a cross-linkable monomer such as range acrylate is exemplified.

 Examples of the acrylate include methyl acrylate, ethyl acrylate, propyl acrylate, hexyl acrylate, and 2-ethyl hexyl acrylate in addition to butyl acrylate. Examples of the crosslinkable monomer include, in addition to petylene diacrylate, esters of polyol and acrylic acid or methacrylic acid such as petylene dimethacrylate, trimethylolpropane trimethacrylate, divinylbenzene, vinyl acrylate, Vinyl conjugates such as vinyl methacrylate, aryl acrylate, aryl methacrylate, diaryl malate, diaryl fumarate, diaryl itaconate, monoaryl maleate, monoallyl fumarate, triaryl sinurate And allyl compounds. 》

 Examples of the graft polymerizable monomer include, in addition to methyl methacrylate, methacrylates such as ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate, styrene, and acrylonitrile. Can be A part of the graft polymerizable monomer may be used for producing a polymer by polymerizing the acrylate and the crosslinkable monomer, and may be copolymerized.

In the impact-resistant PBT composition of the present invention, the content of the impact modifier (F) is usually 0.5 to 40 parts by weight, preferably 1 to 35 parts by weight, based on 100 parts by weight of PBT. Parts, more preferably 2 to 30 parts by weight. If the content of the impact modifier (F) is less than 5 parts by weight, no improvement in impact resistance ゃ heat shock resistance is observed. If it exceeds 40 parts by weight, mechanical properties such as tensile strength and bending strength are significantly reduced.

 In the impact-resistant PBT composition of the present invention, the type and content of the reinforcing filler (D) are the same type and content as described in the above-mentioned hydrolysis-resistant PBT composition. .

 (Flame retardant PBT composition)

 The flame-retardant PBT composition of the present invention comprises 3 to 50 parts by weight of a brominated aromatic compound-based flame retardant (G) and 1 to 30 parts by weight of an antimony compound (H) based on 100 parts by weight of the PBT (A). The anti-dripping agent (I) contains 0 to 15 parts by weight and the reinforcing filler (D) 0 to 200 parts by weight.

The brominated aromatic compound-based flame retardant (G) used in the present invention is an aromatic compound known as a brominated flame retardant used in a resin. For example, an epoxy compound of tetrabromobisphenol A Oligomer, poly (pentabromobenzyl acrylate), polybromophenyl ether, brominated polystyrene, brominated epoxy, brominated imide, brominated polycarbonate, and the like. Antimony compound used in the present invention as the (H), for example, include oxide antimony Ya antimonate salts, specific examples, antimony trioxide (Sb ₂ 〇 _3), antimony tetroxide (Sb ₂ 0 ₄₎ , antimony salts such as oxides or antimonate Natoriumu such antimony pentoxide (Sb ₂ 〇 _5).

 The anti-dripping agent (I) used in the present invention refers to a compound having a property of preventing dripping of a resin during combustion, and specific examples thereof include silicone oil, silica, asbestos, fluororesin, and talc. Other examples include layered silicates such as my force. Particularly, from the viewpoint of the flame retardancy of the composition, preferred anti-dripping agents are fluorine-containing polymers or layered silicates.

Specific examples of the fluororesin used as the anti-dripping agent (I) include polytetrafluoroethylene, tetrafluoroethylene perfluoro-mouth alkyl vinyl ether copolymer, And fluorinated polyolefins, such as tetrafluoroethylene Z ethylene copolymer, vinylidene fluoride, and polytetrafluoroethylene. Among these, polytetrafluoroethylene, tetrafluoroethylene perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene Ethylene / ethylene copolymer is preferred, and polytetrafluoroethylene and tetrafluoroethylene / hexafluoropropylene copolymer are more preferred.

As the polytetrafluoroethylene, those having a fibril-forming ability are preferable. That is, it is easily dispersed in a resin, and shows a tendency to form a fibrous material by combining polymers, and functions as an anti-dripping agent. Polytetrafluoroethylene having the ability to form fibrils is classified into Type 3 according to the ASTM standard. For example, “Polyflon FA-500” or “F-201L” by Daikin Chemical Industries, Ltd., Asahi Glass Co., Ltd. ) Is commercially available as Teflon (R) 6 J from Mitsui. DuPont Fluorochemicals, Inc. The melt viscosity of the fluororesin used as the anti-dripping agent (I) at 350 ° C. is usually 1.0 × 10 ² to 1.0 × 10 ¹⁵ (Pa · s), preferably 1.0 × 10 ³ 11.0 × 10 ¹⁴ (Pa · s), and more preferably 1.0 × 10 ¹⁰ to 1.0 × 10 ¹² (Pa−s). If the melt viscosity is less than 1,0 X 10 ² (P a * s), the ability to prevent dripping during combustion is insufficient, and a composition larger than 1.0 X 10 ¹⁵ (P a Has a markedly reduced fluidity.

It is preferable to use a layered silicate as the anti-dripping agent (I) from the viewpoint of the fluidity of the resin composition of the present invention at the time of melting. Examples of the layered silicate include a layered silicate, a modified layered silicate (a layered silicate in which a quaternary organic cation is inserted between layers), and a layered silicate having a reactive functional group or a modified layered silicate. From the viewpoint of the dispersibility of the layered silicate in the resin composition of the present invention and the ability to prevent dripping, a modified layered silicate, a layered silicate to which a reactive functional group is added, or a modified layered silicate is preferable. Group, oxazoline group, sulfoxyl group, acid anhydride, etc. The layered silicate or modified layered silicate to which the reactive functional group is added is preferably used. As a method of imparting a functional group, a method of treating with a functionalizing reagent (silane coupling agent) is simple and preferable.

 Examples of the functionalizing reagent include chlorosilanes having an epoxy group, chlorosilanes having a carbonyl group, chlorosilanes having a mercapto group, alkoxysilanes having an amino group, alkoxysilanes having an epoxy group, and the like. No. In particular, chlorosilanes having an epoxy group such as 3-daricidyloxypropyldimethylchlorosilane, β- (3,4-epoxycyclohexyl) ethyldimethylchlorosilane, 3-daricidyloxypropyltrichlorosilane, Has an amino group such as 3-aminopropyltriethoxysilane, Ν— (2-aminoethyl) -1-3-aminopropyltrimethoxysilane, Ν— (2-aminoethyl) -3-aminopropylmethyldimethoxysilane Epoxy groups such as alkoxysilanes, 3-daricidyloxypropylmethyljetoxysilane, 3-glycidyloxypropyl trimethoxysilane, r- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Alkoxysilanes having the following are preferred. The contact of these functionalizing reagents with the layered silicate is preferably carried out without solvent or by mixing in an polar solvent.

 Specific examples of the layered silicate used in the present invention include smectite-based clay minerals such as montmorillonite, hectorite, fluorine hectorite, savonite, suberite and subchinsite, Li-type fluorine teniolite, and Na-type fluorine teniolite. And swellable synthetic mica such as Na-type tetrasilicon fluoromica, Li-type tetrasilicon fluoromica, and the like, and any of natural products and synthetic products may be used. Particularly, smectite clay minerals such as montmorillonite and hectorite, and swellable synthetic mica such as Li-type fluorine teniolite, Na-type fluorine teniolite, and Na-type tetrasilicon fluorine mica are preferable.

The quaternary cation inserted between the layers of the modified layered silicate used in the present invention includes, for example, trimethyloctylammonium, trimethyldecylane Monium, trimethyl dodecyl ammonium,

Trimethylalkylammonium, such as dimethyl, trimethylhexadecylammonium and trimethyloctadecylammonium, dimethyldioctylammonium methylditetraammonium, dimethyldihexadecylammonium, and dimethyl.

 Silicone oil is also preferred as the dripping inhibitor (I). The silicone oil is a compound having a dimethylpolysiloxane skeleton represented by the following general formula (1), and a terminal or a part or all of a side chain thereof is amino-modified, epoxy-modified, carboxyl-modified, or carbinol. Modified, methacryl-modified, mercapto-modified, phenol-modified, polyether-modified, methylstyryl-modified, alkyl-modified, higher fatty acid ester-modified, higher alkoxy-modified, and fluorine-modified may be functionalized.

滴下防止剤 （I) として使用するシリコンオイルの粘度は、 25°Cにおいて、 通常 1000〜 30000 (c s. ) 、 好ましくは 2000〜 25000 (c s. ) 、 更に好ましくは 3000〜 20000 (c s. ) である。 粘度が 10 00 (c s. ) 未満の場合は、 燃焼中の滴下防止作用が充分でなくなり難燃性 が大きく低下し、 30000 (c s. ) より大きい場合は、 増粘効果により組 成物の流動性が著しく低下する。

The viscosity of the silicone oil used as the anti-dripping agent (I) at 25 ° C is usually 1000 to 30000 (cs), preferably 2000 to 25000 (cs), more preferably 3000 to 20000 (cs). .). If the viscosity is less than 1000 (c s.), The effect of preventing dripping during combustion is insufficient, and the flame retardancy is greatly reduced.If the viscosity is more than 30,000 (c s.), The composition is thickened due to the thickening effect. Has a markedly reduced fluidity.

In the flame-retardant PBT composition of the present invention, the content of the brominated aromatic compound-based flame retardant (G) is usually 3 to 50 parts by weight, preferably 5 to 50 parts by weight based on 100 parts by weight of PBT. -40 parts by weight, more preferably 6-30 parts by weight. When the content of the brominated aromatic compound-based flame retardant (G) is less than 3 parts by weight, the flame-retardant effect is insufficient, and when it exceeds 50 parts by weight, the mechanical strength is reduced and the heat during melting is reduced. Stability tends to decrease. In the flame-retardant PBT composition of the present invention, the content of the antimony compound (H) is usually 1 to 30 parts by weight, preferably 2 to 25 parts by weight, more preferably 3 to 20 parts by weight with respect to 100 parts by weight of PBT. Department. If the content of the antimony compound (H) is less than 1 part by weight, a sufficient flame retardant effect cannot be obtained.If the content exceeds 30 parts by weight, the mechanical strength is reduced and the thermal stability during melting is reduced. easy.

 In the flame retardant PBT composition of the present invention, the content of the anti-dripping agent (I) is usually 0 to 15 parts by weight based on 100 parts by weight of PBT. If the content of the anti-dripping agent (I) exceeds 15 parts by weight, the fluidity and mechanical properties may be reduced. In the flame-retardant PBT composition of the present invention, the type and content of the reinforcing filler (D) are the same type and content as described in the above-mentioned hydrolysis-resistant PBT composition.

 (Non-octogen flame retardant PBT composition)

 The flame-retardant PBT composition of the present invention comprises a compatibilizer (K) based on a total of 100 to 50 parts by weight of the PBT (A) and 5 to 50 parts by weight of the polyolefin ether resin (J). ) 0.05 to 10 parts by weight, at least one compound selected from phosphate esters or phosphonitrile (L) 2 to 45 parts by weight, reinforcing filler (D) 0 to 200 parts by weight, anti-drip agent (I ) 0 to 15 parts by weight, melamine cyanurate (M) 0 to 45 parts by weight and metal borate (N) 0 to 50 parts by weight.

The polyphenylene ether resin (J) (hereinafter abbreviated as PPE) used in the present invention is a homopolymer or a copolymer having a structure represented by the following general formula (2).

(Wherein, R ^1Q represents a hydrogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, or a hydrocarbonoxy group, R ¹¹ represents a primary or secondary alkyl group, Represents an aryl group or an alkylamino group, and r represents an integer of 10 or more.)

Examples of the primary alkyl group represented by R ^1Q include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-amyl group, an n-hexyl group, an isoamyl group, a 2-methylbutyl group, Examples include a 2,3-dimethylbutyl group, a 2-, 3- or 4-methylpentyl group or a heptyl group. Preferable examples of the secondary alkyl group include an isopropyl group, a sec-butyl group and a 1-ethylpropyl group. Suitable homopolymers of PPE are, for example, those comprising 2,6-dimethyl-1,4-phenylene ether units. A preferred copolymer is a random copolymer composed of a combination of the above units and 2,3,6-trimethylylene 1,4-phenylene ether units.

The intrinsic viscosity of the PPE (J) used in the present invention at 30 ° C measured in a black mouth form is usually 0.20 to 0.70 dL / g, preferably 0.25 to 0.70 dLZg, and Preferably it is 0.30 to 0.60 dL / g. When the intrinsic viscosity is less than 0.20 dLZg, the impact resistance of the composition is insufficient, and when it exceeds 0.80 dL // g, the gel component is large and the appearance of the molded article tends to deteriorate. What is the compatibilizer (K) used in the present invention? Can you go to the middle of eight? ? It is a compound that improves the dispersibility of £, selected from the group consisting of polycarbonate resin, carboxylic acid group, carboxylic acid ester group, acid amide group, imide group, acid anhydride group, epoxy group, oxazolinyl group, amino group, and hydroxyl group. A compound having one or more functional groups A phosphite compound or the like can be used.

 Specific examples of the compound having a functional group include an epoxy group-added PPE resin, a hydroxyalkylated PPE resin, a oxazoline-terminated PPE resin, a polyester in which a lipoxyl group end is modified with polystyrene, and an OH group end modified with polyethylene. Polyester and the like.

 As the compatibilizer (K), a phosphite or a polycarbonate resin is preferred from the viewpoints of hydrolysis resistance, crystallinity, mechanical properties, and flame retardancy of the composition of the present invention, and phosphite is preferred. Is preferably a phosphite triester, and particularly preferably a phosphite triester represented by the following general formula (3) or (4).

R ¹² 0— P— 0 R 14

 (3)

 0 R 13

(Wherein, R ^{12 to} R ¹⁴ each independently may contain an oxygen atom, a nitrogen atom, a sulfur atom, an alkyl group having 1 to 20 carbon atoms or a substitution or 6 to 30 carbon atoms. Represents an unsubstituted aryl group.)

 Specific examples of the general formula (3) include trioctyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, triisooctyl phosphite, tris (nonylphenyl) phosphite, and tris

(2,4-Dinonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, triphenyl phosphite, tris (octylphenyl) phosphite, diphenylisooctylphosphite, diphenyl Examples include sodecyl phosphite, octyl diphenyl phosphite, dilauryl phenyl phosphite, diisodecyl phenyl phosphite, bis (nonylphenyl) phenyl phosphite, and diisooctyl phenyl phosphite.

(In the formula, u is 1 or 2, and R ¹⁵ is the same or different and may contain an oxygen atom, a nitrogen atom or a sulfur atom, an alkyl group having 1 to 20 carbon atoms or a carbon number of 6 to And 30 represents a substituted or unsubstituted aryl group having 30. When u is 1, R ¹⁶ represents an alkylene group having 1 to 20 carbon atoms or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; When is 2, it represents an alkyltetrayl group having 4 to 18 carbon atoms.)

Examples of R ¹⁵ include methyl, ethyl, propyl, octyl, isooctyl, isodecyl, decyl, stearyl, lauryl, phenyl, 21,3- or 4-methylphenyl, 2 , 4,1- or 2,6-dimethylphenyl, 2,3,6-trimethylphenyl, 2-, 3_ or 4-ethylphenyl, 2-, 4_ or 2-, 6-methylethyl, 2,3,6-triethylphenyl, 2-, 3- or 4-tert-butylphenyl, 2,4- or 2,6-ditert-butylphenyl, 2,6-di-tert-butyl _ 4 _Methylphenyl group, 2,6-ditert-butyl-4-ethylphenyl group, octylphenyl group, isooctylphenyl group, 2-, 3_ or 4-nonylphenyl group, 2,4 dinonylphenyl Group, biphenyl group, Such as Fuchiru group, and the like. In particular, substituted or unsubstituted aryl groups are preferred. Examples of R ¹⁶ include polymethylene groups such as 1,2-phenylene group, ethylene, propylene, 1, limethylene, tetramethylene, and hexamethylene when u = l in the general formula (4).

As specific examples of the compound of the general formula (4), when u is 1, for example, (phenyl) (1,3-propanediol) phosphite, (4-methylphenyl) (1, 3-propanediol) phosphite, (2,6-dimethylphenyl) (1,3-propanediol) phosphite, (4-tert-butylphenyl)

(1,3_propanediol) phosphite, (2,4-di-tert-butylphenyl) (1,3-propanediol) phosphite, (2,6-di-tert-butylphenyl) (1,3_propane) Diol) phosphite, (2,6-di-tert-butyl_4-monomethylphenyl) (1,3_propanediol) phosphite, (phenyl) (1,2-ethanediol) phosphite,

(4-Methylphenyl) (1,2-ethanediol) phosphite, (2,6-dimethylphenyl) (1,2-ethanediol) phosphite, (4-tert-butylbutyl) (1,2-ethanediol) ) Phosphite, (2,6-G te 1-t-butylphenyl) (1,2 ethanediol) phosphite,

(2,6-Di-tert-butyl-4-methylphenyl) (1,2-ethanediol) phosphite, (2,6-di-tert-butyl-14-methylphenyl) (1,4-butanediol) Phosphite and the like.

When u = 2, R ¹⁶ is a tetrayl group having a pentaerythrityl structure represented by the following general formula (5).

Five

(In the formula, v, w, x, and y each represent an integer of 0 to 6.)

 Specific examples include diisodecyl penyl erythritol diphosphite, diaryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, diphenyl pentaerythritol diphosphite, and bisphenol erythritol diphosphite.

(2-methylphenyl) pentaerythritol diphosphite, bis (3-methylphenyl) pentaerythritol diphosphite, bis (4-methylphenyl Nyl) pentaerythritol diphosphite, bis (2,4-dimethylphenyl) pentaerythr! ^ Ildiphosphite, bis (2,6-dimethylphenyl) pentaerythritol diphosphite, bis (2,3,6-trimethylphenyl) bentaerythritol diphosphite, bis (2_tert-butylphenyl) pentaeryth Litho ^ / diphosphite, bis (3-tert-butylylphenyl) pentaerythri 1 ^ -ldiphosphite, bis (4-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol Phosphite, bis (2,6-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di_tert-butyl-4 4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyldiphenyl) 6-G tert-Butyl 4-Ethylphenol) Pennis Ellis Litridiphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (biphenyl) pentaerythritol diphosphite, dinaphthylpentaerythritol diphosphite and the like. Among the phosphite triesters described above, a compound in which u is 1 or 2 in the formula (4) is preferable. Further, when u = 2 in the formula (4), R ¹⁶ is a compound represented by the general formula (5) Compounds having a tetrayl group having a pentaerythrityl structure shown below are more preferable. Among them, bis (nonylphenyl) pentaerythryl 1-diphenyl phosphite, bis (2,4-g-tert-butylphenyl) pentaerythritol-l-diphenyl phosphite, bis (2,6-g-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, etc. More preferably, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di_tert-butyl-4-methylphenyl) pentaerythr! ^ Irdiphosphite is preferred. The composition of the present invention may contain a compound generated by the decomposition (hydrolysis, thermal decomposition, etc.) of these phosphite triesters.

As the polycarbonate resin used as the compatibilizer (K) in the present invention Examples thereof include aromatic dihydroxy compounds or a thermoplastic aromatic polycarbonate polymer or copolymer which may be produced by reacting a small amount of the polyhydroxy compound with phosgene or a carbonic acid diester. Can be As aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis

(4-Hydroxyphenyl) 1 p-diisopropylbenzene, hydroquinone, resorcinol, 4,4-dihydroxydiphenyl and the like are preferred, and bisphenol A is preferred.

 In order to obtain a branched polypropionate resin, fluorodarucine, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2,4,6-dimethyl-2,4,6-tritol 'J (4-hydroxyphenyl) hebutane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-1,3,1,3,5-tris (4-hydroxyphenyl) benzene , 1, 1, 1—Tris

Polyhydroxy compounds represented by (4-hydroxyphenyl) phenyl, or 3,3-bis (4-hydroxyaryl) oxyindole (= isatin bisphenol), 5-chlorisatin, 5,7 Dichlorosatin, 5-bromosatin and the like may be used as a part of the aromatic dihydroxy compound, and its use amount is usually from 0.1 to 10 mol%, preferably from 0.1 to 2 mol%.

 The aromatic polycarbonate resin is preferably a polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, or 2,2-bis (4-hydroxyphenyl) propane and another aromatic dihydroxy resin. And a polycarbonate copolymer derived from the compound.

The molecular weight of the polycarbonate resin used as the compatibilizing agent (K) is usually 160000-1000 as the viscosity average molecular weight converted from the solution viscosity measured at a temperature of 25 ° C using methylene chloride as a solvent. It is 30, 000, preferably 18, 000 to 23, 000. As a polycarbonate resin, two or more types It is also possible to use a mixture of a lithium carbonate resin.

 The phosphate ester compound (L) used in the present invention includes a wide range of phosphate esters. Specific examples thereof include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxetyl phosphate, triphenyl phosphate, tricresyl rephosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, and the like. Among them, a compound represented by the following general formula (6) is particularly preferable.

(Wherein, ¹ to! ^ ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m is 0 or an integer of 1 to 4. R ⁹ is p-phenyl Diene group, m-phenylene group, 4,4′-biphenylene group or a divalent group selected from the following.)

前記の一般式 （6 ) において、 ！^〜 ⁸は、 本発明組成物の耐加水分解性を 向上させる観点から、 好ましくは炭素数 6以下のアルキル基、 更に好ましくは 炭素数 2以下のアルキル基、 特に好ましくはメチル基である。 mは、 好ましく は 1〜3、 更に好ましくは 1である。 R ⁹は、 好ましくは p—フエ二レン基ま たは m—フエ二レン基、 更に好ましくは m—フエ二レン基である。

In the general formula (6),! ^ To ⁸ are preferably an alkyl group having 6 or less carbon atoms, more preferably an alkyl group having 2 or less carbon atoms, and particularly preferably a methyl group, from the viewpoint of improving the hydrolysis resistance of the composition of the present invention. m is preferably 1 to 3, and more preferably 1. R ⁹ is preferably a p-phenylene group. Or m-phenylene group, more preferably m-phenylene group.

 Further, as the component (L), a phospho: tolylic compound Rx Xl Di RlI having a group represented by the following general formula (7) is also suitably used.

(In the formula, X represents —0—, 1 S—, —NH— or a direct bond. R ¹⁷ and R ¹⁸ represent an aryl group, an alkyl group, or a cycloalkyl group having 1 to 20 carbon atoms. ^{R 1 7-X-, R 18} - X- may be the same or different and n indicates to the 1 to 1 2 integer)..

In the general formula (7), specific examples of R ¹⁷ and R ¹⁸ include an optionally substituted alkyl group such as a methyl group, an ethyl group, a butyl group, a hexyl group and a benzyl group; and a cycloalkyl group such as a cyclohexyl group. And aryl groups such as an alkyl group, a phenyl group, and a naphthyl. n is preferably from 3 to 10, more preferably 3 or 4. The phosphonitrile compound of the general formula (7) may be a linear polymer or a cyclic polymer, but is preferably a cyclic polymer. X is preferably 10- or -NH-, particularly preferably 10-.

 Specific examples of the phosphonitrile compound represented by the general formula (7) include hexaphenoxycyclotriphosphazene, hexa (hydroxyphenoxy) cyclotri phosphazene, octaphenoxycyclotetraphosphazene, and octa (hydroxyphenoxy) cyclo. Tetraphosphazene and the like.

Melamine cyanurate (M) used in the present invention is defined as It is a substantially equimolar reactant, and can be obtained, for example, by mixing an aqueous solution of sialic acid and an aqueous solution of melamine, reacting the mixture at a temperature of 90 to 100 ° C. with stirring, and filtering the resulting precipitate. The particle size of melamine cyanurate is usually from 0.01 to 1000 m, preferably from 0.01 to 500 m. Some of the amino or hydroxyl groups of melamine cinurate may be substituted with other substituents.

The metal borate (N) used in the present invention is preferably one which is stable under the commonly used processing conditions and has no volatile components. Examples of the metal borate (N) include alkali metal borate (eg, sodium tetraborate, potassium metaborate, etc.) and alkaline earth metal salts (eg, calcium borate, magnesium orthoborate, barium orthoborate, zinc borate, etc.) ) And the like. Le ^ zinc borate, zinc borate is preferably Among them is generally indicated by _{2 Z ηθ · 3 B 2 0} 3 · xH 2 0 (x = 3. 3~ 3. 7). The hydrated zinc borate, and preferably, 2 shall Zetaitaomikuron-3 [beta] ₂ 〇 ₃ · 3. stable up to 5 Eta ₂ is represented by 0 formula and 260 ° C or higher temperatures.

 In the non-halogen flame-retardant PBT composition of the present invention, the content of polyphenylene ether (J) (PPE) is 95: 5 to 50:50, preferably 92: 8 to 50 by weight as PBT: PPE. 55:45, more preferably 90:10 to 60:40. When the ratio of PPE is less than 5, the flame retardancy and hydrolysis resistance of the composition become insufficient, and when it exceeds 50, the fluidity and chemical resistance of the composition are significantly reduced.

 In the non-octalogen flame-retardant PBT composition of the present invention, the content of the compatibilizer (K) is 0.05 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total of PBT and PPE. The amount is 1 to 8 parts by weight, more preferably 0.3 to 5 parts by weight. Compatibilizer

If the content of (K) is less than 0.05 parts by weight, the physical properties of the composition, particularly the mechanical strength and flame retardance, are reduced. Surface appearance deteriorates. In the non-halogen flame-retardant PBT composition of the present invention, the content of the phosphate ester or the phosphonium (L) is based on 100 parts by weight of the total of PBT and PPE. On the other hand, it is 2 to 45 parts by weight, preferably 3 to 40 parts by weight, more preferably 5 to 30 parts by weight. If the content of phosphate ester or phosphonium (L) exceeds 2 parts by weight, the flame retardancy of the composition will be insufficient, and if it exceeds 45 parts by weight, mechanical properties, hydrolysis resistance, molding Properties are significantly reduced.

 In the non-halogen flame-retardant PBT composition of the present invention, the type and content of the reinforcing filler (D) are the same type and content as described in the above-mentioned hydrolysis-resistant PBT composition.

 In the non-halogen flame-retardant PBT composition of the present invention, the type and content of the anti-dripping agent (I) are the same as those described in the flame-retardant PBT composition.

 When a layered silicate is used as the anti-dripping agent (I) in the non-halogen flame-retardant PBT composition of the present invention, its content is usually 0 to 15 parts by weight based on 100 parts by weight of the total of PBT and PPE. Parts, preferably 0.3 to 12 parts by weight, more preferably 0.5 to 10 parts by weight. When the content of the layered silicate exceeds 15 parts by weight, the fluidity and mechanical properties are extremely reduced. One type of layered silicate may be used, or two or more types may be used in combination.

 When silicone oil is used as the anti-dripping agent (I) in the non-halogen flame-retardant PBT composition of the present invention, its content is 0 to 15 parts by weight with respect to 100 parts by weight of PBT and PPE in total. , Preferably 0.005 to 8 parts by weight, more preferably 0 to 5.0 parts by weight. If the silicon oil content exceeds 15 parts by weight, the fluidity and mechanical properties will be significantly reduced.

 In the non-octadene flame-retardant PBT composition of the present invention, the content of melamine cyanurate (M) is 0 to 45 parts by weight, preferably 3 to 40 parts by weight, based on 100 parts by weight of PBT and PPE in total. And more preferably 5 to 30 parts by weight. When the content of melamine (M) cyanurate exceeds 45 parts by weight, the toughness and ductility are reduced, and bleed-out and plate-out are caused.

In the non-halogen flame-retardant PBT composition of the present invention, a phosphate ester or phospho The ratio of at least one compound selected from nitriles (L) to melamine cynate (M) is usually 1: 9 to 9: 1, preferably 2: 8 to 8: 2, and more preferably 2.5. : 7.5 to 7.5: 2.5.

 In the non-octalogen flame-retardant PBT composition of the present invention, the content of the metal borate (N) is 0 to 50 parts by weight, preferably 2 to 45 parts by weight, based on 100 parts by weight of the total of PBT and PPE. More preferably, it is 3 to 40 parts by weight. If the content of the metal borate (N) exceeds 50 parts by weight, the mechanical properties tend to deteriorate.

 (Other functional PBT composition-1)

 The other functional PBT composition-1 of the present invention comprises 5 to 100 parts by weight of a polycarbonate resin (O) and 0.01 to 1 part by weight of an organic phosphorus compound (P) based on 100 parts by weight of the PBT (A). A reinforcing filler (D) from 0 to 200 parts by weight and an impact modifier (F) from 0 to 50 parts by weight. This functional PBT composition 11 is excellent in dimensional stability, especially when it is formed into a molded product, in which the shrinkage and the warpage are reduced.

 The polycarbonate resin (O) used in the present invention includes an aromatic dihydroxy compound or an optionally branched polycarbonate resin produced by reacting an aromatic dihydroxy compound or a small amount of a polyhydroxy compound with phosgene or a carbonic acid diester. Copolymers or copolymers are mentioned.

 As aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene And dihydroquinone, resorcinol, 4,4-dihydroxydiphenyl and the like, and bisphenol A is preferred.

In order to obtain a branched aromatic polycarbonate resin, fluorodarucine, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-1,2,4,6-dimethyl_2,4,6-tris ( 4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene 1,3,1,3,5-Polyhydroxy compound represented by tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, or 3,3- Bis (4-hydroxyaryl) oxyindole (= isatin bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-bromomisatin, etc. may be used as a part of the aromatic dihydroxy compound. The amount is usually from 0.01 to 10 mol%, preferably from 0.1 to 2 mol%.

 The aromatic polycarbonate resin is preferably a polycarbonate resin produced by reacting 2,2-bis (4-hydroxyphenyl) propane with phosgene or a carbonic acid diester, or 2,2-bis (4-hydroxyphenyl). Polycarbonate copolymers produced using propane and other aromatic dihydroxy compounds. Further, two or more kinds of polycarbonate resins may be mixed and used.

 The molecular weight of the polycarbonate resin is usually 15,000 to 30,000, preferably 16,000 to 25, as the viscosity average molecular weight calculated from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent. , 000.

 Examples of the organic phosphorus compound (P) used in the present invention include an organic phosphate compound, an organic phosphite compound, and an organic phosphonite compound. Of these, organic phosphate compounds are preferred. In particular, a long-chain alkyl acid phosphate compound represented by the following general formula (8) is preferable.

^ Ro) _n P (0) (OH) _3-n (8)

(In the formula, R represents an alkyl group having 8 to 30 carbon atoms, and n is 1 or 2.) In the general formula (8), as a specific example of the alkyl group having 8 to 30 carbon atoms represented by R Is n-octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, dodecyl, tridecyl, Examples include a sotridecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an eicosyl group, and a triancotyl group. Further, a monoalkyl phosphate having n of 1, dialkyl acid phosphate having n of 2, or a mixture thereof is also used.

 In another functional PBT composition 11 of the present invention, the content of the polycarbonate resin (O) is 5 to 100 parts by weight, preferably 7 to 90 parts by weight, more preferably 10 to 100 parts by weight with respect to 100 parts by weight of PBT. 80 parts by weight. If the content of the polycarbonate resin (O) is less than 5 parts by weight, the effect of reducing the shrinkage and warpage of the molded article is insufficient, and if it exceeds 100 parts by weight, the crystallization speed is slow and the melt viscosity is high and extremely high. In addition, the moldability deteriorates.

 In the other functional PBT composition 11 of the present invention, the content of the organic phosphorus compound (P) is usually 0.01 to 1 part by weight, preferably 0.05 to 0. 6 parts by weight, more preferably 0.1 to 0.4 part by weight. When the content of the organophosphorus compound (P) is less than 0.01 parts by weight, the effect of improving the heating stability and retention stability of the composition is reduced. When the content exceeds 1 part by weight, the hydrolysis resistance is improved. Cause a decline. The organic phosphorus compounds (P) may be used alone or in combination of two or more.

 In another functional PBT composition 11 of the present invention, the type and content of the reinforcing filler (D) are the same type and content as described in the above-mentioned hydrolysis-resistant PBT composition. You.

 In the other functional PBT composition 11 of the present invention, as the type of the impact modifier (F), the same type as described in the above impact-resistant PBT composition is used. The content is 0 to 50 parts by weight, preferably 1 to 45 parts by weight, more preferably 2 to 40 parts by weight, based on 100 parts by weight of PBT. When the content of the impact modifier (F) exceeds 50 parts by weight, mechanical properties such as tensile strength and bending strength are significantly reduced.

(Other functional PBT composition-1) The other functional PBT composition 1-2 of the present invention comprises 100 to 100 parts by weight of the above-mentioned PBT (A), and 5 to 100 parts by weight of an aromatic polyester resin (Q) other than PBT and reinforced. The filler (D) is characterized by containing 0 to 200 parts by weight. This functional PBT composition 12 is excellent in surface appearance (transparency) especially when it is formed into a molded article.

 Examples of the aromatic polyester (Q) other than PBT used in the present invention include polyalkylene terephthalate and polyalkylene naphthalate. Specific examples thereof include poly 1,4-cyclohexane dimethylene terephthalate.

(PCT), polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polyethylene naphthalate (PEN), polypropylene naphthalate (PPN), polybutylene naphthalate (PBN), and the like. Is preferred.

The polyethylene terephthalate as used herein is a polymer obtained by polycondensing terephthalic acid or an ester-forming derivative thereof with an alkylene glycol having 2 carbon atoms or an ester-forming derivative thereof. A copolymer containing the above may be used. As monomers to be copolymerized, dibasic acid components other than terephthalic acid and its lower alcohol esters include aliphatic acids such as isophthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, and succinic acid. , An aromatic polybasic acid or an ester-forming derivative thereof, and the like, as a glycol component other than ethylene glycol, a common alkylene glycol such as diethylene glycol, propylene glycol, trimethylene glycol, and hexamethylene glycol. , Neopentyl glycol, cyclohexane dimethanol, etc., lower alkylene glycol such as 1,3-octanediol, ethylene oxide 2 mol adduct of bisphenol A, propylene oxide 3 mol addition of bisphenol A A such as the body · The Renokisaido adduct alcohols, glycerol, port of pentaerythritol Examples include a rehydroxy compound or an ester-forming derivative thereof.

 In the present invention, the polypropylene terephthalate resin means a polymer or copolymer obtained by a polycondensation reaction using terephthalic acid or its ester-forming derivative and 1,3-propanediol as main components. The polymer may be one in which part of terephthalic acid is replaced by another dicarboxylic acid or an ester-forming derivative thereof, and part of 1,3-propanediol is replaced by another diol and a no or triol. It may be replaced. As the ester-forming derivative, an ester, particularly, dimethyl terephthalate is preferable.

 In the other functional PBT composition-2 of the present invention, the content of the aromatic polyester (Q) other than PBT is 5 to 100 parts by weight, preferably 100 to 100 parts by weight of PBT. It is 7 to 90 parts by weight, more preferably 10 to 70 parts by weight. When the content of the aromatic polyester (Q) other than PBT is less than 5 parts by weight, the surface appearance of the molded article is hardly improved, and when it exceeds 100 parts by weight, the molding cycle is increased. In addition, molding problems such as deterioration of mold release properties and deterioration of mechanical properties of molded products occur.

 In another functional PBT composition 12 of the present invention, the type and content of the reinforcing filler (D) are the same type and content as described in the above-mentioned hydrolysis-resistant PBT composition. You. As a method for further improving the surface appearance (transparency), it is effective to add a catalyst that promotes a transesterification reaction. The ester exchange promoting catalysts include oxides, hydroxides, and organic metals of metals belonging to Groups 1A, 2A, 2B, 4A, 4B, 5B, 7A, and 8 Among the metals, sodium, calcium, lithium zinc, cobalt, manganese and the like are preferable, and organic metal salts such as sodium stearate, calcium stearate and magnesium stearate are particularly preferable. . The amount of addition is usually 0.001-1% by weight.

 (Other functional PBT composition 1 3) ''

Another functional PBT composition 13 of the present invention comprises the PBT (A) 100 parts by weight 5 to 100 parts by weight of styrene resin (R), 0 to 40 parts by weight of maleic anhydride-modified polystyrene resin (S) or polycarbonate resin (0), and 0 to 200 parts by weight of reinforcing filler (D) It is characterized by doing. This functional PBT composition 13 has excellent dimensional stability, especially when formed into a molded product, in which the shrinkage and the warpage are reduced.

 The styrene-based resin (R) used in the present invention may be a rubber-modified styrene-based resin, and includes, for example, (1) a homo- or copolymer of an aromatic vinyl monomer, and (2) an aromatic vinyl monomer. At least one copolymer selected from a copolymer monomer (for example, a vinyl cyanide monomer) and a rubber component can be used. Styrene resins can be used alone or in combination of two or more.

 Examples of the aromatic vinyl monomer include styrene, vinyltoluene, 0! -Methylstyrene and the like, and styrene is particularly preferred. Examples of the vinyl cyanide monomer include unsaturated nitriles such as acrylonitrile and methacrylonitrile. These vinyl cyanide monomers can be used alone or in combination of two or more. The preferred vinyl cyanide monomer is acrylonitrile. Examples of the rubber-modified styrene resin include an ABS resin and a HIPS resin.

The number average molecular weight of the styrene-based resin (matrix resin a rubber-modified styrenic resin) is usually ^{5X 10 4 ~ 20 0 X 1} 0 4, preferably in the range of ^{1 X 1 0 4 ~100 X 10} 4. The number average molecular weight decreases the strength of the case of less than ^{0. 5X 10 4, 200 X 10} 4 greater than the fluidity decreases.

The maleic anhydride-modified polystyrene resin (S) used in the present invention means a resin containing maleic anhydride in polystyrene. Examples of a method of including maleic anhydride in polystyrene include a method of simply mechanically blending the two, and a method of copolymerizing a styrene monomer and maleic anhydride. Examples of the latter copolymerization method include an emulsion polymerization method, a solution polymerization method, and a suspension polymerization method. The content of maleic anhydride is usually 1 to 40% by weight, preferably 2 to 30% by weight. %, More preferably 3 to 20% by weight.

 In the PBT composition-3 of the present invention, the content of the styrene-based resin (R) is 5 to 100 parts by weight, preferably 7 to 90 parts by weight, more preferably 100 parts by weight of PBT. Is from 10 to 80 parts by weight. When the content of the styrene-based resin (R) is less than 5 parts by weight, the effect of reducing the shrinkage and warpage of the molded product is insufficient, and when the content exceeds 100 parts by weight, the mechanical properties are significantly reduced. It is.

 In the PBT composition 13 of the present invention, the maleic anhydride-modified polystyrene resin (S) or the polycarbonate resin (O) is used as a compatibilizer between PBT and a styrene-based resin containing no vinyl cyanide monomer such as HIPS. Function. The content of these resins is 0 to 40 parts by weight, preferably 5 to 100 parts by weight per 100 parts by weight of PBT.

It is 30 parts by weight, more preferably 10 to 20 parts by weight. These resin contents

If the amount exceeds 40 parts by weight, mechanical properties are reduced.

In the PBT composition 13 of the present invention, the type and content of the reinforcing filler (D) are the same type and content as described in the above-mentioned hydrolysis-resistant PBT resin. As the above-mentioned polycarbonate resin (O), the same type as described above for the water-resistant decomposition-resistant PBT resin is used. In the present invention, as a method for incorporating various additives into PBT, a method in which additives are added by melt kneading is preferable. As the melt-kneading method, a kneading method commonly used for thermoplastic resins can be applied. For example, after uniformly mixing each component with a component to be added as necessary, using a Henschel mixer, a repump blender, a V-type blender, etc., a single-screw kneading extruder, a multi-screw kneading extruder, a roll, a bumper Mix using a mixer, Brabender, etc. Each component, including additional components, can be supplied to the kneader at once, or can be supplied sequentially. In addition, two or more components selected from each component, including additional components, can be mixed in advance. A reinforcing filler such as glass fiber is added after the resin is melted in the middle of the extruder, thereby avoiding crushing and exhibiting high properties. Add a liquid epoxy compound In the case of adding, the epoxy compound may be added by being pressed into the melt-kneaded PBT from the middle of the extruder.

 The molding method of the PBT and its composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, that is, molding methods such as injection molding, hollow molding, extrusion molding, and press molding are used. Can be applied.

 The PBT of the present invention is excellent in color tone, hydrolysis resistance, thermal stability, transparency, and moldability, and thus is suitable for injection molded parts such as electric, electronic parts, and automobile parts. And excellent transparency and thermal stability, so the improvement effect is remarkable in applications such as films, monofilaments and fibers.

 Next, the film of the present invention will be described. The film of the present invention is characterized by comprising PBT containing titanium and having an amount of 33 ppm or less as titanium atoms. The PBT described above can be used as such a PBT. The intrinsic viscosity of PBT for films is usually from 80 to 2.50 dLZg, preferably from 0.90 to 1.80 dLZg, more preferably from 1.00 to: L. 30 dLZg. Other physical properties of PBT are the same as above.

 The method for forming a PBT film in the present invention is not particularly limited, and is generally used for thermoplastic resins, that is, T-die casting, air-cooled inflation molding, and water-cooled blow molding injection. A molding method, a polysinder roll method, or the like can be applied.

Further, the PBT film of the present invention can be made into a composite film with another resin film. Polyolefin resin (low-density polyethylene: LDPE), linear low-density polyethylene: LLDPE), high-density polyethylene: HDPE), homopolypropylene), resin with 2 to 8 carbon atoms Block copolymerized polypropylene copolymerized with olefins as comonomer, random copolymerized polypropylene, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer partial peroxide (EVOH), ethylene-ethyl acrylate copolymer, Ionomers, Styrene-ethylene copolymer, Etch Lethylene-butylene copolymer, styrene-ethylenebutylene copolymer and the like are preferred.

 In the case of a combination with a polyolefin resin that does not adhere sufficiently to PBT and delaminates easily, an acid-modified or epoxy-modified resin (so-called adhesive resin) is placed between the layers to form a three-layer, three-layer film. It is also possible.

 In addition, a three-layer, three-layer film (PBTZ bonded Z polyamide) using polyamide instead of polyolefin resin to increase strength, and adhesive resin between PBT and polyamide, and polyamide and polyolefin, respectively. Five-layer five-layer film (PBTZ bonded Z polyamide Z bonded polyolefin), and five-layer five-layer film with EVOH instead of polyamide (? 8 / adhesive £ 0H / adhesive / polyolefin). Considering both strength and oxygen barrier properties, a 6-layer film (PBT / EVOHZ polyamide Z polyolefin) in which both polyamide and EVOH are arranged between PBT and polyolefin, and an adhesive resin is arranged between each layer A 6-layer film (PBT / adhesive / EVOH / polyamide / adhesive / polyolefin) can also be used.

 The co-extrusion method is generally used as a method of producing a composite film.After forming a PBT film, it is used to dry the laminate using an adhesive and then extruding, or another molten resin is put on the PBT film. Known methods such as extrusion lamination can also be used.

 In the extrusion lamination method, a coating agent or reactive adhesive such as an epoxy-based, urethane-based, titanate-based, or silicone-based resin is applied to the surface of a previously prepared film, or a known surface treatment such as corona discharge is applied. Can also be.

 The thickness of the PBT film of the present invention (the thickness of the PBT film layer in the case of a composite film) is generally 5 to 200 m. In particular, in the case of a single-layer film, the thickness is usually 10 to 150 nm, preferably 20 to 100 xm.

(PBT film layer), usually 5-100 / im, preferably 10-80 m. The overall thickness of the composite film is usually 20-300 ^ 111, preferably 50-200 / im.

 Generally, the haze of a PBT film is affected by the film thickness and the molding conditions, and the haze increases as the film becomes thicker and as the cooling temperature after discharge increases. Accordingly, in the present invention, when a 50-zm PBT film is formed by the T-die casting method or the water-cooled inflation method, the haze of the film is preferably less than 2%. The cooling temperature for obtaining such a film, that is, the surface temperature of the first-stage cooling roll in the case of the casting method is 60 ° C or less, and the cooling water temperature in the case of the water-cooled inflation method is 70 ° C or less. is there. If the haze of the film formed under these molding conditions exceeds 2%, the film is whitened and devitrified in appearance, and the commercial value is impaired. When an additive is blended in the PBT film of the present invention, the amount of the additive is determined when the crystallization temperature of the PBT resin composition is not higher than 20 (TC, and when the film is 50 m thick). It is preferable to adjust the haze not to exceed 2%.

 As described above, the PBT of the present invention can be copolymerized or blended (alloyed) with other resins. In particular, in a film, the PBT of the present invention can be easily controlled for crystallinity and transparency. In addition, since various mechanical properties are improved, blending with other resins is suitable. Suitable blend resins, especially for films, include polyesters, polycarbonates, polyamides, polyphenylene ethers, polystyrene, polymethacrylic or polymethacrylic esters, polyacrylic or polyacrylic esters, and polyolefins. Further, the blended resin may be a PBT other than the PBT of the present invention. In addition, PBT of the present invention having different compositions and molecular weights can be blended. Among these, polyester is preferred from the viewpoint of compatibility and transparency, and aromatic polyester is particularly preferred. Among the aromatic polyesters, the aromatic polyesters described in the above “Other functional PBT composition-1” are preferable.

Generally, PBT and other poly To maximize its performance, it is important to control the transesterification reaction between them, but if a large amount of catalyst remains in the PBT, the transesterification reaction will be too fast and difficult to control. However, since the amount of the catalyst of the PBT of the present invention is remarkably reduced, the control of the transesterification reaction is facilitated, and a wide range of compounds and molding conditions can be adopted. In particular, the effect of improvement is large in blend systems with polyethylene terephthalate, polyethylene naphthalate, etc., which have a higher melting point than PBT and require a higher molding temperature.

 Also, in a blend system with polyester (preferably aromatic polyester) obtained by copolymerizing polytetramethylene glycol whose decomposition reaction is accelerated by the residual catalyst, the PBT of the present invention in which the residual catalyst is significantly reduced is used. Thus, decomposition can be reduced.

 The blending ratio (weight ratio) of the PBT of the present invention and another resin is not particularly limited, but is usually 99: 1 to 1:99, preferably 95: 5 to 5:95, and more preferably 90: 1. 10-: L 0: 90.

 Since the PBT film of the present invention has the above-mentioned properties, it has a feature that the contents look beautiful, and in addition to a food packaging film, an industrial product packaging film, and a bag material for packaging these, It is suitable for use as a surface coating material film for producing design properties such as shrink film, and as a steel plate laminating film for building applications and food cans.

 Example

 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist of the present invention. The methods for measuring physical properties and evaluation items adopted in the following examples are as follows.

 (1) Esterification rate:

It was calculated from the acid value and saponification value by the following formula (V). The acid value was determined by dissolving the oligomer in dimethylformamide and titrating with a 0.1N KOH / methanol solution. Saponification value is 0.5N KOHZ ethanol The oligomer was hydrolyzed with a solution, and titrated with 0.5 N hydrochloric acid. Esterification rate 2 [(Saponification value monoacid value) / (Saponification value)] X 100 (V)

(2) Terminal lipoxyl group concentration:

 0.5 g of PBT or oligomer was dissolved in 25 mL of benzyl alcohol, and titrated using a 0.01 mol ZL benzyl alcohol solution of sodium hydroxide.

 (3) Intrinsic viscosity (IV):

 It was determined as follows using an Ubbelohde viscometer. That is, using a mixed solvent of phenol / tetrachloroethane (weight ratio: 1Z1), the falling seconds of only the polymer solution with a concentration of 1.0 gZdL and the solvent were measured at 30 ° C and calculated by the following formula (VI). .

[IV] = ((l + 4K H 7 sp) 0 · 5 -? 1)?. / (2KHC) (VI) ( where, ^ = 7 / ?? is an 1, ?? the polymer solution fall seconds the number,? 7. the drop under seconds of the solvent, C is the polymer solution concentration (gZdL), K _H is a constant of Huggins. K _H adopted the 0.33.)

(4) Titanium concentration in PBT:

 PBT was wet-decomposed with high-purity sulfuric acid and nitric acid for electronic industry, and measured using a high-resolution ICP (Induced Coupled Plasma) -MS (Mass Spectrometer) (manufactured by ThermoQuest).

 (5) Terminal methoxycarbonyl group concentration, terminal vinyl group concentration and terminal hydroxyl group concentration:

Approximately 10 mg of PBT was dissolved in ImL of a mixed solvent of formaldehyde / hexafluoroisopropanol = 73 (volume ratio), added with heavy pyridine 36, and ¹ H-NMR was measured at 50 ° C. I asked. The NMR system is manufactured by JEOL Ltd. — 400 ”or“ J NM 270 ”

 (6) Number of foreign substances of 5 Aim or more in PBT:

After dissolving 10 g of PBT at a concentration of 20% by weight in a mixed solvent of hexafluoroisopropanol / chloroform = 2/3 (volume ratio), the solution was filtered through a polytetrafluoroethylene membrane filter with a pore size of 5 / zm. After washing sufficiently with the above-mentioned mixed solvent, the amount of foreign substances left on the filter was observed and counted using an optical microscope.

 (7) Temperature drop crystallization temperature (Tc):

 Using a differential scanning calorimeter (Perkin Elmer Co., model DSC7), the temperature was raised from room temperature to 300 ° C at a temperature rising rate of 20 ° C / min, and then lowered to 80 ° C at a cooling rate of 20 ° C / min. Then, the temperature of the exothermic peak was defined as the cooling crystallization temperature. The higher the Tc, the faster the crystallization rate and the shorter the molding cycle.

 (8) Solution haze:

 2.70 g of PBT was dissolved in 20 mL of a mixed solvent of phenol / tetrachloroethane = 3/2 (weight ratio) at 110 ° C for 30 minutes, and cooled in a thermostat water bath at 30 ° C for 15 minutes. The measurement was performed using a turbidity meter (NDH-300A) with a cell length of 10 mm. The lower the value, the better the transparency.

 (9) Pellet color:

 Using a color difference meter (Z-30OA type) manufactured by Nippon Denshoku Co., Ltd., the yellow index b value was calculated and evaluated. The lower the value, the less yellowish and the better the color tone.

 (10) Increase in terminal lipoxyl group concentration due to thermal decomposition (△ [COOH]): After vacuum-drying PBT to a water content of 300 ppm or less, put it in a glass tube, in a dry nitrogen atmosphere, in an oil bath at 245 ° C. After the heat treatment, the concentration of terminal carboxyl groups and the concentration of terminal hydroxyl groups before and after the heat treatment were measured and calculated by the following formula (VII).

Δ [COOH]-Change in terminal lipoxyl group concentration before and after heat treatment-Change in terminal hydroxyl group concentration before and after heat treatment (VII) (11) Melt mass flow rate:

 According to ISO 1133, the measurement was performed at 250 ° C and a load of 2.16 kg.

 (12) Tensile strength and elongation at break:

 Using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd .: Model S-75ΜΙΠ), at a cylinder temperature of 250 ° C and a mold temperature of 80 ° C, an ISO test piece of the resin composition was molded, and the The tensile strength (TS) and the tensile elongation at break were measured according to the above. In each case, the average value of five times was adopted.

 (13) Flexural properties:

 According to ISO 178, the bending strength and flexural modulus of the same ISO test piece as described above were measured.

 (14) Charpy impact strength:

 After notching the same ISO test piece as above, the Shalby impact strength was measured according to IS0179.

 (15) Hydrolysis resistance (strength retention after hydrolysis test):

 The same ISO test piece as above is placed in a pressure vessel filled with pure water without direct contact with water, sealed, treated under 121 ° C pressure for 100 hours, and a tensile test is performed as above (The average of the tensile strength after the treatment is TS '). Then, the strength retention is calculated by the following equation (VI II). However, the wet heat treatment was performed for 100 hours for the resin composition containing the reinforcing filler, and for 60 hours for the resin composition containing no reinforcing filler. The higher the strength retention, the better the hydrolysis resistance. Strength retention (%) = (TS '/ TS) X 100 (VIII)

(16) Connector hinge characteristics:

At a cylinder temperature of 270 and a mold temperature of 80 ° C, an automotive wire harness connector having a hinge portion was injection molded, and the bending property of the hinge portion was evaluated. When the hinge is bent to 90- at 10 ° C, the hinge The number of pieces containing cracks was measured. The measurement was performed on 40 connectors.

(17) Releasability:

 A 16-pole connector was continuously molded using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd .: Model SG-75 mm), and the shortest cooling time required to continuously mold 20 shots without leaving the molded product in the fixed mold was determined. . The filling time was 1 second, the dwell time was 8 seconds, and the cooling time after the dwell was set. The cylinder temperature was set to 250 ° (:, the initial mold temperature was set to 45 ° C. The shortest cooling time mentioned above means that if the cooling time is shortened, the molded product remains in the fixed mold. This is the shortest cooling time for stable continuous production.

 (18) Evolved gas:

 5 g of the resin composition pellet was placed in a 26-mL glass vial having a content of 26 mL, and heated at 150 ° C. for 2 hours. A sample was collected from the gas phase with a microsyringe and analyzed by gas chromatography. The peak area of the chromatogram was determined, and the weight of tetrahydrofuran in an amount corresponding to the area was expressed as a ratio (ppm) to the resin composition. Most of the generated gas (about 90%) was tetrahydrofuran.

 (19) Warpage:

 Using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd .: Model SG—75 Mill), a disk with a diameter of 100 mm and a thickness of 1.6 mm was molded at a cylinder temperature of 250 ° C. The get is a single point gate on the circumference. One end of the disk was fixed to a flat plate, and the distance from the flat plate floating on the opposite side was measured and defined as the amount of warpage.

 (20) Film haze: A haze having a thickness of 50 m was measured using an auto haze meter (model TC-H3DPK) manufactured by Tokyo Denshoku Co., Ltd.

 Example 1

Through the esterification step shown in FIG. 1 and the polycondensation step shown in FIG. 6, PBT was produced in the following manner. First, a slurry prepared at 60 ° C was prepared by mixing 1.80 moles of 1,4-butanediol with 1.00 moles of terephthalic acid. From the feed line (1) to the reaction vessel (A) for esterification, which has a screw-type stirrer filled with PBT oligomer with an esterification rate of 99% in advance, so as to be 41 kg, h. Supplied. At the same time, the bottom component of the rectification column (C) at 185 ° C was supplied from the recirculation line (2) at 17.2 kg / h, and tetrabutyl at 65 ° C was used as a catalyst from the catalyst supply line (3). A 6.0% by weight solution of titanate in 1,4-butanediol was fed at 97 g / h (30 ppm based on theoretical polymer yield). The water content in this solution was 0.20% by weight.

 The internal temperature of the reactor (A) is 230 ° C, the pressure is 78 kPa, and the generated water, tetrahydrofuran and excess 1,4-butanediol are distilled from the distillation line (5), and rectification is performed. In the column (C), high-boiling components and low-boiling components were separated. After the system is stabilized, 98% by weight or more of the high boiling components at the bottom of the column are 1,4-butanediol, and the extraction line (8) is used so that the liquid level in the rectification column (C) is constant. Some of them were extracted to the outside. On the other hand, low-boiling components are extracted from the top of the tower in gaseous form.

The liquid was condensed in (G), and the liquid was extracted to the outside from the extraction line (13) so that the liquid level in the tank (F) became constant.

 A certain amount of the oligomer produced in the reaction tank (A) is extracted from the extraction line (4) using the pump (B), and the average residence time of the liquid in the reaction tank (A) is 3.3 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 97.5%.

 The internal temperature of the first polycondensation reaction tank (a) was 240 ° C and the pressure was 2.lkPa, and the liquid level was controlled so that the residence time was 120 minutes. The initial polycondensation reaction was performed while extracting water, tetrahydrofuran, and 1,4-butanediol from the vent line (L2) connected to a pressure reducer (not shown). The extracted reaction solution was continuously supplied to the second polycondensation reaction tank (d).

The internal temperature of the second polycondensation reaction tank (d) was 245 ° C, the pressure was 13 OPa, the liquid level was controlled so that the residence time was 90 minutes, and the vent connected to a pressure reducer (not shown) The polycondensation reaction was further advanced while extracting water, tetrahydrofuran and 1,4-butanediol from the line (L4). The obtained polymer was continuously extracted from the die head (g) in the form of a strand via the extraction line (L3) by the extraction gear pump (e), and cut by the rotary cutter (h). . The intrinsic viscosity of the obtained polymer was 0.85 dLZg, and the terminal lipoxyl group concentration was 12.2 / ie Q / g. Other analytical values are summarized in Table 1. PBT with little foreign matter, excellent color tone, good transparency and excellent thermal stability was obtained. Example 2

 Example 1 was repeated, except that the polycondensation step shown in FIG. 7 was employed. As the filter (f) in the polycondensation step shown in Fig. 7, a pleated cylindrical filter made of metal nonwoven fabric and having an absolute filtration accuracy of 20 m was used. PBT with further reduced foreign matter than in Example 1 was obtained. The analytical values are summarized in Table 1.

 Example 3 and Example 4

 In Example 1, the supply amount of tetrabutyl titanate was adjusted so that the Ti content in the polymer was as shown in Table 1, and the pressure in the second polycondensation reaction tank (d) was changed to 100 Pa. Was performed in the same manner as in Example 1. A PBT with less foreign matter, excellent color tone, good transparency and excellent thermal stability was obtained. The analytical values are summarized in Table 1.

 Example 5

 In Example 1, the supply amount of tetrabutyl titanate was adjusted so that the Ti content in the polymer was as shown in Table 1, and the temperature of the second polycondensation reaction tank (d) was changed to 250 ° C. Performed in the same manner as in Example 1. PBT with little foreign matter, excellent color tone, good transparency and excellent thermal stability was obtained. The analytical values are summarized in Table 1.

 Example 6

Same as Example 1 except that the polycondensation step shown in FIG. 8 was employed in Example 1. I went to. At this time, the same conditions as in Example 1 were used up to the second polycondensation reaction tank (d). The internal temperature of the third polycondensation reaction tank (k) was 240 ° C, the pressure was 13 OPa, The time was 60 minutes. PBT with less foreign matter, excellent color tone, good transparency, excellent thermal stability, and a higher molecular weight than Example 1 was obtained. The analytical values are summarized in Table 1.

 Example 7

 Example 6 was carried out in the same manner as in Example 6, except that the polycondensation step shown in FIG. 9 was employed. As the filter (f) in the polycondensation step shown in FIG. 9, a pleated cylindrical filter made of metal nonwoven fabric and having an absolute filtration accuracy of 20 m was used. PBT in which the amount of foreign substances was further reduced than in Example 6 was obtained. The analytical values are summarized in Table 2.

 Example 8

 The procedure was performed in the same manner as in Example 1 except that the ratio of the bottom component of the rectification column (C) supplied from the recirculation line (2) to the reaction tank (A) was changed to 8.0 kgZh. Was. PB with less foreign matter, excellent color tone, good transparency and excellent thermal stability

T was obtained. The analytical values are summarized in Table 2.

 Example 9

 In Example 7, the same conditions as in Example 1 were performed up to the second polycondensation reaction tank (d). The internal temperature of the third polycondensation reaction tank (k) was 245 ° C, the pressure was 13 OPa, and the The time was 70 minutes. A higher viscosity PBT resin was obtained than in Example 7.

 Comparative Example 1

In Example 1, the catalyst supply line (3) in the esterification step shown in Fig. 1 was connected to the raw material supply line (1), and the recirculation line (2) was located in the gas phase of the reaction tank (A). The procedure was carried out except that the supply amount of the 1,4-butanediol solution of tetrabutyl titanate was 194 g / h and the supply amount of the bottom component of the rectification column (C) was 17.1 kg. Performed as in Example 1. As shown in the table, haze and color tone deteriorated, and there were many foreign substances. Table 2 summarizes the analytical values. Comparative Example 2

 In a 200 L stainless steel reactor equipped with a turbine-type stirring blade, 272.9 mol of terephthalic acid, 491.3 mol of 1,4-butanediol, 0.126 mol of tetrabutyl titanate (0.126 mol of titanium) The theoretical yield of the polymer was 100 ppm, and the atmosphere was sufficiently replaced with nitrogen. Subsequently, the temperature of the system was raised, and after 60 minutes, the temperature reached 220 ° (:, pressure reached 80 kPa, and the generated water, tetrafuran-furan, and excess 1,4-butanediol were distilled out of the system. The esterification reaction was carried out for 2 hours (reaction start time was a time when a predetermined temperature and a predetermined pressure were reached.) At this time, a sample was partially taken and the esterification ratio was measured to be 99%. .

 After transferring the oligomer obtained above to a stainless steel reactor having an inner volume of 200 L having a vent tube and double helical stirring blades, the temperature was reached to 245 ° C and a pressure of 100 Pa over 60 minutes. In this state, a polycondensation reaction was performed for 1.5 hours. After the completion of the reaction, the polymer was drawn out into a strand and cut into a pellet. The intrinsic viscosity of the obtained polymer was 0.85, the terminal carboxyl group concentration was as high as 44.5 / ze q / g, the thermal stability was poor, and the Tc was low. The analytical values are summarized in Table 2.

 Comparative Example 3

 In a 200-liter stainless steel reactor equipped with a turbine-type stirring blade, 272.9 mol of dimethyl terephthalate (DMT), 327.5 mol of 1,4-butanediol, and 327.5 mol of tetrabutyl titanate 0.126 Molar (theoretical yield of titanium, 10 O ppm per polymer) was charged and sufficiently substituted with nitrogen. Subsequently, the temperature of the system was raised, and after 60 minutes, transesterification was performed for 2 hours at a temperature of 210 ° C and atmospheric pressure under nitrogen while distilling off the generated methanol, 1,4-butanediol, and tetrahydrofuran outside the system (The reaction start time was a point when a predetermined temperature and a predetermined pressure were reached).

200 L stainless steel with vent tube and double helical stirring blade After the oligomer obtained above was transferred to a reactor made of water, the temperature was raised to 245 ° C and a pressure of 10 OPa over 60 minutes, and a polycondensation reaction was performed for 1.5 hours in that state. After completion of the reaction, the polymer was drawn out into a strand and cut into pellets. The intrinsic viscosity of the obtained polymer was 0.85, the terminal lipoxyl group concentration was as high as 37.4 eq / g, the thermal stability was poor, and the Tc was low. The analytical values are summarized in Table 2.

 Comparative Example 4

 In Example 1, the catalyst supply line (3) in the esterification step shown in Fig. 1 was connected to the raw material supply line (1), and the recirculation line (2) was located in the gas phase of the reaction tank (A). The feed rate of the 1,4-butanediol solution of tetrabutyl titanate was 194 gZh, and the feed rate of the bottom component of the rectification column (C) was 17.1 kg. The procedure was performed in the same manner as in Example 1 except that the polymerization step shown in FIG. 8 was employed. At this time, the same procedure as in Example 1 was performed up to the second polymerization reaction tank (d), the internal temperature of the third polymerization reaction tank (k) was 240 ° C, the pressure was 13 OPa, and the residence time was 60 minutes. . The obtained PBT had many foreign substances and high haze and b-value. The analytical values are summarized in Table 2.

 Comparative Example 5

 In Comparative Example 2, the esterification was carried out in the same manner as in Comparative Example 2 except that the charged amount of tetrabutyl titanate was 0.044 mol (the amount of titanium was 35 ppm per theoretical yield of polymer) and the esterification reaction time was 5 hours. The reaction was performed. The esterification rate after the esterification reaction was 99%.

Subsequently, after the oligomer was transferred to the polycondensation reaction tank, the temperature was increased to 245 ° C and the pressure of 100 Pa over 60 minutes as in Comparative Example 2, and the polycondensation reaction was performed for 5 hours in that state. However, the stirring power leveled off and the viscosity did not increase, so the polymer was extracted. The intrinsic viscosity of the obtained polymer was 1.03, and both the terminal lipoxyl group concentration and the terminal vinyl group concentration were high. Item Unit Example 1 Example 2 Example 3 Example 4 Example 5

BM / TM mol / mol 3.35 3.35 3.35 3.35 3.35

Ti content Ppm 30 30 25 10 10

I V dL / g 0.85 0.85 0.85 0.76 0.85 Terminal concentration of rufo "xyl group concentration lie q / g 12.2 12.2 11.3 8.0 11.5

T c. C 177.5 177.5 176.4 176.0 176.5 Terminal vinyl group concentration e q / g 6.5 6.5 6.3 5.5 9.2 Terminal xylation force) :: Ru group concentration β e qZ g 0.1 or less 0.1 or less 0.1 or less 0.1 or less 0.1 or less

Above 5 Number of foreign substances fgf / lO lima-11 5 9 7 8 Solution Haze% 0.3 0.3 0.2 0.1 0.1 um [COOH] 'L eq / g (40 minutes) 4.3 4.3 3.6 1.7 1.7 Pellet b value -1.6 one 1.6 one 1.8 — 2.0 -0.5

Item Unit Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparative Example 3

BM / TM mol / mol 2.52 3.35 3.35 1.80 1.20

Ti content ppm 30 30 60 100 100

I V dL / g 0.85 1.26 0.85 0.85 0.85 Terminal carpho "xyl group concentration H e q / g 13.0 28.4 13.5 44.5 37.4

T c ° C 179.1 175.0 178.5 175.6 168.7 Terminal vinyl group concentration e q / g 7.8 10.7 6.9 7.0 6.7 Terminal methoxycarbon group concentration e q / g 0.1 or less 0.1 or less 0.1 or less 0.1 or less 2.3

Foreign objects more than 5 m / lOg Lima-20 5 67 20 15 Solution Haze% 1.0 0.2 22.5 0.4 0.1

Δ [COOH] eq / g (40 min;) 2.9 1.5 4.5 9.0 10.1 Pellet b value -1.0-0.8 0.2 0.0 -1.5

Examples 10 to 12 and Comparative Examples 6 to 8 (blend PBT)

 Using the low-viscosity PBT of Example 1, the high-viscosity PBT of Example 6, the low-viscosity PBT of Comparative Example 1, and the high viscosity の of Comparative Example 4, blended with the composition shown in Table 3 to obtain a screw diameter 3 Using an Omm vented twin-screw extruder [Nihon Steel Works Co., Ltd .: TEX30 C], the mixture was melt-kneaded at a temperature of 260 ° C and a screw rotation speed of 200 rpm, extruded into strands, and pelletized. The evaluations shown in Tables 3 and 4 were performed, and the results are shown in the same table. Table 3

 Example 丄 1 Π U 丄 1 1 丄 丄 1 Example 1 -PBT ^ ± リ o Q71 1 丄 Composition (parts by weight)

 Example 6-PBT 60 71 29 Melt mass flow rate g / 10min. 28 24 45 Tensile strength MPa 53 52 54 Tensile elongation at break 0/100 120 90 Mechanical properties Bending strength MPa 80 79 82 Flexural modulus MPa 2280 2200 2350 Impact strength KJ / m 4.0 4.4.3 3. 3 Before wet heat treatment 53 52 54 Tensile strength: MPa

 Water resistance

 After wet heat treatment 39 41 36 Degradable

Strength retention (%) 74 79 66 Number of connector hinge cracks / 40 out of 0 0 Table 4

表 3及び表 4に示した通り、 チタン原子が 33 p pm以下で固有粘度の異な る PBTをブレンドすることにより、 流動性が調節され、 耐加水分解性、 破断 伸度、 コネクターのヒンジ特性が優れた PBTを得ることが出来た。 これは、 チタン触媒量が低減されたため、 耐加水分解性が向上し、 チタン触媒の凝集異 物が少なくなつたためである。

As shown in Tables 3 and 4, by blending PBT with titanium atoms of 33 ppm or less and different intrinsic viscosities, fluidity is adjusted, and hydrolysis resistance, elongation at break, and hinge characteristics of connectors are improved. Excellent PBT was obtained. This is because the amount of titanium catalyst was reduced, the hydrolysis resistance was improved, and the amount of aggregated foreign substances of the titanium catalyst was reduced.

 Examples 13 to 16 and Comparative Examples 9 to 10 (Heat-resistant PBT composition)

Pellet of each PBT obtained in Example 1, Example 6, Comparative Example 1 and Comparative Example 2 9 With respect to 9.7 parts by weight, the following components (1) to (3) were mixed in the composition shown in Table 5 and pelletized in the same manner as in Example 9.

 (1) Penyu erythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) probionate] (Ciba-Geigy, product name: Irgano xl 010)

 (2) Penyu erythritol tetrakis (3-dodecylthiopropionate) (Cipro Kasei Co., Ltd., trade name: SEENOX412 S)

(3) Bis (2,6-di-tert-butyl 4-methylphenyl) Penyu erythritol diphosphite (Asahi Denka Kogyo Co., Ltd., trade name: ADK STAB PEP 36) Mold ISO test pieces from the above pellets The color tone M tensile strength and tensile elongation at break were measured. In addition, in order to evaluate the heat aging resistance, the color tone b value, the tensile strength, and the tensile elongation at break were measured on the ISO test pieces after the heat treatment in a hot air oven at 150 ° C for 250 hours or 500 hours. Hydrolysis resistance was also evaluated using ISO test pieces. Tables 5 and 6 show these results.

Table 5

 Example

13 14 15 Example 1-PBT 99.7 99.7 99.7

Irganox 1010 0.1 0.1 0.1 Composition (parts by weight)

 SEENOX 412S 0.2 1

PEP 36-0.2-Unprocessed-0.3-0.5-0.2 Color tone b value After 250 hours 5. 4. 9. 9

After 500 hours 8. 0 7. 3 13.4 Untreated 52 53 51 Heat resistant

 Tensile strength: MPa After 250 hours 61 60 59 Aging

 After 500 hours 58 56 58 Untreated 65 59 62 Tensile elongation:% After 250 hours 17.4 16.5 15.5

After 500 hours 13.5 14 12.6 Before wet heat treatment 52 53 51 Tensile strength: MPa

Water resistance

 After wet heat treatment 23 17 24 Degradability

Strength retention (%) 44 32 47 Table 6

 Example Comparative example

16 9 10 Example 6-PBT 99.7 Comparative Example 1-PBT 99.7 Comparative Example 2-PBT 99.7 Composition (parts by weight)

 Irganox 1010 0.1 0.1

SEENOX412S 0.3 0.3 0.2 0.2

PEP 36 Unprocessed 0.2 1.1.0 1.3 Tone b value 250 hours later 7.1 7.8 8.2

After 500 hours 9.8 10.2 11.5 Untreated 50 51 50 Heat resistant

 Tensile strength: MPa After 250 hours 60 58 57 Aging

 After 500 hours 61 56 55 Untreated 160 29 57 Tensile elongation:% After 250 hours 19.2 1.7 13.9

After 500 hours 15. 7 9. 3 8. 1 Before wet heat treatment 50 51 50 Water resistance Tensile strength: MPa

 33 19 16 After wet heat treatment

Strength retention (%) 66 37 32 As shown in Tables 5 and 6, where the titanium atom is 33 111 or less? By adding an antioxidant to the eight pieces, a PBT composition having heat resistance, little change in color tone and tensile elongation, and excellent hydrolysis resistance could be obtained. This is because thermal decomposition, oxidation, and hydrolysis were suppressed because the amount of titanium catalyst was reduced.

 Examples 17 to 18 and Comparative Examples 11 to 13 (Releasable PBT compositions) The following (1) and (2) were added to 100 parts by weight of each of the PBT obtained in Example 1, Comparative Example 1 and Comparative Example 2. The components were blended in the composition shown in Table 7, melt-kneaded at 260 ° C by a twin-screw extruder, extruded into strands and pelletized.

 (1) Montanic acid ester (manufactured by Toyo Petrolite Co., Ltd., trade name: Luzax Ep, molecular weight 800)

 (2) Polyethylene wax (Mitsui Chemicals Co., Ltd., trade name: Hachiwax 100 P, molecular weight 900)

 The molecular weight of the above-mentioned monmonic acid ester was measured by a melt viscosity method as follows. Fill the thermostatic oil bath with polyethylene glycol, adjust the atlantic viscometer to 135 ° C, hold the viscometer vertically, dilute the required amount of wax with decalin, and let the automatic viscometer flow the sample solution down. The number was measured and converted to the molecular weight.

ISO test pieces were formed from the above pellets, and the releasability was also evaluated. In addition, the resistance to water decomposition was evaluated. Table 7 shows the results.

Table 7

As shown in Table 7, the addition of montanic acid ester as a release agent to PBT with titanium atoms of 33 ppm or less provides excellent hydrolysis resistance and release properties (the molding cycle was shortened). ) A PBT composition was obtained.

 Examples 19 to 20 and Comparative Examples 14 to 15 (Hydrolysis-resistant PBT composition) The following (1) and (2) were used for 100 parts by weight of each PBT pellet of Example 1, Comparative Example 1, and Comparative Example 2. ) Was blended with the composition shown in Table 8 and pelletized in the same manner as in Example 9.

 (1) Glass fiber (manufactured by NEC Corporation: brand name T-187, diameter 13 // m, fiber length 3 mm)

(2) Diglycidyl ether of bisphenol A (manufactured by Asahi Denka Co., Ltd., trade name: Adeiki Saiza EP-17) ISO test pieces were formed from the above pellets, and the hydrolysis resistance was evaluated. The releasability was also evaluated. Table 8 shows the results. Table 8

表 8に示した通り、 チタン原子が 33 ppm以下の PBTに強化系充填材 (ガラス繊維） 及びエポキシ化合物を配合することにより、 耐加水分解性に優 れた強化系 P B T組成物を得ることが出来た。

As shown in Table 8, it is possible to obtain a reinforced PBT composition with excellent hydrolysis resistance by blending a reinforcing filler (glass fiber) and an epoxy compound with PBT containing titanium atoms of 33 ppm or less. done.

 Example 21-22 and Comparative Example 16-17 (impact PBT composition)

 The following components (1) and (2) were blended with 100 parts by weight of the PBT pellets of Example 1, Comparative Example 1, and Comparative Example 2 in the composition shown in Table 9 and pelletized in the same manner as in Example 10. It has become.

(1) Acrylic rubber (chemical name: alkyl acrylate / alkyl methacrylate copolymer, manufactured by Kureha Chemical Industry Co., Ltd., trade name: Kureha Paraloid EXL 23 15) (2) Glass fiber (used in Example 19) Same as glass fiber) Iso test pieces were prepared from the above pellets using an injection molding machine, and the tensile strength, bending strength, flexural modulus, and Charpy impact value were measured. In addition, the hydrolysis resistance was evaluated. Table 9 shows the results. Table 9

表 9に示した通り、 チタン原子が 3 3 p pm以下の ΡΒΤに耐衝撃改良剤 (アクリルゴム） 及び強化充填材 （ガラス繊維） を含有させることにより、 優 れた耐加水分解性と衝撃性とを有する P B T組成物を得ることが出来た。 実施例 2 3〜 24及び比較例 1 8〜 1 9 (難燃性 P B T組成物）

As shown in Table 9, excellent hydrolysis resistance and impact resistance are obtained by incorporating an impact modifier (acrylic rubber) and a reinforced filler (glass fiber) into の with titanium atoms of 33 ppm or less. A PBT composition having the following formula was obtained. Examples 23 to 24 and Comparative Examples 18 to 19 (flame retardant PBT composition)

Pellets of each PBT of Example 1, Comparative Example 1, and Comparative Example 2 The following components (1) to (4) were blended in the composition shown in Table 10, and pelletized in the same manner as in Example 10.

 (1) Brominated aromatic compound: poly (pentabromobenzyl acrylate) (Buchi Mochem Far East Co., Ltd., trade name: PBBPA—FR1025)

 (2) Antimony trioxide (Morirokusha)

 (3) Polytetrafluoroethylene (PTFE) (manufactured by Daikin Industries, trade name: Polyflon FA—500)

 (4) Glass fiber (same glass fiber used in Example 19)

UL-94 test specimens (1/32 inch) were molded from the above pellets and tested for flammability according to UL-94. UL-94 specimens were molded with an injection molding machine (Nippon Steel Works: Model J28SA) at a cylinder temperature of 270 ° (: 80 ° C). The pieces were molded, the hydrolysis resistance was evaluated, and the generated gas was measured from the pellets.

Table 10

表 1 0に示した通り、 チタン原子が 3 3 p pm以下の PBTに、 臭素化芳香 族化合物系難燃剤 （PBBPA) 、 アンチモン化合物 （三酸化アンチモン） 、 滴下防止剤 （PTFE) 、 強化充填材 （ガラス繊維） を配合することにより、 優れた耐加水分解性と難燃性を有し且つ発生ガスも少ない P B T組成物を得る ことが出来た。

As shown in Table 10, PBT with titanium atoms of 33 ppm or less, brominated aromatic compound flame retardant (PBBPA), antimony compound (antimony trioxide), anti-drip agent (PTFE), reinforced filler By blending (glass fiber), it was possible to obtain a PBT composition having excellent hydrolysis resistance and flame retardancy and generating less gas.

Examples 25 to 27 and Comparative Examples 20 to 21 (Non-halogen flame-retardant PBT compositions) The following (1) to 100 parts by weight of each PBT of Example 1, Comparative Example 1, and Comparative Example 2 The component (7) was blended with the composition shown in Table 11, and pelletized in the same manner as in Example 10. 16471

89

 (1) Polyphenylene ether (PPE) (Mitsubishi Engineering Plastics Co., Ltd., product name: Upies (registered trademark), intrinsic viscosity 0.36 dLZg)

(2) Polycarbonate resin (PC) (manufactured by Mitsubishi Engineering-Plastics Corporation: grade 7022 PJ, viscosity average molecular weight: about 21000)

 (3) Phosphate represented by the following formula (8)

 (4) Melamine cyanurate (Mitsubishi Chemical Corporation)

 (5) Glass fiber (same glass fiber used in Example 19)

 (6) Polytetrafluoroethylene (PTFE) (manufactured by Daikin Industries, trade name: Polyflon FA—500)

 (7) Zinc borate (Polux Japan Co., Ltd., trade name: FirebrakeZB)

UL-94 test pieces (1Z32 inch) were molded from the above pellets and tested for flammability according to UL-94. UL-94 specimens were molded with an injection molding machine (Nippon Steel Works: Model J28SA) at a cylinder temperature of 270 ° (: 80 ° C). The test pieces were molded and evaluated for hydrolysis resistance. Table 11

表 11に示した通り、 チタン原子が 33 p pm以下の PBTとポリフエニレ ンェ一テル樹脂に、 相溶化剤 （ポリ力一ポネート） 、 リン酸エステル、 シァヌ ル酸メラミン、 強化充填材 （ガラス繊維） 、 滴下防止剤 （PTFE) 、 硼酸金 属塩を配合することにより、 優れた耐加水分解性と難燃性を有する P B T組成 物を得ることが出来た。 実施例 28〜 30比較例 22〜 25 (他の機能性 P B T組成物一 1 )

As shown in Table 11, PBT with titanium atoms of 33 ppm or less and polyphenylene resin, compatibilizer (polycarbonate), phosphate ester, melamine cyanurate, reinforced filler (glass fiber) By adding a dripping inhibitor (PTFE) and a metal borate salt, a PBT composition having excellent hydrolysis resistance and flame retardancy could be obtained. Examples 28 to 30 Comparative Examples 22 to 25 (Other Functional PBT Compositions 1)

 The following components (1) to (4) were blended in the compositions shown in Tables 12 and 13 with respect to 100 parts by weight of the PBT pellets of Example 1, Comparative Example 1, and Comparative Example 2. Pelletized in a similar manner.

 (1) Polycarbonate resin (PC) (same PC as used in Example 25)

(2) Phosphorus compound: octadecyl acid phosphate [Asahi Denka Kogyo Co., Ltd., trade name: AX-71 (mixture of monoalkyl and dialkyl)]

 (3) Glass fiber (same glass fiber used in Example 19)

(4) Acryl rubber (Chemical name: alkyl acrylate / alkyl methacrylate copolymer, manufactured by Kureha Chemical Industry Co., Ltd., trade name: Kureha Paraloid EXL 2315) The cooling crystallization temperature of the above pellets was measured. An IS0 test piece was prepared from the pellet, and its tensile strength, flexural strength, flexural modulus, and Charpy impact value were measured, and its hydrolysis resistance was evaluated, and the results are shown in Tables 12 and 13.

Table 1 2

表 13

Table 13

表 12及び表 13に示した通り、 チタン原子が 33ppm以下の PBTに、 ポ リカーポネート、 有機リン化合物、 強化充填材 （ガラス繊維） を配合すること により、 耐加水分解性に優れ、 結晶化温度が高く （従って、 成形サイクルを短 くでき、 生産性を上げることが出来る） PBT組成物を得ることが出来た。 実施例 31〜 34及び比較例 26〜 28 (他の機能性 P B T組成物一 2 ) 実施例 1、 比較例 1、 比較例 2の各 PBTのペレット 100重量部に対し、 以下の （1) 〜 （3) の成分を表 14及び表 1 5の組成で配合し、 実施例 1 0 と同様の方法でペレツト化した。

As shown in Tables 12 and 13, blending a polycarbonate, an organic phosphorus compound, and a reinforcing filler (glass fiber) with PBT with titanium atoms of 33 ppm or less provides excellent hydrolysis resistance and a high crystallization temperature. A high PBT composition was obtained (thus, the molding cycle could be shortened and the productivity could be increased). Examples 31 to 34 and Comparative Examples 26 to 28 (Other Functional PBT Composition 1 2) The following (1) to 100 parts by weight of each PBT pellet of Example 1, Comparative Example 1, and Comparative Example 2 The components of (3) were blended in the compositions shown in Tables 14 and 15 and pelletized in the same manner as in Example 10.

 (1) Polyethylene terephthalate (manufactured by Mitsubishi Chemical Corporation, trade name: GS 385, intrinsic viscosity 0.65 dL / g)

 (2) Polypropylene terephthalate [manufactured by Shell Chemicals Co., Ltd., trade name: Cortera CP 509200, intrinsic viscosity 0.92 dL / g: methylene chloride-trifluoroacetic acid (1: 1 by weight) in a mixed solvent at a temperature of 30 ° C Measurement]

 (3) Glass fiber (same glass fiber used in Example 19)

The cooling crystallization temperature of the pellet was measured by DSC. Further, ISO test pieces were prepared from the above pellets, and the tensile strength, the bending strength, the bending elastic modulus, and the Charpy impact value were measured. In addition, hydrolysis resistance was evaluated. The results are shown in Tables 14 and 15.

Table 14

Table 15

表 14及び表 1 5に示した通り、 チタン原子が 3 3 p pm以下の PBTに、 ポリエチレンテレフタレート又はポリプロピレンテレフ夕レ一トと強化充填材 (ガラス繊維） を配合することにより、 耐加水分解性に優れ、 結晶化温度が高 く （従って、 成形サイクルを短くでき、 生産性を上げることが出来る） PBT 組成物を得ることが出来た。 実施例 35〜 39及び比較例 29〜 32 (他の機能性 P B T組成物一 3 ) 実施例 1、 比較例 1、 比較例 2の各 PBTのペレツ卜 100重量部に対し、 以下の （1) 〜 （4) の成分を表 16及び表 17の組成で配合し、 実施例 10 と同様の方法でペレツト化した。

As shown in Table 14 and Table 15, hydrolysis resistance is obtained by blending polyethylene terephthalate or polypropylene terephthalate and reinforced filler (glass fiber) with PBT having titanium atoms of 33 ppm or less. A PBT composition having excellent crystallization temperature and high crystallization temperature (thus shortening the molding cycle and increasing productivity) was obtained. Examples 35 to 39 and Comparative Examples 29 to 32 (Other Functional PBT Compositions 1 to 3) The following (1) was used for 100 parts by weight of each PBT pellet of Example 1, Comparative Example 1, and Comparative Example 2. Components (4) to (4) were blended in the compositions shown in Tables 16 and 17, and pelletized in the same manner as in Example 10.

 (1) HI PS: rubber (polybutadiene) content 8.8% by weight, average rubber particle diameter 1.8 m, number average molecular weight 92,000, weight average molecular weight 230,000, melt flow rate (temperature 200 ° C , Load 5Kg f) 1.8 g / 10 minutes rubber-modified polystyrene resin (A & M, product name: Dialex HT478)

(2) AS: acrylonitrile styrene resin having a number average molecular weight of 96,000 and a weight average molecular weight of 240,000 (manufactured by Techno Polymer Co., Ltd., trade name: SANR EX S 90)

 (3) Dailark: Maleic anhydride content 9% by weight, weight average molecular weight 240,000, melt flow rate (temperature 230 ° C, load 2.16 Kg f) 2.0 g / 10 minutes modified with maleic anhydride Polystyrene (Nova Chemical Japan Co., Ltd., product name: Dailark D 232)

 (4) Polycarbonate resin (PC) (same PC as used in Example 25)

(5) Glass fiber (same glass fiber used in Example 19)

ISO test pieces were prepared from the above pellets, and the tensile strength, bending strength, flexural modulus, and Charpy impact value were measured. In addition, hydrolysis resistance was evaluated. The results are shown in Tables 16 and 17. .

Table 16

 Example

3 5 3 6 3 7 3 8 3 9 Example 1-PBT 100 100 100 100 100

H I P S 29 29 1 29-

A S--43-43 Composition (parts by weight)

 Dailark 14 1-14-

PC C 14---Glass fiber 60 60 60--Warpage mm 8.3 9.2 10.5 13.2 14.3 Tensile strength MPa 118 120 137 38 53 Bending strength MPa 187 189 189 200 72 93 Mechanical properties

 Flexural modulus MPa 8290 8690 9160 2230 2620 Charvi-

KJ / m 11.0 12.7 7.8 2.7 1.3 Impact strength

 38 53 Tensile strength Before wet heat treatment 118 120 137

Water resistance: MPa After moisture heat treatment 59 61 66 24 33 Degradable

Strength retention (%) 50 51 48 64 62 Table 17

実施例 4 0〜 4 7及び比較例 3 3〜 3 4

Examples 40 to 47 and Comparative Examples 33 to 3 4

Using the PBT of the above-mentioned Example and Comparative Example 4 as a raw material, a single-layer film was obtained in the following manner. The above PBT was put into a vacuum dryer, and dried while evacuating for 4 hours or more after the pellet temperature reached 120 ° C. Then, the dried PBT pellets were put into a hopper of an extruder in which a full flight screw having a diameter of 40 φ, L / D = 25 and a compression ratio of 3.5 was inserted. A T-die with a width of 600 mm and a lip opening of 0.4 mm was attached to the tip of the extruder, and extruded into a curtain with a resin temperature of about 260 ° C and a discharge rate of 5 Kg / hr. The extruded resin was continuously extruded onto a mirror-finished metal opening that rotates at a surface temperature of 60 ° (peripheral speed of about 3 mZ) and quenched to obtain a single-layer film. The results are shown in Table 18.

Table 18

実施例 48

Example 48

 Using the polymer obtained in Example 9, a composite film was prepared in the following manner according to the coextrusion method. The equipment used was a three-type, three-layer water-cooled multilayer blown film forming machine. In this apparatus, the extruder for the outer layer has a diameter of 40 φ, a full flight screw with L / D = 24 and a compression ratio of 3.5 is inserted, and the extruders for the middle layer and the inner layer have a diameter of 40 φ, A full flight screw with L / D = 24 and a compression ratio of 2.5 is inserted.

First, PBT was put into a vacuum dryer, and dried while evacuating for 4 hours or more after the pellet temperature reached 120 ° C. Next, the extruder for the outer layer was filled with PBT, and the extruder for the middle and inner layers was filled with LLDPE (Ml = 2.0, density = 0.925 g / cc), respectively, and the expansion ratio (BUR) was 1. Under the conditions of 3, with PBT The olefin resin was co-extruded and cooled with water at a water temperature of 30 ° C. to obtain a two-layer film having a folding diameter of 17 Om m and a PBT layer of 50 m and an olefin layer of 30 m. In this film, the PBT layer and the olefin layer were easily peeled off, and only the PBT layer was used for evaluation. The measured haze of the PBT layer was 0%. Also, almost no foreign matter was observed, and the appearance was good.

 Example 50

Using a 50 zm PBT film produced for haze measurement in Example 49, a composite film was produced in the following manner according to the dry lamination method. That is, first, a two-component dry laminating adhesive (manufactured by Toyo Moton Co., Ltd .: main agent (TM-51), hardener 5 (CA T-RT8)) was used for the above PBT film using Barco Ichiichi. (6/1 weight ratio mixture) was applied so as to have a dry weight of 5 g / m ² and dried. Then, the above coated surface temperature 100 ° (:, at a pressure of 5 gZm ² condition, the thickness of 50 / m linear low density polyethylene (Nippon Polychem Co., Ltd., "Nova Tech UF 230j, MI: 21. 1. Density: 0.921 (: () was dry-laminated. Haze was 1.5%, high transparency, and good film with almost no foreign matter was obtained.

 According to the present invention described above, films, monofilaments, fibers, electrical and electronic parts, automobile parts, etc., which are excellent in color tone, hydrolysis resistance, thermal stability, transparency, and formability, and have reduced foreign matter The present invention provides PBT of stable quality that can be suitably used for the present invention, and the industrial value of the present invention is remarkable.

Claims

 The scope of the claims 1) Polybutylene terephthalate containing titanium and having an amount of 33 ppm or less as a titanium atom.  2) The polybutylene terephthalate according to 1, wherein the temperature-reducing crystallization temperature measured by a differential scanning calorimeter at a temperature lowering rate of 20 ° C / min is 170 to 200 ° C.  3) The polybutylene terephthalate according to 1 or 2, wherein the terminal vinyl group concentration is 0.1 to 10 eQ / g.  4) Solvent haze is 10% or less when 2.7 g of polybutylene terephthalate is dissolved in 20 mL of phenol / tetrachloroethane mixed solvent (3/2 by weight) and measured. The polybutylene terephthalate according to any one of the above.  5) The increase in the terminal lipoxyl group concentration excluding the hydrolysis reaction when heated at 245 ° C for 40 minutes in an inert gas atmosphere is 0.1 to 30 eq / g. Polybutylene terephthalate.  6) Any number of foreign substances of 5 / xm or more is less than 50 / 10g polymer. 7) The polybutylene terephthalate according to any one of 1 to 6, wherein the lower limit of the titanium content is 1 ppm.  8) The polybutylene terephthalate according to any one of 1 to 7, wherein the lower limit of the titanium content is 3 ppm.  9) A polybutylene terephthalate having an intrinsic viscosity of 0.60 to 0.90 dL / g and a polybutylene terephthalate having an intrinsic viscosity of 0.91 to 1.50 dL / g are 5 to 95 by weight. : The polybutylene terephthalate according to any one of 1 to 8, which is contained in a proportion of 95 to 5. 10) A method for producing a polybutylene terephthalate having a step of performing an esterification reaction by continuously supplying terephthalic acid and 1,4-butanediol in the presence of a titanium catalyst in an esterification reaction tank. Low in 1,4-butanediol At least a part is supplied to the esterification reaction tank independently of terephthalic acid, and at least 10% by weight of the 1,4-butanediol supplied to the esterification reaction tank independently of terephthalic acid is a reaction liquid. A method for producing polybutylene terephthalate, comprising supplying 10% by weight or more of a titanium catalyst to a liquid phase of a reaction liquid independently of terephthalic acid.  1 1) 1,4-Butanediol distilled from the esterification reactor is condensed by a condenser provided in the esterification reactor, and at least a part of the condensed 1,4-butanediol is converted to terephthalic acid. 10. The production method according to 10 above, which is independently re-supplied to the esterification reactor.  1 2) The molar ratio of terephthalic acid to 1,4-butanediol supplied to the esterification reactor per unit time (1,4-butanediol Z terephthalic acid) is 1.6 to 4.5. 10. The method for producing the polybutylene terephthalate according to 10 or 11. '  13) A method for producing polybutylene terephthalate, which comprises a step of continuously supplying dialkyl terephthalate and 1,4-butanediol in a transesterification reaction tank in the presence of a titanium catalyst to carry out a transesterification reaction, At least part of 1,4-butanediol is supplied to the transesterification reactor independently of the dialkyl terephthalate, and is fed to the transesterification reactor independently of the dialkyl terephthalate. A polybutanediol, wherein at least 10% by weight of butanediol is supplied to the liquid phase of the reaction liquid, and at least 10% by weight of the titanium catalyst is supplied to the liquid phase of the reaction liquid independently of terephthalic acid. A method for producing butylene terephthalate.  14) 1,4-butanediol distilled from the transesterification reaction tank is condensed by a condenser provided in the transesterification reaction tank, and at least a part of the condensed 1,4-butanediol is dialkyl terephthalate. 13. The production method according to 13 above, which is independently resupplied to the transesterification reactor. 15) Molar ratio of 1,2-butanediol to 1,4-butanediol (1,4-butanediol / terephthalate) 13. The production method according to 13 or 14, wherein dialkyl tartrate) is 1.1 to 1.8. 16) The titanium catalyst is supplied as a 0.01 to 30% by weight solution of 1,4-butanediol to the liquid phase of the reaction liquid independently of terephthalic acid or dialkyl terephthalate. The production method described in Crab.  17) The production method according to 16, wherein the 1,4-butanediol solution of the titanium catalyst contains 0.05 to 1.0% by weight of water.  18) The method according to any one of 10 to 17, wherein the titanium catalyst is an organic titanium compound.  19) The production method according to any one of 10 to 18, wherein the reaction temperature of the esterification reaction or transesterification reaction is equal to or higher than the boiling point of 1,4-butanediol at the reaction pressure.  20) The temperature of 1,4-butanediol supplied to the esterification tank or the esterification reaction tank independently of terephthalic acid or dialkyl terephthalate is in the range of 100 to 200 ° C. The production method according to any one of 0 to 19.  21) The process according to item 16, wherein 1,4-butanediol used as a solvent for the titanium catalyst is condensed by a condenser.  22) The production method according to any one of 10 to 21, comprising a step of performing a polycondensation reaction following the esterification reaction or the transesterification reaction. 23) Polybutylene terephthalate, which has a process of continuously esterifying terephthalic acid and 1,4-butanediol in excess of terephthalic acid in the presence of a titanium catalyst in an esterification reaction tank In the process for the production of terephthalic acid, the molar ratio of terephthalic acid to 1,4-butanediol supplied to the esterification reactor per unit time (moles of 1,4-butanediol / moles of terephthalic acid) was kept constant. A method for producing polybutylene terephthalate, characterized in that it is controlled so as to keep it. 24) Polybutylene having a process of continuously transesterifying dialkyl terephthalate and excess 1,4-butanediol with respect to dialkyl terephthalate in the presence of a titanium catalyst in a transesterification reaction tank Manufacture of terephthalate In the method, the molar ratio of dialkyl terephthalate to 1,4-butanediol supplied to the transesterification reactor per unit time (moles of 1,4-butanediol / moles of terephthalic acid) is kept constant. A method for producing polybutylene terephthalate, characterized by controlling.  25) The production method according to 23 or 24, wherein the titanium catalyst is an organic titanium compound. 26) The production method according to 23 to 25, comprising a step of performing a polycondensation reaction following the esterification reaction or the transesterification reaction.  27) The polybutylene terephthalate described in any of 1 to 9 above, a phenolic antioxidant (B1), a zeolite antioxidant (B2) and a phosphorus antioxidant (B 3) A heat-resistant polybutylene terephthalate composition comprising at least one antioxidant selected from the group consisting of:  28) A fatty acid ester (C) comprising a fatty acid residue having 12 to 36 carbon atoms and an alcohol residue having 1 to 36 carbon atoms with respect to 100 parts by weight of the polybutylene terephthalate described in any of 1 to 9 above. 1) and a release agent selected from the group consisting of paraffin wax and polyethylene wax (C2) (C), containing 0.01 to 2 parts by weight of a good release polybutylene terephthalate. Composition.  29) 100 to 100 parts by weight of the polybutylene terephthalate described in any of 1 to 9, containing 0 to 200 parts by weight of the reinforcing filler (D) and 0.01 to 20 parts by weight of the epoxy compound (E) A hydrolysis-resistant polybutylene terephthalate composition characterized by the following.  30) With respect to 100 parts by weight of polybutylene terephthalate described in any of 1 to 9, 0.5 to 40 parts by weight of impact modifier (F) and 0 to 200 parts by weight of reinforcing filler (D) An impact-resistant polybutylene terephthalate composition comprising: 31) 100 parts by weight of the polybutylene terephthalate according to any of 1 to 9, 3 to 50 parts by weight of a brominated aromatic compound flame retardant (G), 3 to 50 parts by weight of an antimony compound (H):! Anti-dripping agent (I) 0 to 15 parts by weight and reinforcing filler (D) A flame-retardant polybutylene terephthalate composition containing 0 to 200 parts by weight.  32) Compatibilizer (K) based on a total of 100 parts by weight of 50 to 95 parts by weight of polybutylene terephthalate described in any of 1 to 9 and 5 to 50 parts by weight of polyphenylene ether resin (J) 0.05 to 10 parts by weight, at least one compound selected from phosphate esters or phosphonitrile (L) 2 to 45 parts by weight, reinforcing filler (D) 0 to 200 parts by weight, anti-drip agent (I) 0 1 to 15 parts by weight, 0 to 45 parts by weight of melamine cyanurate (M) and 0 to 50 parts by weight of a metal borate (N). object. 33) For 100 parts by weight of the polybutylene terephthalate described in any of 1 to 9, 5 to 100 parts by weight of a polycarbonate resin (O), 0.01 to 1 part by weight of an organic phosphorus compound (P), and a reinforcing filler ( D) A polybutylene terephthalate composition comprising 0 to 200 parts by weight and an impact modifier (F) 0 to 50 parts by weight.  34); 100 to 100 parts by weight of the polybutylene terephthalate described in any of! To 9; 5 to 100 parts by weight of an aromatic polyester resin other than polybutylene terephthalate (Q) and a reinforcing filler (D ) A polybutylene terephthalate composition comprising 0 to 200 parts by weight.  35) With respect to 100 parts by weight of the polybutylene terephthalate described in any one of 1 to 9, 5 to 100 parts by weight of a styrene resin (R), a maleic anhydride-modified polystyrene resin (S) or a polyacrylonitrile resin ( Ii) A polybutylene terephthalate composition comprising 0 to 40 parts by weight and 0 to 200 parts by weight of a reinforcing filler (D).  36) A film comprising titanium and containing polybutylene terephthalate having a titanium atom content of 33 ppm or less. 37) The fill according to 36, wherein the cooling crystallization temperature measured by a differential scanning calorimeter of polybutylene terephthalate at a cooling rate of 20 ° C / min is 170 to 200 ° C. M  38) The film according to 36 or 37, wherein the polybutylene terephthalate has an intrinsic viscosity of 0.60 to 2. S OdLZg.  39) The film according to any one of 36 to 38, wherein the terminal lipoxyl group concentration of polybutylene terephthalate is 1 to 45 ne dZg.  40) The film according to any one of 36 to 39, wherein 50 foreign substances having a length of 5 m or more in the polyethylene terephthalate are not more than Z10 g polymer.  41) The film according to any one of 36 to 40, which has a thickness of 5 to 200 iim. 42) A composite film comprising two or more different resin layers, wherein at least one layer is the polybutylene terephthalate film according to any of 36 to 41, and at least one other layer is a polyolefin-based film. A composite film, characterized in that:  43) The composite film according to 42, wherein the outermost layer is composed of a polybutylene terephthalate film and a Z or polyolefin-based resin.  44) 1 to 99% by weight of poly (propylene terephthalate) containing titanium and having an amount of 33 ppm or less as titanium atoms and 1 to 99% by weight of polyethylene terephthalate A film characterized by comprising 99% by weight (the total of both is 100% by weight).  45) 1 to 99% by weight of an aromatic polyester obtained by copolymerizing polytetramethylene glycol with 1 to 99% by weight of polybutyrene terephthalate containing titanium and having an amount of 33 ppm or less as a titanium atom. (Total is 100% by weight). -